JP5681990B2 - Method for producing denitration catalyst - Google Patents
Method for producing denitration catalyst Download PDFInfo
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- JP5681990B2 JP5681990B2 JP2011131208A JP2011131208A JP5681990B2 JP 5681990 B2 JP5681990 B2 JP 5681990B2 JP 2011131208 A JP2011131208 A JP 2011131208A JP 2011131208 A JP2011131208 A JP 2011131208A JP 5681990 B2 JP5681990 B2 JP 5681990B2
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- 239000003054 catalyst Substances 0.000 title claims description 65
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 44
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 15
- 229910052720 vanadium Inorganic materials 0.000 claims description 12
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004480 active ingredient Substances 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 description 16
- 238000002156 mixing Methods 0.000 description 15
- 229910010413 TiO 2 Inorganic materials 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- 239000010936 titanium Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 6
- 229940010552 ammonium molybdate Drugs 0.000 description 6
- 235000018660 ammonium molybdate Nutrition 0.000 description 6
- 239000011609 ammonium molybdate Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 4
- -1 oxo acid salt Chemical class 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003682 vanadium compounds Chemical class 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
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Description
本発明はアンモニア接触還元用脱硝触媒の製造方法に関し、バナジウムなどの活性成分を含むチタン酸化物の組成物とバナジウムなどの活性成分を含まないチタン酸化物とを混合、乾燥、焼成して得られる、高い脱硝率を得ることができる触媒の製造方法に関する。 The present invention relates to a method for producing a denitration catalyst for catalytic catalytic reduction, and is obtained by mixing, drying and firing a titanium oxide composition containing an active ingredient such as vanadium and a titanium oxide containing no active ingredient such as vanadium. The present invention relates to a method for producing a catalyst capable of obtaining a high denitration rate.
酸化チタンを主成分とするアンモニア還元法脱硝触媒は、活性が高く耐久性が優れるため、国内外でボイラなどの排煙処理に広く用いられ、脱硝触媒の主流となっている。また、これらの脱硝触媒について、脱硝反応器のコンパクト化に対し脱硝性能が高い触媒の需要が高まっている。このような背景に対し、高い脱硝性能を有する脱硝触媒を提供する方法として、触媒表面に活性成分を集中させたコーティング層を有する触媒（特許文献１）や、物理混合によって活性成分が不均質に担持された触媒（特許文献２）などの方法が開示されている。 The ammonia reduction method denitration catalyst mainly composed of titanium oxide has high activity and excellent durability, and is therefore widely used for flue gas treatment of boilers and the like at home and abroad, and has become the mainstream of denitration catalyst. In addition, for these denitration catalysts, there is an increasing demand for catalysts having high denitration performance as the denitration reactor becomes compact. Against such a background, as a method for providing a denitration catalyst having high denitration performance, a catalyst having a coating layer in which an active component is concentrated on the catalyst surface (Patent Document 1), or an active component inhomogeneous by physical mixing. A method such as a supported catalyst (Patent Document 2) is disclosed.
上記した従来技術で示した触媒表面に活性成分を集中させる方法は、実機運転時に表層部に担持したコーティング層が剥離することがあり、これによって、脱硝性能が低下する現象が生じる。また、後者の物理混合によって活性成分を不均一に担持させる方法では、用いる原料によっては高い脱硝性能が得られないことがあり、これには改善する余地がある。 In the above-described method for concentrating active components on the catalyst surface shown in the prior art, the coating layer supported on the surface layer part may be peeled off during operation of the actual machine, thereby causing a phenomenon that the denitration performance is lowered. Further, in the latter method in which the active ingredient is loaded non-uniformly by physical mixing, high denitration performance may not be obtained depending on the raw materials used, and there is room for improvement.
本発明の解決しようとする課題は、上記従来技術を鑑み、活性成分を不均一に担持させる方法において、高い脱硝性能を有する触媒の製造方法を提供することにある。 The problem to be solved by the present invention is to provide a method for producing a catalyst having high denitration performance in a method for supporting an active component in a non-uniform manner in view of the above prior art.
