KR20140103126A - Titanium-containing granular powder and method for production thereof, and exhaust gas treatment catalyst using same and method for production thereof - Google Patents

Abstract

Disclosed is a titanium-containing particulate powder having good moldability into a honeycomb structure, high abrasion resistance, and reduced specific surface area after firing, a method for producing the particulate powder, a honeycomb-shaped exhaust gas treating catalyst obtained from the particulate powder, to provide.
The present invention relates to a titanium-containing granular powder containing at least one additive selected from a composite oxide containing at least one of tungsten and molybdenum and titanium, and a nitrogen compound, sulfur compound and chlorine compound containing tungsten or molybdenum in a predetermined ratio And a honeycomb-shaped exhaust gas treating catalyst formed by molding the granular powder into a honeycomb structure.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a titanium-containing granular powder, an exhaust gas treating catalyst using the same,

TECHNICAL FIELD [0001] The present invention relates to a titanium-containing granular powder for producing an exhaust gas treating catalyst having good moldability into a honeycomb structure, an exhaust gas treating catalyst using the same, and a process for producing the same.

Nitrogen oxides, which cause photochemical smog, are contained in the combustion exhaust gas discharged from thermal power plants, various factories, and refuse incineration plants. As a result, various exhaust gas denitration techniques for removing these nitrogen oxides from the exhaust gas have been proposed. One of the widely used exhaust gas denitration technologies is Selective Catalytic Reduction (SCR) in which ammonia is injected into an exhaust gas and then brought into contact with a catalyst to reduce nitrogen oxides to nitrogen gas and water. In this SCR method, a catalyst carrying an active component such as vanadium oxide, tungsten oxide, or the like is supported on a titanium oxide carrier. Normally, the denitration catalyst of the SCR method is disposed in the smoke passage so as to advance the denitration reaction by contacting with the exhaust gas. However, in order to suppress the increase of the pressure loss in the smoke passage and to increase the contact area with the exhaust gas, The catalyst is used, for example, by molding into a honeycomb shape.

The honeycomb-shaped denitration catalyst is a method of extruding a powdery carrier component into a honeycomb shape and then impregnating and supporting the active component. In the method of kneading the carrier component and the active component together with a molding aid and extrusion molding into a honeycomb shape . Therefore, it is preferable that the titanium oxide powder serving as the carrier component has high extrusion moldability. Here, the titanium oxide powder calcined at a relatively high temperature has good extrusion-formability, but the crystallization progresses, so that the specific surface area is lowered and the denitration performance is lowered in some cases. On the other hand, the titanium oxide powder calcined at a relatively low temperature has a small decrease in specific surface area, but has a problem of difficulty in molding into a honeycomb shape because of poor extrudability.

Patent Document 1 discloses a technique of combining titanium dioxide and tungsten oxide complex oxides by adding ammonium paratungstate to a titanium dioxide precursor and firing the mixture at 500 ° C for 3 hours. In Patent Document 2, titanium dioxide Ammonium paratungstate and ammonium metavanadate were added to the precursor, and the mixture was calcined at 550 DEG C for 2 hours to obtain a titanium-containing powder for producing the denitration catalyst. However, for example, in the case of ammonium paratungstate, it is known that ammonia is decomposed at a temperature of about 450 ° C., resulting in tungsten oxide. Namely, since the titanium-containing powders for producing the catalyst for dehydration described in Patent Documents 1 and 2 do not contain the ammonium salt, when the honeycomb structured body was produced using them, the moldability at the time of extrusion molding was not good.

On the other hand, in the catalyst for exhaust gas denitration described in Patent Document 3, ammonium metatungstate is added to titanium dioxide powder calcined at 600 to 1000 ° C, and then the honeycomb is shaped and further calcined at a temperature of 500 to 600 ° C Thereby obtaining a denitration catalyst. However, when the titanium dioxide powder is fired at 600 to 1000 占 폚, the crystallization proceeds and the specific surface area of the powder becomes small, and as a result, the activity of the denitration catalyst is sometimes lowered.

Japanese Patent Application Laid-Open No. 10-235206 Japanese Patent Application Laid-open No. 11-226360 Japanese Patent Application Laid-Open No. 9-47637

The object of the present invention is to provide a titanium-containing particulate powder having good moldability and a reduced specific surface area after firing, a method for producing the particulate powder, and a honeycomb-shaped exhaust gas containing the titanium- And a process for producing the same.

The first invention relates to a composite oxide (X) of at least one of tungsten and molybdenum and a metal element containing titanium and at least one of a composite oxide (X) of tungsten, a tungsten-containing sulfur compound, (iii) containing particulate powder for producing a honeycomb-shaped exhaust gas treating catalyst, which contains an additive (Y) selected from the group consisting of molybdenum-containing nitrogen compounds, iv) molybdenum-containing nitrogen compounds, (v) molybdenum-containing sulfur compounds, and (vi) molybdenum-

(1) When the additive (Y) contains (i) a tungsten-containing nitrogen compound or (iv) a molybdenum-containing nitrogen compound, the number of moles of titanium atoms contained in the titanium- Containing granular powder has a molar ratio (B / A) in the range of 8.70 x 10 < ^-4 > to 2.78 x 10 < ^-1 &

(2) When the additive (Y) contains (ii) a sulfur-containing tungsten compound or (v) a sulfur compound containing molybdenum, the number of moles of titanium atoms contained in the titanium- Containing granular powder is represented by C, the molar ratio (C / A) thereof is in the range of 6.96 × 10 ^-3 to 5.55 × 10 ^-1 ,

(3) When the additive (Y) contains (iii) a tungsten-containing chlorine compound or (vi) a molybdenum-containing chlorine compound, the number of moles of titanium atoms contained in the titanium- Containing granular powder is represented by D, the molar ratio (D / A) of the chlorine atom contained in the granular powder is in the range of 6.96 x 10 ^-3 to 6.94 x 10 ^-1

Containing particulate powder for producing a honeycomb-shaped exhaust gas treating catalyst.

Further, it is preferable that the first aspect of the invention has the following requirements.

(a) when the titanium-containing granular powder is measured by X-ray diffraction, the titanium oxide contained in the titanium-containing granulated powder has an anatase crystal structure and the peak intensity of the (101) face of the anatase crystal is P ¹ and the peak intensity of the (101) plane of the anatase-type crystal in the reference powder of titanium dioxide (MC-90 manufactured by Ishihara Sangyo K.K.) is represented by P ⁰ , the peak intensity ratio (P ¹ / P ⁰ ) is in the range of 0.30 to 1.3, and the specific surface area of the titanium-containing particulate powder is in the range of 40 to 300 m ² / g.

(b) the titanium-containing granular powder is a granular material having a particle diameter of not less than 45 占 퐉 not less than 99.9% by weight of the total amount of the titanium-containing granular powder.

(c) the molybdenum-containing nitrogen compound is at least one selected from the group consisting of ammonium tungstate, ammonium metatungstate, ammonium tungstate, ammonium tetantiotungstate, and (i) At least one member selected from the group consisting of ammonium ammonium, ammonium phosphomolybdate and ammonium tetrathiomolybdate.

(d) the tungsten-containing sulfur compound (ii) is tungsten disulfide, and (v) the molybdenum-containing sulfur compound is molybdenum disulfide.

(e) the (iii) tungsten-containing chlorine compound is tungsten hexachloride, and (vi) the molybdenum-containing chlorine compound is molybdenum contaminated.

The second invention is a honeycomb-shaped exhaust gas treating catalyst characterized by containing a titanium-containing particulate powder and an active component, wherein the content ratio of the titanium-containing particulate powder is 60 wt% or more.

It is preferable that the second invention has the following requirements.

(a) the active ingredient is vanadium oxide.

(b) the honeycomb-shaped exhaust gas treating catalyst is a nitrogen oxide removing catalyst.

The third invention relates to a composite oxide (X) of at least one of tungsten and molybdenum and a metal element containing titanium and at least one of a composite oxide (X) of tungsten and at least one element selected from the group consisting of (i) a tungsten-containing nitrogen compound, (ii) and a step of mixing the additive (Y) selected from the following: (iv) a molybdenum-containing nitrogen compound, (v) a molybdenum-containing sulfur compound, and (vi) a molybdenum- Containing granular powder,

(1) In the case where (i) a tungsten-containing nitrogen compound or (iv) a molybdenum-containing nitrogen compound is used as the additive (Y), the number of moles of titanium atoms contained in the titanium- (B / A) of 8.70 x 10 < ^-4 > to 2.78 x 10 < ^-1 > when the number of moles of nitrogen atoms contained in the granular powder Comprising:

(2) In the case of using (ii) a sulfur-containing tungsten compound or (v) a sulfur compound containing molybdenum as the additive (Y), the number of moles of titanium atoms contained in the titanium- Containing granular powder is mixed with the additive in such a ratio that the molar ratio (C / A) thereof is in the range of 6.96 × 10 ^-3 to 5.55 × 10 ^-1 , , And further comprises

(3) In the case of using (iii) a tungsten-containing chlorine compound or (vi) a molybdenum-containing chlorine compound as the additive (Y), the number of moles of titanium atoms contained in the titanium- when revealed the molar number of chlorine atoms contained in the granulated powder containing a D, its molar ratio (D / a) is 6.96 × 10 ^-3 to mixing the composite oxide and the additive at a ratio in the range of 6.94 × 10 ^-1 Including the steps of

Containing particulate powder for producing a honeycomb-shaped exhaust gas treating catalyst.

It is preferable that the third invention has the following requirements.

(i) a tungsten-containing nitrogen compound, (ii) a tungsten-containing sulfur compound, (iii) a tungsten-containing chlorine compound, (iv) a molybdenum-containing nitrogen compound , (V) a sulfur compound containing molybdenum, and (vi) at least one additive (Y) selected from a chlorine compound containing molybdenum.

A fourth aspect of the present invention is a method for producing a honeycomb-shaped exhaust gas treating catalyst, comprising: (1) mixing a water-containing vanadium oxide or a precursor thereof with titanium-containing granular powder for producing a honeycomb-shaped exhaust gas treating catalyst produced by the production method according to the third invention, ,

(2) a step of adding a structural reinforcement to the slurry liquid and kneading the mixture to obtain a mixture containing the above components,

(3) a step of extruding and forming the mixed material to obtain a honeycomb structured body, and

(4) drying the honeycomb structured body, and further calcining the honeycomb structured body under a temperature condition of 400 to 700 ° C.