上記課題を達成するため、本願で特許請求される発明は、以下のとおりである。
（１）チタン酸化物に少なくともバナジウムを含む活性成分を担持後予備焼成した組成物を第一成分とし、バナジウムを含まないチタン酸化物を含む組成物を第二成分として、これらを混合後、成形、乾燥、焼成する脱硝触媒の製造方法であって、第一成分のチタン酸化物の比表面積が30〜120m2/gになるように調整することを特徴とする脱硝触媒の製造方法。
（２）前記第二成分が、チタン酸化物のみであることを特徴とする（１）に記載の脱硝触媒の製造方法。
（３）前記第二成分が、モリブデンまたはタングステンを含む組成物であることを特徴とする（１）に記載の脱硝触媒の製造方法。
To achieve the above object, the invention claimed in the present application is as follows.
(1) A composition obtained by supporting an active ingredient containing at least vanadium in titanium oxide and pre-baked is used as a first component, and a composition containing titanium oxide containing no vanadium is used as a second component. A method for producing a denitration catalyst that is dried, calcined, wherein the specific surface area of the first component titanium oxide is adjusted to 30 to 120 m 2 / g.
(2) The method for producing a denitration catalyst according to (1), wherein the second component is only titanium oxide.
(3) The method for producing a denitration catalyst according to (1), wherein the second component is a composition containing molybdenum or tungsten.
本願発明の方法によれば、酸化チタンを主成分とする二酸化硫黄の酸化を抑制した排ガス用脱硝触媒において、活性成分を担持するチタン酸化物として比表面積が30〜120m2/gの範囲内のものを用いて触媒を調製することにより、脱硝性能の高活性化を図ることが可能となる。 According to the method of the present invention, in the denitration catalyst for exhaust gas in which the oxidation of sulfur dioxide containing titanium oxide as a main component is suppressed, the specific surface area is within a range of 30 to 120 m 2 / g as titanium oxide supporting an active component. By using a catalyst to prepare a catalyst, it is possible to increase the denitration performance.
[原理・作用]
酸化チタンおよびバナジウムを主成分とする触媒は、TiO2上に担持されたバナジウムなどの活性成分が、（１）式で示されるNH3が還元剤である脱硝反応の活性点となる。ここで、活性点とは（１）式の反応が主に進行する場を意味する。
[Principle / Action]
In the catalyst mainly composed of titanium oxide and vanadium, an active component such as vanadium supported on TiO 2 serves as an active point of a denitration reaction in which NH 3 represented by the formula (1) is a reducing agent. Here, the active site means a place where the reaction of the formula (1) mainly proceeds.
NH3 + NO +1/4O2 → N2 + 3/2H2O （１）
ところが、TiO2原料の仕様によっては調製に用いたバナジウムなどの活性成分が全て活性点としての機能していないことが分かった。これについて、本発明者らは鋭意検討した結果、特に活性成分を担持するTiO2原料の比表面積が大きい条件では、用いるバナジウムなどの活性成分が活性点として機能しない割合がより高いことを明らかにし、本出願に至った。
NH 3 + NO + 1 / 4O 2 → N 2 + 3 / 2H 2 O (1)
However, depending on the specifications of the TiO 2 raw material, it was found that not all active components such as vanadium used for the preparation function as active sites. As a result of intensive studies, the present inventors have clarified that the ratio of the active component such as vanadium used as an active site is higher, particularly under the condition that the specific surface area of the TiO 2 raw material supporting the active component is large. This led to the present application.