Since the titanium-containing particulate powder of the present invention contains a composite oxide of at least one of tungsten and molybdenum with titanium, it is possible to suppress the progress of crystallization during firing of the exhaust gas treating catalyst after forming the honeycomb, High catalytic activity can be maintained. Further, since the additive includes a nitrogen compound, a sulfur compound and a chlorine compound containing tungsten or molybdenum, these additives serve to improve the moldability of the titanium-containing granulated powder and as a result, the honeycomb shape It is possible to obtain a honeycomb structure having little or no defects or the like.

Fig. 1 is a conceptual diagram of a honeycomb structured body according to the present invention, and more particularly, shows a plan view seen from one end side in a penetrating direction of a honeycomb hole.

Hereinafter, preferred embodiments of the present invention will be described in detail.

[Titanium-containing granular powder]

The titanium-containing particulate powder (hereinafter, simply referred to as " titanium-containing particulate powder ") for use in the production of a honeycomb type exhaust gas treating catalyst in the present invention includes a complex oxide of at least one of tungsten and molybdenum and a metal element containing titanium .

The composite oxide is a compound of at least one of a metal element of tungsten (W) and molybdenum (Mo), and a titanium (Ti) metal element and oxygen (O). For example, a part of the composite oxide containing titanium (IV), tungsten (IV) and oxygen is represented by the general formula (I).

The composite oxide contains a crystal structure portion corresponding to anatase-type titanium dioxide.

Specific examples of the composite oxide composite oxide including titanium and tungsten (For convenience this TiO _4/2 -WO _4/2 indicated by), the composite oxide containing titanium and molybdenum (For convenience this TiO _4/2 -MoO _4/2 represents a) a binary system compound oxide, titanium oxide, complex oxide comprising tungsten and molybdenum, such as (ternary composite oxide of them for convenience _{TiO 4/2 -WO 4/2} -TiO 4/2 -MoO 4 / indicated by ₂₎ . These two won based or ternary composite oxide to have a structure introduced into, WO _4/2, dispersion and the like MoO _4/2 in the titanium molecular oxidation of TiO _4/2 As shown in the above general formula (I) I think. Furthermore, in the WO _4/2 or MoO _4/2 is the time of heating the firing of the honeycomb structural body is obtained from a titanium-containing granulated powder containing the compound oxide, titanium dioxide (TiO ₂₎ was incorporated into the TiO _4/2 titanium oxide molecules It seems to play a role of suppressing the progress of crystallization or the transition to rutile type titanium dioxide (TiO ₂ ).

The content of _{WO 4/2, MoO 4/} 2 from among the composite oxide is desired to be less than the amount of TiO _4/2. When more specifically described, these WO _4/2 or MoO _4/2 when converted to oxide of WO ₃ or MoO ₃ (stage, TiO _4/2 is referred to as TiO _2), each alone or in a total amount, and 0 weight % And not more than 20% by mass. Here, WO _4/2 or when the content of MoO _4/2 more than the amount of TiO _4/2, the honeycomb-shaped exhaust gas treating catalyst with the honeycomb structural body is obtained from a titanium-containing granulated powder containing the compound oxide, especially nitrogen oxide In the removal catalyst, excellent effects such as resistance to sulfur compounds contained in the exhaust gas and abrasion resistance may not be obtained.

When the specific surface area (SA) and the titanium-containing granular powder are measured by X-ray diffraction as described above, the titanium-containing granular powder containing the composite oxide and the additive is preferably a 101) plane peak intensity is within a predetermined range. The specific surface area of the titanium-containing granular powder may be in the range of 40 to 300 m ² / g, more preferably in the range of 50 to 120 m ² / g. If the specific surface area is less than 40 m ² / g, the specific surface area after baking the honeycomb structure formed by using the titanium-containing particulate powder becomes small, so that sufficient catalytic activity as an exhaust gas treating catalyst can not be obtained , It is difficult to obtain a titanium-containing granular powder having a specific surface area exceeding 300 m ² / g. The specific surface area of the titanium-containing granular powder can be controlled within the above-mentioned range by heating or firing the granular powder. However, as the additive is decomposed to gaseous nitrogen-containing compound used herein (e.g., NH _4), the gaseous sulfur compounds (e.g., SO ₂₎ and the gaseous chlorine compounds (e.g., ClO ₂₎ release and the like Do not heat up to the temperature. For example, when ammonium paratungstate is used as an additive, the compound decomposes at a temperature of about 450 ° C to release ammonia. Therefore, it is necessary not to heat the compound to a temperature higher than the above temperature. If the honeycomb structure is formed by using the titanium-containing granular powder from which the gaseous nitrogen compound, the gaseous sulfur compound, the gaseous chlorine compound, or the like is released from the additive component, the moldability of the honeycomb structure is deteriorated .

Further, the surface peak intensity 101 of the anatase type crystal contained in the titanium-containing granulated powder as P ^1, and the reference powder (Ishihara Sangyo whether or sikki manufactured Preparation MC-90), anatase-type crystal in the titanium dioxide (101) plane When the peak intensity is represented by P ⁰ , the peak intensity ratio (P ¹ / P ⁰ ) thereof is preferably in the range of 0.30 to 1.3, more preferably 0.6 to 1.2. When the peak intensity ratio exceeds 1.3, it indicates that the crystallization of titanium dioxide is proceeding, leading to a decrease in specific surface area and catalyst performance. In addition, it is difficult to prepare a titanium-containing granular powder having a peak strength ratio lower than 0.30. A more preferable range of the peak intensity ratio is 0.9 to 1.1. In this range, the effect of adding the additive in improving moldability is maximized. The peak intensity ratio (P ¹ / P ⁰ ) can be adjusted to the above-described range by heating or firing the titanium-containing granular powder. However, as in the above case, the additive used here is decomposed to form a gaseous nitrogen compound (for example, NH ₄ ), a gaseous sulfur compound (for example, SO ₂ ) or a gaseous chlorine compound ₂ ) It should not be heated to the temperature which emits light. The reason is as described above.

In the titanium-containing granular powder according to the embodiment, an additive for improving the formability at the time of molding is added to the honeycomb structured body. The additive serves to make the titanium-containing granular powder prepared for extrusion molding have an appropriate viscosity for the release. By providing the bladder with a viscosity, it is possible to form the honeycomb structured body with little or no part of the honeycomb-like shape, since the bladder fed to the spinneret (die) of the vacuum extrusion molding machine or the like is hardly cut off . Here, the term " part of the honeycomb shape defect " means that a part of the partition wall forming the honeycomb structured body becomes insufficient as shown in Fig. 1, and in some cases, have. As a result, the specific surface area of the honeycomb structured body may be reduced, or the mechanical strength of the honeycomb structured body may be lowered. Generally, in a vacuum extrusion molding machine, extrusion molding continues even if some defects of the honeycomb shape occur during the molding. Therefore, once the extrusion molding machine is stopped, it is necessary to repair or dispose of the problems. Therefore, in the titanium-containing granular powder according to the present invention, an additive capable of suppressing the occurrence of such honeycomb defects is added to the granular powder.

The additive added to the titanium-containing granular powder is selected from the group of additives consisting of a tungsten-containing nitrogen compound, a tungsten-containing sulfur compound, a tungsten-containing chlorine compound, a molybdenum-containing nitrogen compound, a molybdenum-containing sulfur compound and a molybdenum-containing chlorine compound.

Examples of the tungsten-containing nitrogen compound include ammonium tungstate such as ammonium paratungstate, ammonium metatungstate, ammonium tungstate and ammonium tetantiotungstate. Examples of the tungsten-containing sulfur compound include tungsten disulfide, . Examples of the tungsten-containing chlorine compound include tungsten hexachloride, tungsten dichloride, tungsten trichloride, tungsten tetrachloride, tungsten tin chloride, tungsten dioxide, and tungsten tetrachloride.

Examples of the molybdenum-containing nitrogen compound include ammonium molybdate such as ammonium molybdate, ammonium molybdate, ammonium tetrathiomolybdate, and the like. Examples of the molybdenum-containing sulfur compound include molybdenum disulfide, molybdenum trisulfide, molybdenum disulfide, . Examples of the molybdenum-containing chlorine compound include molybdenum contamination, molybdenum dichloride, molybdenum trichloride, molybdenum tetrachloride, and polluted molybdenum trioxide.

Further, these additives are oxidized to tungsten oxide (WO ₃ ) or molybdenum oxide (MoO ₃ ) when the honeycomb structure thus formed is calcined to obtain an exhaust gas treating catalyst. The tungsten oxide or molybdenum oxide is obtained here, is contained in the composite oxide as the addition of titanium dioxide (TiO _4/2) introduced in said WO _4/2 or MoO _4/2 is different from the form of their compounds. However, inhibiting the WO _4/2 or MoO _4/2 with the action of a specific surface area decreases to determine upset of the titanium dioxide during the exhaust gas treatment catalyst calcined accompanying, and catalyst deactivation contained in the composite oxide And so on.

It is desired that the titanium-containing granular powder in the present invention contains the above additives in the proportions shown below.

In the case where the additive contains a tungsten-containing nitrogen compound or a molybdenum-containing nitrogen compound, a value obtained by dividing the mass of the titanium atom contained in the titanium-containing particulate powder by its atomic weight is represented by A, When the value obtained by dividing the mass of the nitrogen atom by the atomic amount thereof is represented by B, the ratio (B / A) thereof is preferably in the range of 8.70 x 10 ^-4 to 2.78 x 10 ^-1 .

When the additive contains a tungsten-containing sulfur compound or a molybdenum-containing sulfur compound, a value obtained by dividing the mass of the titanium atom contained in the titanium-containing particulate powder by the atomic weight thereof is represented by A, (C / A) is preferably in the range of 6.96 x 10 ^-3 to 5.55 x 10 ^-1 , when the value obtained by dividing the mass of the sulfur atom contained by the atomic amount thereof by C is preferable.

When the additive contains a tungsten-containing chlorine compound or a molybdenum-containing chlorine compound, the value obtained by dividing the mass of the titanium atom contained in the titanium-containing particulate powder by the atomic weight thereof is represented by A, (D / A) in the range of 6.96 x 10 < ^-3 > to 6.94 x 10 < ^{-1 &} gt ;, when the value obtained by dividing the mass of the chlorine atom contained by the atomic amount thereof by D is preferable.

When the content of the additive is less than the above-mentioned range, there is a possibility that the generation of the honeycomb defect can not be sufficiently suppressed. If the amount of the additive exceeding the above range is included, the heat generated when the additive is oxidized becomes large, and cracking or cracking may occur at the time of baking the honeycomb structured body.

In addition, it is preferable that the titanium-containing granular powder according to the present invention is a granular material having a particle diameter of not more than 45 탆 in 99.9% by weight or more of the powder. When the particles in the particle diameter range is less than 99.9 mass% of the total weight, that is, when the particulate matter having a particle diameter larger than 45 占 퐉 is contained in an amount of more than 0.1 mass%, a part of the partition wall or a part And a desired honeycomb structure may not be obtained.

[Method for producing complex oxide]

An example of a method for producing a titanium-containing granular powder having the above-described characteristics will be described. First, a method for producing a composite oxide of a metal element containing at least one of tungsten and molybdenum and titanium is described.

A titanium-containing solution such as a raw material of meta-titanic acid, titanium dioxide, and finally added to the raw material as contained in the composite oxide in the form of _4/2 or WO MoO _4/2, WO ₃ and these raw materials To 5 to 10% by mass in terms of oxide of MoO ₃ . As the raw material, for example, a substance similar to the above-mentioned additive can be used. Specific examples thereof include tungsten-containing nitrogen compounds such as ammonium paratungstate, ammonium metatungstate, ammonium tungstate and ammonium tetantiotungstate, tungsten-containing sulfur compounds such as tungsten disulfide and tungsten trisulfide, tungsten hexachloride, Tungsten-containing chlorine compounds such as tungsten, tungsten trichloride, tungsten tetrachloride, tungsten tin chloride, tungsten dioxide, and tungsten oxide tetrachloride, molybdenum-containing nitrogen compounds such as ammonium molybdate, ammonium molybdate, ammonium tetrathiomolybdate, , Molybdenum-containing sulfur compounds such as molybdenum trisulfide and molybdenum disulfide, molybdenum-containing chlorine compounds such as contaminated molybdenum, molybdenum dichloride, molybdenum trichloride, molybdenum tetrachloride, and contaminated molybdenum trioxide.

The addition amount of these raw materials in the WO _4/2 or MoO _4/2 and so on contained in the dehydrated, and even during the sintering a titanium-containing granular powder, and more particularly, a composite oxide by pre-experiment WO ₃ or MoO ₃ oxide basis And the relationship between the content of tungsten or molybdenum converted into the amount of each raw material and the amount of each raw material to be added.

It is also preferable to use a titanium sulfate solution obtained in the production process of titanium dioxide by a sulfuric acid method as a raw material of metatitanic acid and further hydrolyze the titanium sulfate to obtain metatitanic acid.

An acid such as sulfuric acid or an alkali such as ammonia is added to a solution containing at least one of tungsten and molybdenum thus obtained and titanium to adjust the pH of the solution to a predetermined value within the range of 2 to 10.5 It is preferable to adjust it.

Thus, after obtaining a slurry solution containing at least one of tungsten and molybdenum and titanium and adjusting the pH to a predetermined value, the slurry solution is heated to a temperature range of, for example, 50 to 100 DEG C for 0.5 to 24 hours Aging. Then, the slurry solution after the heat aging is dehydrated, the dehydrated cake obtained is washed with distilled water or the like, and dehydrated again to obtain a dehydrated cake.

The dried composite obtained by drying the moisture in the obtained dewatered cake is sintered in a kiln or the like in an atmospheric environment at a temperature in the range of 400 to 700 ° C for 0.5 to 20 hours to obtain the composite oxide.

In the present invention, if necessary, the composite oxide is further pulverized by a ball mill or the like to obtain a composite oxide having a particle diameter of not less than 45 mu m of not less than 99.9 mass% of the total.

[Method for producing titanium-containing granular powder]

A tungsten-containing nitrogen compound, a tungsten-containing sulfur compound, a tungsten-containing chlorine compound, a molybdenum-containing nitrogen compound, a molybdenum-containing sulfur compound, and a molybdenum-containing compound are mixed with a composite oxide of at least one of tungsten and molybdenum produced by the above- And the additive selected from the additive group consisting of a chlorine compound are mixed to prepare the titanium-containing granular powder according to the present invention.

That is, when a tungsten-containing nitrogen compound or a molybdenum-containing nitrogen compound is used as the additive, the value obtained by dividing the mass of the titanium atom contained in the titanium-containing particulate powder by the atomic weight thereof is represented by A, (B / A) of 8.70 x 10 < ^-4 > to 2.78 x 10 < ^{-1 &} gt ;, when the value obtained by dividing the mass of nitrogen atoms contained in the composite oxide The additives are mixed. For example, the mixing amount of the additive may be determined by, for example, filling the relationship of the B / A ratio between the composite oxide and the titanium-containing granular powder to the mixing amount of the additive, and by inversely calculating the mixing amount of the necessary additives from the design value of B / A .

In the case of using a tungsten-containing sulfur compound or a molybdenum-containing sulfur compound as the additive, a value obtained by dividing the mass of the titanium atom contained in the titanium-containing particulate powder by its atomic weight is represented by A, and the titanium- (C / A) is in the range of 6.96 x ^10-3 to 5.55 x 10 < ^-1 > when the value obtained by dividing the mass of the sulfur atom contained in the composite oxide The additives are mixed. The mixing amount of the additive in this case can also be determined from the relationship between the mixing amount of the additive and the C / A ratio between the composite oxide and the titanium-containing particulate powder.

When a tungsten-containing chlorine compound or a molybdenum-containing chlorine compound is used as the additive, a value obtained by dividing the mass of the titanium atom contained in the titanium-containing particulate powder by the atomic weight thereof is represented by A, and the titanium- (D / A) of 6.96 x 10 < ^-3 > to 6.94 x 10 < ^{-1 &} gt ;, when the value obtained by dividing the mass of the chlorine atom contained in The additives are mixed. In this case, the addition amount of the additive can also be determined from the relationship between the mixing amount of the additive and the D / A ratio between the composite oxide and the titanium-containing particulate powder.

The additive used in the production of the titanium-containing granular powder may be selected from the above-mentioned additive group, or two or more kinds may be selected. The timing at which the additive is added to the complex oxide is not limited to the stage after the grinding of the complex oxide is performed. For example, the additive may be added to the ball mill together with the complex oxide to be pulverized at the same time.

It is preferable that the titanium-containing granular powder obtained in this way is a particulate material having a particle diameter of not more than 45 占 퐉 in a total amount of not less than 99.9 mass%. As a method for producing a titanium-containing particulate powder having a particle diameter within this range, it is also possible to mix an additive and a composite oxide previously pulverized by a ball mill or the like so that the particulate matter having a particle diameter of not less than 45 탆 is not less than 99.9 mass% The mixture may be pulverized after mixing the composite oxide and the additive, and the powder may have a particle diameter within the above range.

[Honeycomb shaped exhaust gas treating catalyst]

The honeycomb-shaped exhaust gas treating catalyst according to the present invention is an exhaust gas treating catalyst comprising the above-described honeycomb structured body, wherein the titanium-containing particulate powder is contained in an amount of 60 mass% or more, preferably 70 to 99.9 mass% . When the content of the titanium-containing granular powder is less than 60% by mass, the desired denitration activity may not be obtained. As described above, when the titanium-containing granular powder of the present invention is contained in an amount of 60 mass% or more, for example, the granular powder of the present invention which does not contain the composite oxide and the additive of the present invention Titanium dioxide powder, etc.) may be contained in an amount of less than 40 mass%.

The honeycomb-shaped exhaust gas treating catalyst further contains an active component for removing nitrogen oxides. Examples of the active ingredient include vanadium (V), tungsten (W), molybdenum (Mo), chromium (Cr), manganese (Mn), iron (Fe), nickel (Ni), copper Metal components such as Ag, Iron, Pd, Y, Ce, Nd, In and Ir.

Of the above-mentioned active ingredients, vanadium oxide (V ₂ O ₅ ) is suitably used because it is relatively inexpensive and has a high removal rate of nitrogen oxides. In addition, the content of the active component used in the exhaust gas treating catalyst for removing nitrogen oxides is preferably in the range of 0.1 to 30 mass% of the total catalyst weight as the metal oxide.

As described above, the honeycomb-shaped exhaust gas treating catalyst formed by containing at least 60 mass% of the titanium-containing particulate powder containing the composite oxide has a tendency to suppress the crystallization progress of the titanium dioxide during firing of the honeycomb structure containing the active component In addition, when the exhaust gas treatment is carried out using this, a high removal rate of nitrogen oxides can be achieved.

In addition, in the titanium-containing granular powder of the present invention the titanium oxide contained in the granulated powder (TiO _4/2) are WO _4/2 and / or MoO _4/2 so that forming the as composite oxide, for example the temperature The crystallization of titanium dioxide can be suppressed.

Even in the additives in the titanium-containing particulate powder, as well as containing the molybdenum, such as WO _4/2 tungsten or MoO _{4 /} such as ₂ in the composite oxide, used in order to improve the moldability of the extrusion molding, And raw materials which are finally fired to become oxides such as WO ₃ and MoO ₃ are included. Thus, even when the honeycomb structure formed by using the titanium-containing particulate powder is fired, the progress of crystallization of the titanium dioxide can be suppressed and the reduction of the specific surface area can be suppressed. The honeycomb-shaped exhaust gas treating catalyst in which the progress of crystallization of titanium dioxide is suppressed is difficult to lower its specific surface area, and the denitration activity close to the initial activity can be maintained for a long period of time. Further, the additive used in the present invention can enhance the moldability when extrusion molding of the honeycomb structured body is performed, so that it is possible to suppress the occurrence of honeycomb defects or the like.

[Manufacturing Method of Honeycomb-like Exhaust Gas Treatment Catalyst]

The honeycomb-shaped exhaust gas treating catalyst according to the present invention can be produced by (a) kneading the titanium-containing granular powder of the present invention and the active component or its precursor together with a molding aid or the like to obtain a raw material, extruding it into a desired honeycomb shape, (Kneading method); (b) kneading the titanium-containing granular powder of the present invention together with a molding aid or the like into a raw material, extruding it into a desired honeycomb shape, drying and firing the carrier, (Impregnation method), or the like.

Particularly, the catalyst prepared by the kneading method of (a) is a solid type catalyst, and in view of achieving high denitration activity, a honeycomb type exhaust gas treating catalyst containing vanadium oxide as an active material by a kneading method The following description will be made by way of example.