なお、TiO2原料の比表面積が大きい条件において、活性点の形成におけるロスが多い理由については、詳しくは明らかとはなっていないが、本発明者らは次のように推定している。すなわち、活性成分がTiO2細孔外部のTiO2表層部とTiO2表層部の粒子間に担持された場合や、TiO2細孔内部に担持された場合、加熱によってTiO2粒子のシンタリングが生じ、その結果、上記した活性成分がTiO2粒子間や細孔内部に閉じ込められ、反応ガスと接触できないようになることが考えられる。そこで、本発明者らは、この現象を抑制する手段について鋭意検討を行ったところ、上述したTiO2粒子のシンタリングは、高比表面積のTiO2で顕著であり、特に300〜600℃での熱処理で著しいことが分かった。よって、予め熱処理を施すなどの処理により触媒原料として、30〜120m2/gの比表面積のTiO2原料を選定し、活性成分を担持すれば、その後の予備焼成で活性成分が閉じ込められることを抑えることができることが分かった。これにより、調製に用いた活性成分は活性点としてのロスが減り、脱硝活性の高い触媒となる。 Although the reason why there is a large loss in the formation of active sites under the condition that the specific surface area of the TiO 2 raw material is large is not clear in detail, the present inventors presume as follows. That, and if an active ingredient is supported between the particles of the TiO 2 surface layer portion and the TiO 2 surface layer of the TiO 2 pores outside, when it is supported on the inside TiO 2 pores, sintering of TiO 2 particles by heating As a result, it is conceivable that the above-mentioned active component is confined between the TiO 2 particles or inside the pores and cannot come into contact with the reaction gas. Therefore, the present inventors conducted extensive studies on means for suppressing this phenomenon, and the above-described sintering of the TiO 2 particles is remarkable with TiO 2 having a high specific surface area, particularly at 300 to 600 ° C. It was found that the heat treatment was remarkable. Therefore, if a TiO 2 raw material with a specific surface area of 30 to 120 m 2 / g is selected as a catalyst raw material by a treatment such as heat treatment in advance, and the active component is supported, the active component is confined in the subsequent preliminary firing. It turns out that it can be suppressed. Thereby, the active ingredient used for preparation reduces the loss as an active point, and becomes a catalyst with high denitration activity.
また、本発明においては、特に前記第一成分が、チタン酸化物のみ、あるいはチタン酸化物にモリブデンあるいはタングステンを担持した第二成分と物理混合することで、混合前の第一成分の脱硝活性よりも高い脱硝活性を得ることができる。この原理・作用について、詳しくは明らかにはなっていないが、物理混合によって活性成分が不均一で担持されることによるものと推測される。 In the present invention, in particular, the first component is physically mixed with only the titanium oxide, or the second component in which molybdenum or tungsten is supported on the titanium oxide, thereby reducing the denitration activity of the first component before mixing. High denitration activity can be obtained. Although the details of the principle and action are not clarified, it is presumed that the active ingredient is unevenly supported by physical mixing.
本発明は上記したように、少なくともバナジウムを含む活性成分をチタン酸化物に担持後予備焼成した第一成分、バナジウムを含まないチタン酸化物である第二成分の両者を一定の不均質さを保持した状態で混合、成形した脱硝触媒であって、第一成分で用いられるチタン酸化物の比表面積が30〜120m2/gであることを特徴とするものである。 As described above, the present invention maintains a certain degree of inhomogeneity in both the first component pre-fired after supporting the active component containing at least vanadium on titanium oxide and the second component that is titanium oxide not containing vanadium. A denitration catalyst mixed and molded in this state, wherein the specific surface area of the titanium oxide used in the first component is 30 to 120 m 2 / g.