First, the titanium-containing granular powder of the present invention is dispersed in a solvent such as water to prepare a slurry solution. A precursor of vanadium oxide, for example, ammonium metavanadate and monoethanolamine as a solubilizer are added to the slurry solution. Further, a reinforcing material such as glass fiber or acidic white clay, or a lubricant such as polyethylene oxide is added to the slurry solution, kneaded and kneaded with a kneader such as a kneader to produce a blended material suitable for extrusion molding.

The thus-obtained mixture is subjected to extrusion molding, for example, in a vacuum extruder or the like to obtain a honeycomb structure. At this time, the additive contained in the raw material carries an appropriate viscosity to the raw material, thereby making it difficult for the raw material supplied to the cementing member of the vacuum extrusion molding machine to be cut off halfway, and the honeycomb structure . Thereafter, the obtained honeycomb structure is dried, and the dried honeycomb structure is fired in a kiln or the like in an atmospheric environment, for example, at a temperature in the range of 400 to 700 ° C for 0.5 to 24 hours to remove the glass fiber or the titanium oxide , A honeycomb-shaped exhaust gas treatment catalyst containing vanadium oxide as an active metal is obtained.

Generally, when a titanium oxide carrier (for example, a honeycomb structure) in which vanadium oxide or its precursor as an active material is added or impregnated with a suspension aqueous solution thereof is fired, crystallization of titanium dioxide proceeds by the presence of vanadium Is known. Therefore, in the production of the exhaust gas treating catalyst of the present invention, the titanium-containing particulate powder obtained by firing in the absence of vanadium oxide or a precursor thereof (including suspension aqueous solutions thereof) is used. In this respect, it is not preferable to add the vanadium source from the calcination step of the titanium-containing particulate powder, and it is preferable to carry out calcination at the stage of obtaining the catalyst precursor (honeycomb structure) containing the vanadium source. If the catalyst precursor added with the vanadium source is calcined as described above and the catalyst precursor is produced using the titanium-containing granular powder of the present invention, the degree of progress of the crystallization of titanium dioxide can be sufficiently suppressed for the above reasons.

The shape of the honeycomb type exhaust gas treating catalyst (honeycomb structure) thus obtained is not particularly limited, but it is a square column or a rectangular column. In the plane viewed from one end side in the penetrating direction of the honeycomb holes, A plurality of quadrangular honeycomb holes (for example, 4 to 2500) are drilled. However, the honeycomb hole may have a honeycomb shape instead of a quadrangle. The external dimensions of the honeycomb structured body are (1) a plane length (hereinafter, also referred to as " the length of one side of the plane ") of about 30 to 300 mm, preferably about 50 to 200 mm, (ii) a length of one side of the opening forming the honeycomb hole (square) is about 100 to 3,000 mm, preferably about 300 to 1,500 mm, and (iii) (Hereinafter also referred to as " partition wall thickness ") formed between the honeycomb holes is about 0.1 to 2 mm, preferably about 2 to 10 mm, and more preferably about 2 to 10 mm, (V) the opening ratio of the honeycomb structure is in the range of 60 to 85%, preferably 70 to 85%. When the external dimension of the honeycomb structure having the square pillar shape is out of the above-mentioned range, it becomes difficult to form the honeycomb structure, the strength of the honeycomb structure becomes weak, or the denitration activity per unit volume or decomposition of the organic halogen compound The activity may be lowered.

[Method of using honeycomb-shaped exhaust gas treating catalyst]

Honeycomb-shaped exhaust gas treating catalyst of the present invention, the addition of a reducing agent of ammonia, and the like in addition to the heavy metal, the exhaust gas containing dust containing NO _X, SO _X such as exhaust gas, in particular boiler exhaust gas containing NO _X And is suitably used for the NO _x removal method for catalytic reduction. The catalyst is used under the usual denitration treatment conditions. Specifically, the reaction temperature is in the range of 150 to 600 占 폚, preferably 300 to 400 占 폚, and the space velocity (superficial velocity) 100000 ^{hr &lt}; ^{-1 &} gt ;.

Example

[Assessment Methods]

A method for evaluating a honeycomb-shaped exhaust gas treating catalyst produced by using the titanium-containing granular powder of each example will be described below.

[1] Moldability test (occurrence of honeycomb defect)

The criteria for the moldability of the honeycomb structure were determined by continuously molding 20 pieces of the honeycomb structure having a length of 500 mm in the direction of perforation of one quadrangle in a vacuum extrusion molding machine (length of the flat side: about 75 mm, length of one side of the honeycomb hole: about 6.7 mm, the thickness of the partition wall of the honeycomb hole: about 0.75 mm), and it was confirmed how many pieces of the honeycomb shape were missing on the subsequent honeycomb structure.

[2] Wear strength

A honeycomb type exhaust gas treating catalyst including a honeycomb structure having a honeycomb hole number of 9 × 9 and a penetration direction length of 100 mm (cut out and adjusted to have other dimensions) is used as a test sample, and the test sample is supplied to a flow- . In the flow-through type reactor, the gas containing sand was circulated under the following conditions, and the wear rate was measured based on the reduction amount of the catalyst weight based on the following formula (1). The amount of sand passing through the flow-through type reactor was determined by providing a cyclone at the downstream end of the flow-through type reactor and measuring the weight of the sand collected in the cyclone after completion of the abrasion test.

Wear rate (% / kg) = {[weight of catalyst before start of abrasion test (g) - weight of catalyst after completion of abrasion test / weight of catalyst before start of abrasion test] (One)

Exam conditions

Catalyst shape: Number of honeycomb holes 9x9 eyes, length 100mm

Gas flow rate: (16.5 +/- 2) m / s (catalyst cross section)

Gas temperature: room temperature 25 ° C

Gas distribution time: 3 hours

Sand concentration: (40 ± 5) g / Nm ³

Sand: Silica Average particle size 500 ㎛

[3] Heat resistance test

(101) plane peak intensity (P ¹ ) of the anatase type crystal contained in the honeycomb-shaped exhaust gas treating catalyst and the (101) surface intensity of the anatase crystal after maintaining the honeycomb type exhaust gas treating catalyst in the air at 700 ° C for 50 hours, (Peak intensity P ^{1 '} after the heat resistance test / peak intensity P ¹ before the heat resistance test), and the surface peak intensity (P ^1' ). The smaller the value of the peak intensity ratio is, the smaller the increase amount of the anatase type crystal after the heat resistance test is, and thus it can be evaluated as the exhaust gas treatment catalyst having high heat resistance.

[4] Specific surface area

Containing particulate powder or honeycomb-shaped exhaust gas treatment by means of a specific surface area measuring device (Macsorb HM model-1220, manufactured by Kabushiki Kaisha Matsutake) based on the BET method using a mixed gas of 30% nitrogen and 70% The specific surface area of the catalyst was determined.

[5] fine pore volume

The total fine pore volume of the honeycomb-shaped exhaust gas treating catalyst was determined by a mercury intrusion method using a porosimeter (Poremaster 33, manufactured by Quantachrome).

[6] X-ray diffraction

(101) plane peak intensity of anatase type crystals in titanium dioxide (MC-90, manufactured by Ishihara Sangyo Kagaku Co., Ltd.) used as a reference powder in the present invention was measured using an X-ray diffractometer (RINT1400 manufactured by Rigaku Denki Co., Ltd.) P ⁰ (measured value storage) and, respectively, measured by the (101) plane peak intensity P ¹ of the anatase type crystal of titanium oxide contained in the titanium-containing granular powder prepared by the present invention in the X-ray diffraction shown in the above, and his Peak intensity ratio (P ¹ / P ⁰ ) was obtained.

[7] Denitration test

A honeycomb type exhaust gas treating catalyst including a honeycomb structure having a honeycomb hole number of 3 × 3 eyes and a penetration direction length of 300 mm (cut out and adjusted to have other dimensions) is used as a test sample, and the test sample is introduced into a flow- . The model gas of the following composition was circulated in this flow-through reactor and the denitration rate was measured. The denitration rate of nitrogen oxides (NO _x ) in the gas before and after the catalytic contact was obtained by the following equation (2). At this time, the concentration of NO _x was measured by a chemiluminescence-type nitrogen oxide analyzer (ECL-88AO, manufactured by ANATEC Corporation, Yanaco).

Denitration rate (%) =

{[Contactless gas in the NO _X (mass ppm) - in the gas following contact NO _X (mass ppm)] / non-contact gas in the NO _X (mass ppm)} × 100 ... (2)

Exam conditions

Catalyst shape: Number of honeycomb holes 3 x 3 eyes, length 300 mm

Reaction temperature: 380 占 폚, superficial velocity (SV) = 20,000 hr ^-1

Model gas composition: NO _X = 180 mass ppm, NH ₃ = 180 mass ppm, SO ₂ = 500 mass ppm, O ₂ = 2 wt%, H ₂ O = 10 wt%, N ₂ =

[Example 1]

≪ Titanium-containing particulate powder (a) and honeycomb-shaped exhaust gas treating catalyst (A)

(1) Titanium-containing granular powder (a)

The titanium sulfate solution obtained in the production process of titanium dioxide by the sulfuric acid method was thermally hydrolyzed to obtain a metatitanic acid slurry. 23.8 kg of a metatitanic acid slurry in terms of titanium dioxide was added to a stirring tank equipped with a reflux condenser in which 15 kg of 15% by weight aqueous ammonia had been put in advance, 1.13 kg of ammonium paratungstate was further added and sufficiently stirred at 95 캜 for 1 hour . The slurry after the heat aging was cooled and taken out from the stirring tank, and the solid component was filtered and dehydrated to obtain a washing cake. The cleaning cake was dried at a temperature of 110 ° C for 20 hours and then calcined at a temperature of 550 ° C for 5 hours. As a result, the nitrogen atoms contained in the added raw materials and the like were released out of the system as ammonia. Subsequently, this calcined material was previously pulverized by a ball mill to obtain a granular powder (a ') of a composite oxide containing titanium and tungsten metal elements having a particle diameter of not less than 45 占 퐉 as a whole not less than 99.9 mass%.

Subsequently, 0.282 kg of ammonium paratungstate as an additive was added to the granular powder (a ') of the composite oxide and uniformly mixed in a blender to prepare a titanium-containing granular powder (a). The titanium-containing granular powder thus prepared was pulverized using a ball mill to obtain a titanium-containing granular powder (a) having a particle diameter of not less than 45 탆 in a total amount of not less than 99.9% by mass.

Subsequently, a value A obtained by dividing the mass of the titanium atom, which is a metal element constituting the composite oxide, contained in the thus obtained titanium-containing particulate powder (a) by the atomic weight thereof was determined, and the additive (ammonium paratungstate) The value B obtained by dividing the nitrogen atom, which is an element constituting the nitrogen atom, by the atomic amount thereof. As a result, the above-mentioned values A and B were 297 and 0.90, respectively, and the ratio (B / A) was 3.03 10 ^-3 .

When the titanium-containing granular powder (a) was measured by X-ray diffraction as described above, it was found that the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure and the (101) when the surface peak intensity to P ^1, and the reference powder (Ishihara Sangyo whether or sikki manufactured Preparation MC-90) in 101 of the anatase type crystal of titanium dioxide revealed the surface peak intensity P ^0, its peak intensity ratio (P ¹ / P ⁰ ) was 0.97. The specific surface area of the titanium-containing granular powder was measured by the above-mentioned method, and found to be 93 m ² / g.

(2) Honeycomb  The shape exhaust gas treating catalyst (A)

Subsequently, a solution obtained by dissolving 0.174 kg of ammonium metavanadate in 0.250 kg of monoethanolamine was added to 23.6 kg of the titanium-containing granular powder (a) thus obtained, followed by addition of ammonia water and water to adjust the pH of the mixed slurry Was 6 or more. Further, 1.25 kg of glass fiber (hereinafter also referred to as " GF ") as a reinforcing material and 0.500 kg of polyethylene oxide were added to the mixed slurry and heated and kneaded in a kneader to prepare a blown product suitable for extrusion molding. Subsequently, the bladder was extruded in a vacuum extrusion molding machine to obtain a sheet having an outer diameter of 75 mm, a length of about 500 mm, a diameter of 6.7 mm, a thickness of 0.75 mm, and an opening ratio of 80% A honeycomb structure was obtained. The honeycomb structure thus obtained was dried at 60 ° C for 24 hours and then calcined at 600 ° C for 3 hours to obtain a honeycomb structure having a weight composition ratio of TiO ₂ / WO ₃ / V ₂ O ₅ /GF=89.8/4.73/0.50/5.00 was prepared. The honeycomb-shaped exhaust gas treating catalyst (A)

[Example 2]

≪ Titanium-containing particulate powder (b) and honeycomb-shaped exhaust gas treating catalyst (B)

(1) Titanium-containing granular powder (b)

(B ') was prepared in the same manner as in Example 1 except that the addition amount of ammonium paratungstate was changed to 0.845 kg when preparing the granular powder (a') of the complex oxide obtained in Example 1, ).

The titanium-containing particulate powder (b) was prepared in the same manner as in Example 1 except that the amount of ammonium paratungstate added as an additive to the particulate powder (b ') of the composite oxide was changed to 0.564 kg.

Subsequently, a value A obtained by dividing the mass of the titanium atom, which is a metal element constituting the composite oxide, contained in the titanium-containing particulate powder (b) thus obtained by the atomic weight thereof was determined, and the additive (ammonium paratungstate) The value B obtained by dividing the nitrogen atom, which is an element constituting the nitrogen atom, by the atomic amount thereof. As a result, the above-mentioned values A and B were 297 and 1.80, respectively, and the ratio (B / A) thereof was 6.05 × 10 ^-3 .

When the titanium-containing particulate powder (b) was measured by X-ray diffraction as described above, it was found that the titanium oxide contained in the titanium-containing particulate powder had an anatase crystal structure and the peak intensity ratio (P ¹ / P ⁰ ) was 0.95. Further, the specific surface area of the titanium-containing granular powder was measured by the above-mentioned method and found to be 94 m ² / g.

(2) Honeycomb  The shape exhaust gas treating catalyst (B)

Subsequently, a honeycomb type exhaust gas treating catalyst (1) containing a honeycomb structured body was produced in the same manner as in Example 1 except that the titanium-containing particulate powder (b) was used in place of the titanium-containing particulate powder (B). The weight composition ratios of the metal elements contained in the honeycomb structure on the basis of oxides were TiO ₂ / WO ₃ / V ₂ O ₅ /GF = 89.8 / 4.73 / 0.5 / ₅ .

[Example 3]

≪ Titanium-containing particulate powder (c) and honeycomb-shaped exhaust gas treating catalyst (C)

(1) Titanium-containing granular powder (c)

(C ') was prepared in the same manner as in Example 1, except that the addition amount of ammonium paratungstate was changed to 0.281 kg in preparing the granular powder (a') of the complex oxide obtained in Example 1, ).

Further, a titanium-containing particulate powder (c) was prepared in the same manner as in Example 1 except that the amount of ammonium paratungstate added as an additive to the particulate powder (c ') of the composite oxide was changed to 1.13 kg.

Subsequently, a value A obtained by dividing the mass of the titanium atom, which is a metal element constituting the composite oxide, contained in the thus obtained titanium-containing particulate powder (c) by the atomic mass thereof was determined, and the additive (ammonium paratungstate) The value B obtained by dividing the nitrogen atom, which is an element constituting the nitrogen atom, by the atomic amount thereof. As a result, the above-mentioned values A and B were 297 and 3.60, respectively, and the ratio (B / A) thereof was 1.21 x 10 ^-2 .

When the titanium-containing granular powder (c) was measured by X-ray diffraction as described above, it was found that the titanium oxide contained in the titanium-containing granulated powder had an anatase type crystal structure and the peak intensity ratio (P ¹ / P ⁰ ) was 0.96. The specific surface area of the titanium-containing granular powder was measured by the above-mentioned method, and found to be 93 m ² / g.

(2) Honeycomb  The shape exhaust gas treating catalyst (C)

Subsequently, a honeycomb type exhaust gas treating catalyst (1) containing a honeycomb structured body was obtained in the same manner as in Example 1, except that the titanium-containing particulate powder (c) was used in place of the titanium- containing particulate powder (C). The weight composition ratios of the metal elements contained in the honeycomb structure on the basis of oxides were TiO ₂ / WO ₃ / V ₂ O ₅ /GF = 89.8 / 4.73 / 0.5 / ₅ .

[Example 4]

<Titanium-containing particulate powder (d) and honeycomb-shaped exhaust gas treating catalyst (D)>

(1) Titanium-containing granular powder (d)

The procedure of Example 1 was repeated except that 22.5 kg of the metatitanic acid slurry in terms of titanium dioxide and the amount of ammonium paratungstate added were changed to 1.41 kg in preparing the granular powder (a ') of the composite oxide obtained in Example 1 To obtain a particulate powder (d ') of a composite oxide.

The titanium-containing particulate powder (d) was prepared in the same manner as in Example 1 except that the amount of ammonium paratungstate added as an additive to the particulate powder (d ') of this composite oxide was changed to 1.41 kg.

Subsequently, a value A obtained by dividing the mass of the titanium atom, which is a metal element constituting the composite oxide, contained in the thus obtained titanium-containing particulate powder (d) by the atomic weight thereof was determined, and the additive (ammonium paratungstate) The value B obtained by dividing the nitrogen atom, which is an element constituting the nitrogen atom, by the atomic amount thereof. As a result, the above values A and B were 282 and 4.49, respectively, and the ratio (B / A) thereof was 1.60 x 10 ^-2 .

When the titanium-containing granular powder (d) was measured by X-ray diffraction as described above, it was found that the titanium oxide contained in the titanium-containing granulated powder had an anatase crystal structure and the peak intensity ratio (P ¹ / P ⁰ ) was 0.91. The specific surface area of the titanium-containing granular powder was measured by the above-mentioned method and found to be 88 m ² / g.

(2) Honeycomb  The shape exhaust gas treating catalyst (D)

Subsequently, a honeycomb type exhaust gas treating catalyst (1) containing a honeycomb structured body was produced in the same manner as in Example 1, except that the titanium-containing particulate powder (d) was used in place of the titanium- (D). The weight composition ratios of the metal elements contained in the honeycomb structure on the basis of oxides were TiO ₂ / WO ₃ / V ₂ O ₅ /GF = 85.1 / 9.45 / 0.5 / ₅ .

[Example 5]

&Lt; Titanium-containing particulate powder (e) and honeycomb-shaped exhaust gas treating catalyst (E)

(1) Titanium-containing granular powder (e)

The procedure of Example 1 was repeated except that 20.0 kg of the metatitanic acid slurry in terms of titanium dioxide and the amount of ammonium paratungstate added were changed to 2.81 kg in preparing the granular powder (a ') of the composite oxide obtained in Example 1 To obtain a granular powder (e ') of a composite oxide.

Further, a titanium-containing particulate powder (e) was prepared in the same manner as in Example 1 except that the amount of ammonium paratungstate added as an additive to the particulate powder (e ') of this composite oxide was changed to 2.81 kg.

Subsequently, a value A obtained by dividing the mass of the titanium atom, which is a metal element constituting the composite oxide, contained in the thus obtained titanium-containing particulate powder (e) by its atomic weight was determined, and the additive (ammonium paratungstate) The value B obtained by dividing the nitrogen atom, which is an element constituting the nitrogen atom, by the atomic amount thereof. As a result, the above-mentioned values A and B were 250 and 8.99, respectively, and the ratio (B / A) was 3.59 x 10 ^-2 .

When the titanium-containing granular powder (e) was measured by X-ray diffraction as described above, it was found that the titanium oxide contained in the titanium-containing granulated powder had an anatase type crystal structure and the peak intensity ratio (P ¹ / P ⁰ ) was 0.83. The specific surface area of the titanium-containing granular powder was measured by the above-mentioned method and found to be 76 m ² / g.

(2) Honeycomb  The shape exhaust gas treating catalyst (E)

Subsequently, a honeycomb type exhaust gas treating catalyst (1) containing a honeycomb structured body was produced in the same manner as in Example 1, except that the titanium-containing particulate powder (e) was used in place of the titanium-containing particulate powder (E). The weight composition ratios of the metal elements contained in the honeycomb structure on the basis of oxides were TiO ₂ / WO ₃ / V ₂ O ₅ /GF = 75.6 / 18.9 / 0.5 / ₅ .