ここで、予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、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を混合する他に、モリブデンもしくはタングステンの酸化物、またはオキソ酸塩などの熱分解により酸化物を生成する化合物などを混合することができる。これらを加熱混練、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℃で焼成することが好ましい。また、第二成分は、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のみか、あるいはモリブデンもしくはタングステンの酸化物、またはオキソ酸塩などの熱分解により酸化物を生成する化合物を混合して得ることができる。 Here, the first component prepared in advance is a mixture of titanium oxide, orthotitanic acid or metatitanic acid slurry, or a mixture of the above powder with water and a vanadium compound such as ammonium metavanadate or vanadyl sulfate. In addition, an oxide of molybdenum or tungsten, a compound that generates an oxide by thermal decomposition such as oxo acid salt, or the like can be mixed. It is preferable that these are carried while evaporating water 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. Further, the second component is a slurry of titanium oxide, orthotitanic acid or metatitanic acid, or only the above powder added with water, or an oxide of molybdenum or tungsten, or oxide by thermal decomposition such as oxo acid salt. Can be obtained by mixing the compounds that produce
第一成分と第二成分とは混合に先立ち粉砕され、好ましくは、両者の比が10/90から90/10になるように混合され、水とともにニーダなど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など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、円筒状などに成形されるか、ローラを用いてメタルラスなど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600℃で焼成されることが望ましい。 The first component and the second component are pulverized prior to mixing, preferably mixed so that the ratio of the two becomes 10/90 to 90/10, and kneaded in a paste form with a kneader such as a kneader. . At this time, a ceramic fiber, an organic or inorganic binder or the like can be added as necessary. The obtained catalyst paste is directly formed into a honeycomb, columnar shape, cylindrical shape, etc. using an extrusion molding machine, or applied to a metal substrate such as a metal lath or ceramic, a glass net woven fabric, etc. using a roller. It is formed into a shape. Thereafter, it is desirable that the molded body is cut and molded into a required shape, dried and fired at 400 ° C. to 600 ° C.
第一成分は予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。また、第二成分は、高比表面積である方が高い脱硝性能を得やすく、そのため第二成分は予め焼成されていないことが好ましい。また、第二成分を予め焼成する場合は、モリブデンあるいはタングステンを担持するとチタン酸化物のシンタリングを抑制できるため、これらの成分を担持した後に焼成することが好ましい。 The first component is desirably calcined in advance, and the active component is insolubilized at this stage, and the active component is dissolved and mixed with each other in the subsequent mixing operation to prevent the non-uniformity from decreasing. In addition, it is preferable that the second component has a high specific surface area to obtain high denitration performance, and therefore the second component is preferably not pre-fired. In the case where the second component is fired in advance, sintering of titanium oxide can be suppressed by supporting molybdenum or tungsten. Therefore, firing is preferably performed after supporting these components.
第一成分と第二成分の混合比は触媒の使用条件化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一成分/第二成分の重量比が90/10ないし10/90程度の範囲が選ばれる。 The mixing ratio of the first component and the second component is determined in combination with the above composition under the use conditions of the catalyst, and may be any ratio, but is difficult to make if the mixing ratio is too large. On the contrary, if it is small, the effect becomes small. In a normal operation by kneading, the weight ratio of the first component / second component is selected in the range of about 90/10 to 10/90.
さらに第一成分と第二成分とは混合に先立ち粉砕され、その粒子径は通常100から350メッシュとすることが好ましい。脱硝性能面からは微粉が好ましいが、SO2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、第一成分粒子中に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 diameter is preferably 100 to 350 mesh. From the viewpoint of denitration performance, fine powder is preferable, but from the viewpoint of suppressing SO 2 oxidation, coarse particles are preferable. In order to suppress SO 2 oxidation, it is preferable that pores of 500 angstroms or more exist in the first component particles in a certain amount or more, and good results can be obtained when the second component particles are used as coarse particles.
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]
メタバナジン酸アンモニウム1.78gを水84ｇに溶解させ、これに酸化チタン(石原産業社製、商品名MC90、比表面積約90m2/g)56ｇを入れ、加熱混練を行った。これを40℃で一時間保温した後、120℃で一時間乾燥後、500℃で2時間焼成して触媒を得た。本触媒の組成はTi/V=97.9/2.1 原子比である。これとは別に、水36gに酸化チタン(ミレニアム社製、商品名G5、比表面積300m2/g)24gを入れ、加熱混練を行い、これを40℃で一時間保温した後、120℃で一時間乾燥して触媒を得た。Ti/V粉末、上記調製法の酸化チタンのみの粉末それぞれを425〜500μｍの粒径に揃えた。さらに、Ti/V粉末と酸化チタンのみの粉末をポリエチレン製の袋の中で物理混合した粉末に対し(重量比70/30)、加圧成型器を用いて、約1.3t/cm2で加圧し、粒状に成型した。物理混合後の触媒の組成はTi/V=98.5/1.5 原子比である。
Hereinafter, the present invention will be described in detail using specific examples.