[Example 6]

&Lt; Titanium-containing particulate powder (f) and honeycomb-shaped exhaust gas treating catalyst (F)

(1) Titanium-containing granular powder (f)

Containing particulate powder (f) was obtained in the same manner as in Example 1 except that the additive added to the particulate powder (a ') obtained in Example 1 was replaced by tungsten disulfide (added amount: 0.267 kg).

Subsequently, a value A obtained by dividing the mass of the titanium atom, which is a metal element constituting the composite oxide, contained in the thus obtained titanium-containing particulate powder (f) by the atomic weight thereof was determined, and the value A obtained by dividing the weight of the additive (tungsten disulfide) The value C obtained by dividing the nitrogen atom, which is an element which is an element, by the atomic amount thereof. As a result, the above-mentioned values A and C were 297 and 2.16, respectively, and the ratio (C / A) was 7.26 x ^10-3 .

When the titanium-containing granular powder (f) was measured by X-ray diffraction as described above, it was found that the titanium oxide contained in the titanium-containing granulated powder had an anatase crystal structure and the peak intensity ratio (P ¹ / P ⁰ ) was 0.95. Further, the specific surface area of the titanium-containing granular powder was measured by the above-mentioned method and found to be 94 m ² / g.

(2) Honeycomb  The shape exhaust gas treating catalyst (F)

Next, a honeycomb type exhaust gas treating catalyst (1) containing a honeycomb structured body was produced in the same manner as in Example 1, except that the titanium-containing particulate powder (f) was used in place of the titanium- containing particulate powder (F). The weight composition ratios of the metal elements contained in the honeycomb structure on the basis of oxides were TiO ₂ / WO ₃ / V ₂ O ₅ /GF = 89.8 / 4.73 / 0.5 / ₅ .

[Example 7]

&Lt; Titanium-containing particulate powder (g) and honeycomb-shaped exhaust gas treating catalyst (G)

(1) Titanium-containing granular powder (g)

(G) was obtained in the same manner as in Example 1 except that the additive added to the granular powder (b ') of the complex oxide obtained in Example 2 was replaced by tungsten disulfide (the addition amount was 0.535 kg). Subsequently, a value A obtained by dividing the mass of the titanium atom, which is a metal element constituting the composite oxide, contained in the thus obtained titanium-containing particulate powder (g) by the atomic weight thereof was determined, and the value A obtained by dividing the weight of the additive (tungsten disulfide) The value C obtained by dividing the nitrogen atom, which is an element which is an element, by the atomic amount thereof. As a result, the above-mentioned values A and C were 297 and 4.31, respectively, and the ratio (C / A) thereof was 1.45 x 10 ^-2 .

When the titanium-containing granular powder (g) was measured by X-ray diffraction as described above, it was found that the titanium oxide contained in the titanium-containing granulated powder had an anatase type crystal structure and the peak intensity ratio (P ¹ / P ⁰ ) was 0.95. Further, the specific surface area of the titanium-containing granular powder was measured by the above-mentioned method and found to be 94 m ² / g.

(2) Honeycomb  The shape exhaust gas treating catalyst (G)

Subsequently, a honeycomb type exhaust gas treating catalyst (1) containing a honeycomb structured body was obtained in the same manner as in Example 1, except that the titanium-containing particulate powder (g) was used in place of the titanium-containing particulate powder (G). The weight composition ratios of the metal elements contained in the honeycomb structure on the basis of oxides were TiO ₂ / WO ₃ / V ₂ O ₅ /GF = 89.8 / 4.73 / 0.5 / ₅ .

[Example 8]

&Lt; Titanium-containing granulated powder (h) and honeycomb-shaped exhaust gas treating catalyst (H)

(1) Titanium-containing granular powder (h)

(H) was obtained in the same manner as in Example 1 except that the additive added to the granular powder (c ') of the complex oxide obtained in Example 3 was replaced by tungsten disulfide (the addition amount was 1.07 kg). Subsequently, the value A obtained by dividing the mass of the titanium atom, which is the metal element constituting the composite oxide, contained in the thus obtained titanium-containing particulate powder (h) by the atomic weight thereof was determined, and the value A obtained by dividing the weight of the additive (tungsten disulfide) The value C obtained by dividing the nitrogen atom, which is an element which is an element, by the atomic amount thereof. As a result, the above-mentioned values A and C were 297 and 8.63, respectively, and the ratio (C / A) was 2.90 x 10 ^-2 .

When the titanium-containing granular powder (h) was measured by X-ray diffraction as described above, it was found that the titanium oxide contained in the titanium-containing granular powder had an anatase crystal structure and the peak intensity ratio (P ¹ / P ⁰ ) was 0.97. Further, the specific surface area of the titanium-containing granular powder was measured by the above-mentioned method and found to be 94 m ² / g.

(2) Honeycomb  The shape exhaust gas treating catalyst (H)

Subsequently, a honeycomb type exhaust gas treating catalyst (1) containing the honeycomb structured body was obtained in the same manner as in Example 1, except that the titanium-containing particulate powder (h) was used in place of the titanium-containing particulate powder (H). The weight composition ratios of the metal elements contained in the honeycomb structure on the basis of oxides were TiO ₂ / WO ₃ / V ₂ O ₅ /GF = 89.8 / 4.73 / 0.5 / ₅ .

[Example 9]

&Lt; Titanium-containing particulate powder (i) and honeycomb-shaped exhaust gas treating catalyst (I)

(1) Titanium-containing granular powder (i)

The titanium-containing particulate powder (i) was obtained in the same manner as in Example 1 except that the additive added to the particulate powder (a ') obtained in Example 1 was changed to tungsten hexachloride (amount of addition: 0.43 kg). Subsequently, a value A obtained by dividing the mass of the titanium atom, which is a metal element constituting the composite oxide, contained in the thus obtained titanium-containing particulate powder (i) by the atomic weight thereof was determined, and the additive (tungsten hexachloride) And a value D obtained by dividing the nitrogen atom as the constituent element by the atomic amount thereof was obtained. As a result, the above-mentioned values A and D were 297 and 6.47, respectively, and the ratio (D / A) thereof was 2.18 x 10 ^-2 .

When the titanium-containing particulate powder (i) was measured by X-ray diffraction as described above, it was found that the titanium oxide contained in the titanium-containing particulate powder had an anatase crystal structure and the peak intensity ratio (P ¹ / P ⁰ ) was 0.97. The specific surface area of the titanium-containing granular powder was measured by the above-mentioned method and found to be 91 m ² / g.

(2) Honeycomb  The shape exhaust gas treating catalyst (I)

Next, a honeycomb type exhaust gas treating catalyst (1) containing a honeycomb structured body was produced in the same manner as in Example 1, except that the titanium-containing particulate powder (i) was used in place of the titanium- (I). The weight composition ratios of the metal elements contained in the honeycomb structure on the basis of oxides were TiO ₂ / WO ₃ / V ₂ O ₅ /GF = 89.8 / 4.73 / 0.5 / ₅ .

[Example 10]

&Lt; Titanium-containing particulate powder (j) and honeycomb-shaped exhaust gas treating catalyst (J)

(1) Titanium-containing granular powder (j)

(J) was obtained in the same manner as in Example 1 except that the additive added to the particulate powder (b ') of the complex oxide obtained in Example 2 was replaced by tungsten hexachloride (the addition amount was 0.86 kg). Subsequently, a value A obtained by dividing the mass of the titanium atom, which is a metal element constituting the composite oxide, contained in the thus obtained titanium-containing particulate powder (j) by its atomic weight was determined, and the additive (tungsten hexachloride) And a value D obtained by dividing the nitrogen atom as the constituent element by the atomic amount thereof was obtained. As a result, the above-mentioned values A and D were 297 and 12.9, respectively, and the ratio (D / A) thereof was 4.35 × 10 ^-2 .

When the titanium-containing granular powder (j) was measured by X-ray diffraction as described above, it was found that the titanium oxide contained in the titanium-containing granulated powder had an anatase type crystal structure and the peak intensity ratio (P ¹ / P ⁰ ) was 0.96. The specific surface area of the titanium-containing granular powder was measured by the above-mentioned method, and found to be 92 m ² / g.

(2) Honeycomb  The shape exhaust gas treating catalyst (J)

Next, a honeycomb type exhaust gas treating catalyst (1) containing a honeycomb structure was produced in the same manner as in Example 1, except that the titanium-containing particulate powder (j) was used in place of the titanium-containing particulate powder (J). The weight composition ratios of the metal elements contained in the honeycomb structure on the basis of oxides were TiO ₂ / WO ₃ / V ₂ O ₅ /GF = 89.8 / 4.73 / 0.5 / ₅ .

[Example 11]

<Titanium-containing particulate powder (k) and honeycomb-shaped exhaust gas treating catalyst (K)>

(1) The titanium-containing granular powder (k)

(K) was obtained in the same manner as in Example 1 except that the additive added to the granular powder (c ') of the complex oxide obtained in Example 3 was changed to tungsten hexachloride (the amount of addition was 1.71 kg). Subsequently, a value A obtained by dividing the mass of the titanium atom, which is a metal element constituting the composite oxide, contained in the thus obtained titanium-containing particulate powder (k) by its atomic weight was determined, and the additive (tungsten hexachloride) And a value D obtained by dividing the nitrogen atom as the constituent element by the atomic amount thereof was obtained. As a result, the above-mentioned values A and D were 297 and 25.9, respectively, and the ratio (D / A) thereof was 8.71 × 10 ^-2 .

When the titanium-containing granular powder (k) was measured by X-ray diffraction as described above, it was found that the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure and the peak intensity ratio (P ¹ / P ⁰ ) was 0.95. Further, the specific surface area of the titanium-containing granular powder was measured by the above-mentioned method and found to be 94 m ² / g.

(2) Honeycomb  The shape exhaust gas treating catalyst (K)

Subsequently, a honeycomb type exhaust gas treating catalyst (hereinafter referred to as a &quot; honeycomb type exhaust gas treating catalyst &quot;) including a honeycomb structure was produced in the same manner as in Example 1 except that the titanium- containing particulate powder (k) was used in place of the titanium- K). The weight composition ratios of the metal elements contained in the honeycomb structure on the basis of oxides were TiO ₂ / WO ₃ / V ₂ O ₅ /GF = 89.8 / 4.73 / 0.5 / ₅ .

[Example 12]

&Lt; Titanium-containing particulate powder (1) and honeycomb-shaped exhaust gas treating catalyst (L)

(1) The titanium-containing granular powder (l)

A particulate titanium-containing particulate powder (1) was obtained in the same manner as in Example 1 except that the additive added to the particulate powder (b ') of the composite oxide obtained in Example 2 was changed to ammonium molybdate (amount of addition: 0.613 kg). Subsequently, a value A obtained by dividing the mass of the titanium atom, which is a metal element constituting the composite oxide, contained in the thus obtained titanium-containing particulate powder (1) by its atomic weight was determined, and the additive (ammonium molybdate) The value B obtained by dividing the nitrogen atom as the constituent element by the atomic amount thereof was obtained. As a result, the above-mentioned values A and B were 297 and 2.98, respectively, and the ratio (B / A) thereof was 1.00 x 10 ^-2 .

When the titanium-containing granular powder (1) was measured by X-ray diffraction as described above, it was found that the titanium oxide contained in the titanium-containing granulated powder had an anatase type crystal structure and the peak intensity ratio (P ¹ / P ⁰ ) was 0.98. The specific surface area of the titanium-containing granular powder was measured by the above-mentioned method, and found to be 93 m ² / g.

(2) Honeycomb  The shape exhaust gas treating catalyst (L)

Subsequently, a honeycomb type exhaust gas treating catalyst (1) was obtained in the same manner as in Example 1, except that the titanium-containing particulate powder (1) was used instead of the titanium-containing particulate powder (a) L). The weight composition ratios of the metal elements contained in the honeycomb structure on the basis of oxides were TiO ₂ / WO ₃ / MoO ₃ / V ₂ O ₅ /GF = 89.8 / 2.84 / 1.89 / 0.500 / 5.00.

[Example 13]

<Titanium-containing particulate powder (m) and honeycomb-shaped exhaust gas treating catalyst (M)>

(1) Titanium-containing granular powder (m)

(M) was obtained in the same manner as in Example 1 except that the additive added to the granular powder (b ') of the composite oxide obtained in Example 2 was changed to molybdenum disulfide (the addition amount was 0.562 kg). Subsequently, a value A obtained by dividing the mass of the titanium atom, which is a metal element constituting the composite oxide, contained in the thus obtained titanium-containing particulate powder (m) by its atomic weight was determined, and further, the above additive (molybdenum disulfide) The value C obtained by dividing the nitrogen atom, which is an element which is an element, by the atomic amount thereof. As a result, the above-mentioned values A and C were 297 and 6.95, respectively, and the ratio (C / A) thereof was 2.34 x 10 ^-2 .

The titanium-containing granular powder (m) was measured by X-ray diffraction as described above, and it was found that the titanium oxide contained in the titanium-containing granulated powder had an anatase type crystal structure and the peak intensity ratio (P ¹ / P ⁰ ) was 0.97. The specific surface area of the titanium-containing granular powder was measured by the above-mentioned method, and found to be 92 m ² / g.

(2) Honeycomb  The shape exhaust gas treating catalyst (M)

Subsequently, a honeycomb type exhaust gas treating catalyst (1) containing a honeycomb structured body was obtained in the same manner as in Example 1 except that the titanium-containing particulate powder (m) was used in place of the titanium-containing particulate powder (M). The weight composition ratios of the metal elements contained in the honeycomb structure on the basis of oxides were TiO ₂ / WO ₃ / MoO ₃ / V ₂ O ₅ /GF = 89.8 / 2.84 / 1.89 / 0.500 / 5.00.

[Example 14]

&Lt; Titanium-containing particulate powder (n) and honeycomb-shaped exhaust gas treating catalyst (N)

(1) The titanium-containing granular powder (n)

(N) was obtained in the same manner as in Example 1 except that the additive added to the granular powder (b ') of the complex oxide obtained in Example 2 was changed to molybdenum contaminated (added amount: 0.951 kg). Subsequently, a value A obtained by dividing the mass of the titanium atom, which is a metal element constituting the composite oxide, contained in the thus obtained titanium-containing particulate powder (n) by its atomic weight was determined, and the additive (molybdenum contaminated) And a value D obtained by dividing the nitrogen atom as the constituent element by the atomic amount thereof was obtained. As a result, the above-mentioned values A and D were 297 and 17.4, respectively, and the ratio (D / A) thereof was 5.84 × 10 ^-2 .

When the titanium-containing granular powder (n) was measured by X-ray diffraction as described above, it was found that the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure and the peak intensity ratio (P ¹ / P ⁰ ) was 0.98. The specific surface area of the titanium-containing granular powder was measured by the above-mentioned method, and found to be 92 m ² / g.

(2) Honeycomb  The shape exhaust gas treating catalyst (N)

Subsequently, a honeycomb type exhaust gas treating catalyst (1) containing a honeycomb structured body was produced in the same manner as in Example 1, except that the titanium-containing particulate powder (n) was used in place of the titanium- containing particulate powder (N). The weight composition ratios of the metal elements contained in the honeycomb structure on the basis of oxides were TiO ₂ / WO ₃ / MoO ₃ / V ₂ O ₅ /GF = 89.8 / 2.84 / 1.89 / 0.500 / 5.00.

[Example 15]

<Titanium-containing particulate powder (o) and honeycomb-shaped exhaust gas treating catalyst (O)>

(1) Titanium-containing granular powder (o)

(O) was obtained in the same manner as in Example 1 except that the additive added to the particulate powder (d ') of the composite oxide obtained in Example 4 was changed to ammonium molybdate (addition amount 1.53 kg). Subsequently, a value A obtained by dividing the mass of the titanium atom, which is a metal element constituting the composite oxide, contained in the thus obtained titanium-containing particulate powder (o) by its atomic weight was determined, and the additive (ammonium molybdate) The value B obtained by dividing the nitrogen atom as the constituent element by the atomic amount thereof was obtained. As a result, the above values A and B were 282 and 7.45, respectively, and the ratio (B / A) thereof was 2.64 x 10 ^-2 .

When the titanium-containing granular powder (o) was measured by X-ray diffraction as described above, it was found that the titanium oxide contained in the titanium-containing granular powder had an anatase crystal structure and the peak intensity ratio (P ¹ / P ⁰ ) was 0.90. The specific surface area of the titanium-containing particulate powder was measured by the above-mentioned method and found to be 85 m ² / g.

(2) Honeycomb  The shape exhaust gas treating catalyst (O)

Next, a honeycomb type exhaust gas treating catalyst (1) containing a honeycomb structured body was obtained in the same manner as in Example 1, except that the titanium-containing particulate powder (o) was used in place of the titanium-containing particulate powder (O). The weight composition ratios of the metal elements contained in the honeycomb structure on the basis of oxides were TiO ₂ / WO ₃ / MoO ₃ / V ₂ O ₅ /GF = 85.1 / 4.73 / 4.73 / 0.500 / 5.00.

[Example 16]

<Titanium-containing granulated powder (p) and honeycomb-shaped exhaust gas treating catalyst (P)>

(1) The titanium-containing granular powder (p)

(P) was obtained in the same manner as in Example 1, except that the additive added to the particulate powder (e ') of the complex oxide obtained in Example 5 was changed to ammonium molybdate (amount of addition: 3.07 kg). Subsequently, a value A obtained by dividing the mass of the titanium atom, which is a metal element constituting the composite oxide, contained in the thus obtained titanium-containing particulate powder (p) by its atomic weight was determined, and the additive (ammonium molybdate) The value B obtained by dividing the nitrogen atom as the constituent element by the atomic amount thereof was obtained. As a result, the above-mentioned values A and B were 250 and 14.9, respectively, and the ratio (B / A) was 5.95 × 10 ^-2 .

When the titanium-containing granular powder (p) was measured by X-ray diffraction as described above, it was found that the titanium oxide contained in the titanium-containing granular powder had an anatase crystal structure and the peak intensity ratio (P ¹ / P ⁰ ) was 0.83. The specific surface area of the titanium-containing particulate powder was measured by the above-mentioned method, and found to be 78 m ² / g.

(2) Honeycomb  The shape exhaust gas treating catalyst (P)

Subsequently, a honeycomb type exhaust gas treating catalyst (1) containing a honeycomb structured body was produced in the same manner as in Example 1 except that the titanium-containing particulate powder (p) was used in place of the titanium- containing particulate powder (P). The weight composition ratios of the metal elements contained in the honeycomb structure on the basis of oxides were TiO ₂ / WO ₃ / MoO ₃ / V ₂ O ₅ /GF = 75.6 / 9.45 / 9.45/0.500/5.00.

[Comparative Example 1]

&Lt; Particulate powder (q) of complex oxide and honeycomb-shaped exhaust gas treating catalyst (Q)

(1) Particulate phase of composite oxide Powder (q)

The composite oxide (a ') obtained in Example 1 was produced in the same manner as in Example 1 except that 23.6 kg of the metatitanic acid slurry in terms of titanium dioxide and the addition amount of ammonium paratungstate were changed to 1.41 kg, A granular powder (q) of the composite oxide was obtained in the same manner as in the preparation of the granular powder (a ').

The titanium oxide contained in the granular powder of the composite oxide had an anatase crystal structure and the peak intensity ratio (P ¹ (P ¹ )) of the composite oxide was measured by X-ray diffraction as described above, / P ⁰ ) was 0.97. The specific surface area of the particulate powder of the composite oxide was measured by the above-mentioned method and found to be 92 m ² / g.

(2) Honeycomb  The shape exhaust gas treating catalyst (Q)

Subsequently, honeycomb-shaped exhaust gas treatment including the honeycomb structured body was carried out in the same manner as in Example 1, except that the particulate powder (q) of the composite oxide was used in place of the titanium-containing particulate powder (a) Catalyst (Q) was prepared. The weight composition ratios of the metal elements contained in the honeycomb structure on the basis of oxides were TiO ₂ / WO ₃ / V ₂ O ₅ /GF = 89.8 / 4.73 / 0.5 / ₅ .

[Comparative Example 2]

&Lt; Particulate powder (r) of titanium dioxide and ammonium paratungstate and honeycomb-shaped exhaust gas treating catalyst (R) >

(1) titanium dioxide and Of ammonium paratungstate  standing statue Powder (r)

(R ') of titanium dioxide was prepared in the same manner as in (a') of Example 1, except that ammonium metatitanate slurry (25.0 kg in terms of titanium dioxide) was not added with ammonium paratungstate. Subsequently, 1.41 kg of ammonium paratungstate was added to the particulate powder of titanium dioxide (r ') and mixed uniformly in a blender to prepare a particulate powder (r) of titanium dioxide and ammonium paratungstate. The granular powder of the titanium dioxide and the ammonium paratungstate thus prepared was pulverized using a ball mill, and 99.9 mass% or more of the total amount of the particles was dispersed in a granular powder of ruthenium dioxide and ammonium paratungstate having a particle diameter of 45 탆 or less ).