[Example 1]
1.78 g of ammonium metavanadate was dissolved in 84 g of water, and 56 g of titanium oxide (trade name MC90, manufactured by Ishihara Sangyo Co., Ltd., specific surface area of about 90 m 2 / g) was added thereto, followed by heating and kneading. This was kept at 40 ° C. for 1 hour, dried at 120 ° C. for 1 hour, and calcined at 500 ° C. for 2 hours to obtain a catalyst. The composition of this catalyst is Ti / V = 97.9 / 2.1 atomic ratio. Separately, 24 g of titanium oxide (made by Millennium, trade name G5, specific surface area 300 m 2 / g) is added to 36 g of water, kneaded with heating, kept at 40 ° C. for 1 hour, and then kept at 120 ° C. for 1 hour. The catalyst was obtained by drying for a period of time. Each of the Ti / V powder and the titanium oxide-only powder prepared in the above-described preparation method was aligned to a particle size of 425 to 500 μm. Furthermore, a powder of only Ti / V powder and titanium oxide powder physically mixed in a polyethylene bag (weight ratio 70/30) was added at about 1.3 t / cm 2 using a pressure molding machine. Pressed and molded into granules. The composition of the catalyst after physical mixing is Ti / V = 98.5 / 1.5 atomic ratio.
[実施例２]
実施例２で用いた第一成分で用いた酸化チタンとして石原産業社製、商品名MC90、比表面積約90m2/gを予め700℃で２時間焼成して比表面積を30m2/gとしてから用いるように変えた以外は、実施例１と同様にして触媒を調製した。
[Example 2]
Titanium oxide used as the first component used in Example 2 manufactured by Ishihara Sangyo Co., Ltd., trade name MC90, specific surface area of about 90 m 2 / g was calcined at 700 ° C. for 2 hours in advance and the specific surface area was adjusted to 30 m 2 / g. A catalyst was prepared in the same manner as in Example 1 except that the usage was changed.
[実施例３]
実施例１で用いた第一成分で用いた酸化チタンを堺化学社製、商品名SSP-M、比表面積120m2/gに変えた以外は、実施例１と同様に触媒を調製した。
[Example 3]
A catalyst was prepared in the same manner as in Example 1, except that the titanium oxide used in the first component used in Example 1 was changed to Sakai Chemical Co., Ltd., trade name SSP-M, and specific surface area 120 m 2 / g.
[比較例１]
実施例１で用いた第一成分で用いた酸化チタンをミレニアム社製、商品名G5、比表面積300m2/gに変えた以外は、実施例１と同様に触媒を調製した。
[Comparative Example 1]
A catalyst was prepared in the same manner as in Example 1 except that the titanium oxide used in the first component used in Example 1 was changed to Millennium's trade name G5, specific surface area 300 m 2 / g.
[比較例２]
実施例１で用いた第一成分で用いた酸化チタンをミレニアム社製、商品名G5を予め300℃で２時間焼成して、比表面積200m2/gに変えた以外は、実施例１と同様に触媒を調製した。
[Comparative Example 2]
The titanium oxide used in the first component used in Example 1 was manufactured by Millennium, and the product name G5 was previously calcined at 300 ° C. for 2 hours to change the specific surface area to 200 m 2 / g. A catalyst was prepared.
[比較例３]
メタバナジン酸アンモニウム1.78gを水120ｇに溶解させ、これに酸化チタン(石原産業社製、比表面積約90m2/g)80ｇを入れ、加熱混練を行った。これを40℃で一時間保温した後、120℃で一時間乾燥後、500℃で2時間焼成して触媒を得た。本触媒の組成はTi/V=98.5/1.5 原子比である。得られた触媒粉末を425〜500μｍの粒径に揃え、この粉末に対し加圧成型器を用いて、約1.3t/cm2に加圧し、粒状成型した。
[Comparative Example 3]
1.78 g of ammonium metavanadate was dissolved in 120 g of water, and 80 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., specific surface area of about 90 m 2 / g) was added and kneaded by heating. This was kept at 40 ° C. for 1 hour, dried at 120 ° C. for 1 hour, and calcined at 500 ° C. for 2 hours to obtain a catalyst. The composition of the catalyst is Ti / V = 98.5 / 1.5 atomic ratio. The obtained catalyst powder was aligned to a particle size of 425 to 500 μm, and this powder was pressed to about 1.3 t / cm 2 using a pressure molding machine and granulated.
[実施例４]
第一成分で用いる酸化チタンを72g、第二成分で用いる酸化チタンを8gにそれぞれ変えた以外は、実施例１と同様に触媒を調製した。
[Example 4]
A catalyst was prepared in the same manner as in Example 1 except that 72 g of titanium oxide used as the first component was changed to 8 g of titanium oxide used as the second component.
[実施例５]
第一成分で用いる酸化チタンを40g、第二成分で用いる酸化チタンを40gにそれぞれ変えた以外は、実施例１と同様に触媒を調製した。
[Example 5]
A catalyst was prepared in the same manner as in Example 1 except that 40 g of titanium oxide used as the first component was changed to 40 g of titanium oxide used as the second component.
[実施例６]
第一成分で用いる酸化チタンを8g、第二成分で用いる酸化チタンを72gにそれぞれ変えた以外は、実施例１と同様に触媒を調製した。
[Example 6]
A catalyst was prepared in the same manner as in Example 1 except that 8 g of titanium oxide used as the first component was changed to 72 g of titanium oxide used as the second component.
[実施例７]
第二成分で用いる酸化チタンを石原産業社製、商品名MC90、比表面積約90m2/gに変えた以外は、実施例１と同様に触媒を調製した。
[Example 7]
A catalyst was prepared in the same manner as in Example 1 except that the titanium oxide used in the second component was changed to Ishihara Sangyo Co., Ltd., trade name MC90, and a specific surface area of about 90 m 2 / g.
[実施例８]
第二成分で用いる酸化チタンとして石原産業社製、商品名MC90、比表面積約90m2/gを、予め700℃で２時間焼成して比表面積を30m2/gとしてから用いるように変えた以外は、実施例１と同様にして触媒を調製した。
[Example 8]
Except for the titanium oxide used in the second component, manufactured by Ishihara Sangyo Co., Ltd., trade name MC90, specific surface area of about 90 m 2 / g, previously calcined at 700 ° C. for 2 hours to have a specific surface area of 30 m 2 / g. Prepared a catalyst in the same manner as in Example 1.
[実施例９]
メタバナジン酸アンモニウム1.78g、モリブデン酸アンモニウム2.73gを水84ｇに溶解させ、これに酸化チタン(石原産業社製、商品名MC90、比表面積約90m2/g)56ｇを入れ、加熱混練を行った。これを40℃で一時間保温した後、120℃で一時間乾燥後、500℃で2時間焼成して触媒を得た。本触媒の組成はTi/Mo/V=95.8/2.1/2.1 原子比である。これとは別に、水36gに酸化チタン(石原産業社製、比表面積約90m2/g)24gを入れ、加熱混練を行い、これを40℃で一時間保温した後、120℃で一時間乾燥して触媒を得た。Ti/Mo/V粉末、上記調製法の酸化チタンのみの粉末それぞれを425〜500μｍの粒径に揃えた。さらに、Ti/Mo/V粉末と酸化チタンのみの粉末をポリエチレン製の袋の中で物理混合した粉末に対し(重量比70/30)、加圧成型器を用いて、約1.3t/cm2で加圧し、粒状に成型した。物理混合後の触媒の組成はTi/Mo/V=97.0/1.5/1.5 原子比である。
[Example 9]
1.78 g of ammonium metavanadate and 2.73 g of ammonium molybdate were dissolved in 84 g of water, and 56 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., trade name MC90, specific surface area of about 90 m 2 / g) was added and kneaded by heating. This was kept at 40 ° C. for 1 hour, dried at 120 ° C. for 1 hour, and calcined at 500 ° C. for 2 hours to obtain a catalyst. The composition of this catalyst is Ti / Mo / V = 95.8 / 2.1 / 2.1 atomic ratio. Separately, 24 g of titanium oxide (Ishihara Sangyo Co., Ltd., specific surface area of about 90 m 2 / g) is added to 36 g of water, kneaded with heating, kept at 40 ° C for 1 hour, and then dried at 120 ° C for 1 hour As a result, a catalyst was obtained. The Ti / Mo / V powder and the titanium oxide-only powder prepared as described above were each adjusted to a particle size of 425 to 500 μm. Furthermore, for a powder obtained by physically mixing Ti / Mo / V powder and titanium oxide-only powder in a polyethylene bag (weight ratio 70/30), using a pressure molding machine, about 1.3 t / cm 2 And pressed into a granular shape. The composition of the catalyst after physical mixing is Ti / Mo / V = 97.0 / 1.5 / 1.5 atomic ratio.
[実施例１０]
実施例１における第二成分の調製に用いる水にモリブデン酸アンモニウム2.73gを溶解させ、酸化チタンを入れるように変えた以外は、実施例１と同様にして触媒を調製した。
[Example 10]
A catalyst was prepared in the same manner as in Example 1 except that 2.73 g of ammonium molybdate was dissolved in water used for preparation of the second component in Example 1 and titanium oxide was added.
[比較例４]
メタバナジン酸アンモニウム1.78g、モリブデン酸アンモニウム2.73gを水120ｇに溶解させ、これに酸化チタン(石原産業社製、商品名MC90、比表面積約90m2/g)80ｇを入れ、加熱混練を行った。これを40℃で一時間保温した後、120℃で一時間乾燥後、500℃で2時間焼成して触媒を得た。本触媒の組成はTi/Mo/V=97.0/1.5/1.5 原子比である。Ti/Mo/V粉末を425〜500μｍの粒径に揃え、加圧成型器を用いて、約1.3t/cm2で加圧し、粒状に成型した。
[Comparative Example 4]
1.78 g of ammonium metavanadate and 2.73 g of ammonium molybdate were dissolved in 120 g of water, and 80 g of titanium oxide (made by Ishihara Sangyo Co., Ltd., trade name MC90, specific surface area of about 90 m 2 / g) was added thereto and kneaded by heating. This was kept at 40 ° C. for 1 hour, dried at 120 ° C. for 1 hour, and calcined at 500 ° C. for 2 hours to obtain a catalyst. The composition of this catalyst is Ti / Mo / V = 97.0 / 1.5 / 1.5 atomic ratio. Ti / Mo / V powders were aligned to a particle size of 425 to 500 μm, and pressed with a pressure molding machine at about 1.3 t / cm 2 to be molded into granules.
[実施例１１]
実施例９における第一成分のモリブデン酸アンモニウム2.73gをメタタングステンアンモニウム3.59gに変えた以外は、実施例９と同様にして触媒を調製した。
[Example 11]
A catalyst was prepared in the same manner as in Example 9, except that 2.73 g of ammonium molybdate as the first component in Example 9 was changed to 3.59 g of metatungsten ammonium.
[実施例１２]
実施例１０における第二成分のモリブデン酸アンモニウム2.73gをメタタングステンアンモニウム3.59gに変えた以外は、実施例１０と同様にして触媒を調製した。
[Example 12]
A catalyst was prepared in the same manner as in Example 10 except that 2.73 g of the second component ammonium molybdate in Example 10 was changed to 3.59 g of metatungsten ammonium.
[比較例５]
比較例３におけるモリブデン酸アンモニウム2.73gをメタタングステンアンモニウム3.59gに変えた以外は、比較例３と同様にして触媒を調製した。
[Comparative Example 5]
A catalyst was prepared in the same manner as in Comparative Example 3 except that 2.73 g of ammonium molybdate in Comparative Example 3 was changed to 3.59 g of metatungsten ammonium.
[試験例]
上記実施例の効果を示すため以下のような模擬試験を行った。実施例及び比較例の触媒を表１の粒子径に揃え、表１の条件で脱硝率を測定した。得られた結果を表２、表３および表４に纏めて示した。
[Test example]
In order to show the effects of the above examples, the following simulation tests were conducted. The catalysts of Examples and Comparative Examples were aligned with the particle diameters shown in Table 1, and the denitration rate was measured under the conditions shown in Table 1. The obtained results are summarized in Table 2, Table 3 and Table 4.
表２において、実施例１〜３の触媒が比較例１や比較例２、３の触媒よりも活性が高いことが分かる。また、混合比が異なる実施例４〜６の触媒が比較例２よりも活性が高いことが明らかである。このことから、本発明の触媒が高い脱硝活性を有していることが分かる。さらに、実施例１、７、８の結果から、第二成分に用いられるTiO2の比表面積は大きい程、高い活性が得られることが分かる。さらに、表３の実施例９、１０の触媒が比較例４の触媒よりも活性が高いことが分かる。このことから、本発明の触媒が高い脱硝活性を有していることが分かる。そして、実施例１０の結果からモリブデンは第二成分の方に担持されている方が、活性が高いことが明らかである。 In Table 2, it can be seen that the catalysts of Examples 1 to 3 have higher activity than the catalysts of Comparative Example 1 and Comparative Examples 2 and 3. In addition, it is clear that the catalysts of Examples 4 to 6 having different mixing ratios are higher in activity than Comparative Example 2. This shows that the catalyst of the present invention has a high denitration activity. Furthermore, from the results of Examples 1, 7, and 8, it can be seen that the higher the specific surface area of TiO 2 used for the second component, the higher the activity. Further, it can be seen that the catalysts of Examples 9 and 10 in Table 3 are higher in activity than the catalyst of Comparative Example 4. This shows that the catalyst of the present invention has a high denitration activity. From the results of Example 10, it is clear that molybdenum is more active when it is supported on the second component.
また、表４の実施例１１、１２の触媒が比較例５の触媒よりも活性が高いことが分かる。このことから、本発明の触媒が高い脱硝活性を有していることが分かる。そして、実施例１２の結果からタングステンは第二成分の方に担持されている方が、活性が高いことが明らかである。 Moreover, it turns out that the activity of the catalysts of Examples 11 and 12 in Table 4 is higher than that of the catalyst of Comparative Example 5. This shows that the catalyst of the present invention has a high denitration activity. From the results of Example 12, it is clear that tungsten is more active when it is supported on the second component.
Claims (1)
バナジウム、モリブデンおよびタングステンを含まず、且つチタン酸化物を含む組成物を第二成分とし、
第一成分と第二成分とを混合し、次いで成形する脱硝触媒の製造方法であって、
第一成分のチタン酸化物の比表面積が30〜120m2/gであることを特徴とする脱硝触媒の製造方法。 The first component is a composition pre-fired after supporting an active ingredient containing at least vanadium in titanium oxide,
A composition that does not contain vanadium , molybdenum and tungsten and contains titanium oxide is the second component ,
A first component and a second component engaged mixed, then a method for producing a denitration catalyst that be molded,
Method for producing a denitration catalyst having a specific surface area of the titanium oxide of the first component is characterized in that it is a 30~120m 2 / g.
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