Subsequently, a value A obtained by dividing the mass of the titanium atom, which is a metal element constituting the composite oxide, contained in the granular powder (r) of the titanium dioxide and ammonium paratungstate thus obtained by the atomic weight thereof was determined, (Ammonium paratungstate) was divided by its atomic weight to obtain a value B obtained by dividing the nitrogen atom, which is an element constituting the element (ammonium paratungstate). As a result, the above-mentioned values A and B were 297 and 4.49, respectively, and the ratio (B / A) thereof was 1.51 x 10 ^-2 .

When the titanium dioxide and the titanium paratungstate particulate powder (r) were measured by X-ray diffraction as described above, it was found that the titanium oxide contained in the particulate powder of the titanium dioxide and ammonium paratungstate was anatase type crystal structure , And the peak intensity ratio (P ¹ / P ⁰ ) was 0.97. The specific surface area of the particulate powder of titanium dioxide and ammonium paratungstate was measured by the above-mentioned method and found to be 95 m ² / g.

(2) Honeycomb  The shape exhaust gas treating catalyst (R)

Subsequently, a honeycomb structure including the honeycomb structured body was obtained in the same manner as in Example 1, except that the particulate powder (r) of titanium and ammonium paratungstate was used in place of the titanium-containing particulate powder (a) Shaped exhaust gas treating catalyst (R). The weight composition ratios of the metal elements contained in the honeycomb structure on the basis of oxides were TiO ₂ / WO ₃ / V ₂ O ₅ /GF = 89.8 / 4.73 / 0.5 / ₅ .

[Comparative Example 3]

&Lt; Particulate powder (s) of complex oxide and honeycomb-shaped exhaust gas treating catalyst (S) >

(1) Particulate phase of composite oxide Powder (s)

(D ') of the complex oxide of Example 4 except that the addition amount of ammonium paratungstate was changed to 2.81 kg when the granular powder (d') of the composite oxide obtained in Example 4 was produced To obtain a granular powder (s) of a composite oxide.

The titanium oxide contained in the granular powder of the composite oxide had an anatase crystal structure and the peak intensity ratio (P ¹ (P ¹ )) was measured by X-ray diffraction as described above, / P ⁰ ) was 0.97. The specific surface area of the particulate powder of the composite oxide was measured by the above-mentioned method and found to be 92 m ² / g.

(2) Honeycomb  The shape exhaust gas treating catalyst (S)

Subsequently, honeycomb-shaped exhaust gas treatment including the honeycomb structured body was carried out in the same manner as in Example 1, except that the particulate powder (s) of the composite oxide was used in place of the titanium-containing particulate powder (a) To prepare a catalyst (S). The weight composition ratios of the metal elements contained in the honeycomb structure on the basis of oxides were TiO ₂ / WO ₃ / V ₂ O ₅ /GF = 85.1 / 9.45 / 0.5 / ₅ .

[Comparative Example 4]

<Particulate Powder (t) of Titanium Dioxide and Ammonium Paratungstate and Honeycomb-like Exhaust Gas Treatment Catalyst (T)>

(1) titanium dioxide and Of ammonium paratungstate  standing statue Powder (t)

The same procedure as in Comparative Example 2 was carried out except that 22.5 kg of the particulate powder (r) of the titanium dioxide and the ammonium paratungstate of Comparative Example 2 were mixed with ammonium paratungstate (2.81 kg) to prepare a mixture of titanium and ammonium paratungstate To thereby obtain a granular powder (t).

Subsequently, a value A obtained by dividing the mass of the titanium atom, which is a metal element constituting the composite oxide, contained in the particulate powder (t) of the titanium and ammonium paratungstate thus obtained by its atomic weight was determined, and the additive And a value B obtained by dividing the nitrogen atom, which is an element constituting ammonium tungstate (ammonium paratungstate), by the atomic amount thereof. As a result, the above values A and B were 282 and 8.99, respectively, and the ratio (B / A) was 3.19 x 10 ^-2 .

When the titanium dioxide and the titanium paratungstate particulate powder (t) were measured by X-ray diffraction as described above, it was found that the titanium oxide contained in the particulate powder of the titanium dioxide and the ammonium paratungstate was anatase type crystal structure , And the peak intensity ratio (P ¹ / P ⁰ ) was 0.92. The specific surface area of the particulate powder of titanium dioxide and ammonium paratungstate was measured by the above method and found to be 85 m ² / g.

(2) Honeycomb  Shaped exhaust gas treatment catalyst (T)

Subsequently, except that the particulate powder (t) of titanium dioxide and ammonium paratungstate was used in place of the titanium-containing particulate powder (a) described in Example 1, a honeycomb structured body A honeycomb-shaped exhaust gas treating catalyst (T) was produced. The weight composition ratios of the metal elements contained in the honeycomb structure on the basis of oxides were TiO ₂ / WO ₃ / V ₂ O ₅ /GF = 85.1 / 9.45 / 0.5 / ₅ .

[Comparative Example 5]

&Lt; Particulate powder (u) of complex oxide and honeycomb-shaped exhaust gas treating catalyst (U)

(1) Particulate phase of composite oxide Powder (u)

(E ') of the composite oxide of Example 5 was obtained in the same manner as in the granular powder (e') of Example 5 except that the addition amount of ammonium paratungstate was changed to 5.63 kg when the granular powder (e ') of the composite oxide obtained in Example 5 was produced To obtain a granular powder (u) of a composite oxide.

When the titanium oxide contained in the granular powder of the composite oxide had an anatase crystal structure and the peak intensity ratio (P ¹ (P ¹ )) was measured by X-ray diffraction as described above, / P ⁰ ) was 0.86. The specific surface area of the particulate powder of the composite oxide was measured by the above method, and found to be 79 m ² / g.

(2) Honeycomb  The shape exhaust gas treating catalyst (U)

Subsequently, honeycomb-shaped exhaust gas treatment including the honeycomb structured body was carried out in the same manner as in Example 1, except that the particulate powder (u) of the composite oxide was used in place of the titanium-containing particulate powder (a) To prepare a catalyst (U). The weight composition ratios of the metal elements contained in the honeycomb structure on the basis of oxides were TiO ₂ / WO ₃ / V ₂ O ₅ /GF = 75.6 / 18.9 / 0.5 / ₅ .

[Comparative Example 6]

&Lt; Particulate Powder (v) of Titanium Dioxide and Ammonium Paratungstate and Honeycomb-like Exhaust Gas Treatment Catalyst (V) >

(1) titanium dioxide and Of ammonium paratungstate  standing statue Powder (v)

The same procedure as in Comparative Example 2 was carried out except that 20.0 kg of the particulate powder (r) of the titanium dioxide and the ammonium paratungstate of Comparative Example 2 were mixed with ammonium paratungstate (5.63 kg), and titanium dioxide and paratungstic acid To obtain a granular powder (v) of ammonium.

Subsequently, a value A obtained by dividing the mass of the titanium atom, which is a metal element constituting the composite oxide, contained in the particulate powder (v) of titanium dioxide and ammonium paratungstate thus obtained by the atomic weight thereof was determined, (Ammonium paratungstate) was divided by its atomic weight to obtain a value B obtained by dividing the nitrogen atom, which is an element constituting the element (ammonium paratungstate). As a result, the above values A and B were 250 and 18.0, respectively, and the ratio (B / A) was 7.18 x 10 ^-2 .

When the titanium dioxide and the paratungstic acid ammonium particulate powder (v) were measured by X-ray diffraction as described above, it was found that the titanium oxide contained in the particulate powder of the titanium dioxide and the ammonium paratungstate was anatase type crystal structure , And the peak intensity ratio (P ¹ / P ⁰ ) was 0.80. The specific surface area of the particulate powder of the titanium dioxide and the ammonium paratungstate was measured by the above method and found to be 75 m ² / g.

(2) Honeycomb  The shape exhaust gas treating catalyst (V)

Subsequently, honeycomb including the honeycomb structured body was obtained in the same manner as in Example 1, except that the particulate powder (v) of titanium and ammonium paratungstate was used in place of the titanium-containing particulate powder (a) Shaped exhaust gas treating catalyst (V). The weight composition ratios of the metal elements contained in the honeycomb structure on the basis of oxides were TiO ₂ / WO ₃ / V ₂ O ₅ /GF = 75.6/18.9/0.50/5.00.

[Comparative Example 7]

&Lt; Particulate powder (w) of complex oxide and honeycomb-shaped exhaust gas treating catalyst (W)

(1) Particulate phase of composite oxide Powder (w)

(B ') of the complex oxide of Example 2, except that 0.61 kg of ammonium molybdate was added simultaneously with the ammonium paratungstate when the granular powder (b') of the complex oxide obtained in Example 2 was produced To obtain a granular powder (w) of a composite oxide.

The titanium oxide contained in the granular powder of the composite oxide had an anatase crystal structure and the peak intensity ratio (P ¹ (P ¹ )) of the composite oxide was measured by X-ray diffraction as described above, / P ⁰ ) was 0.98. The specific surface area of the particulate powder of the composite oxide was measured by the above-mentioned method and found to be 94 m ² / g.

(2) Honeycomb  The shape exhaust gas treating catalyst (W)

Subsequently, honeycomb-like exhaust gas treatment including the honeycomb structured body was carried out in the same manner as in Example 1, except that the particulate powder (w) of the composite oxide was used in place of the titanium-containing particulate powder (a) To prepare a catalyst (W). The weight composition ratios of the metal elements contained in the honeycomb structure on the basis of oxides were TiO ₂ / WO ₃ / MoO ₃ / V ₂ O ₅ /GF = 89.8 / 2.84 / 1.89 / 0.500 / 5.00.

[Comparative Example 8]

&Lt; Particulate powder (x) of complex oxide and honeycomb-shaped exhaust gas treating catalyst (X)

(1) Particulate phase of composite oxide Powder (x)

(D ') of the composite oxide of Example 4, except that 1.53 kg of ammonium molybdate was added simultaneously with the ammonium paratungstate when the granular powder (d') of the composite oxide obtained in Example 4 was produced To obtain a particulate powder (x) of a composite oxide.

When the titanium oxide contained in the granular powder of the composite oxide had an anatase crystal structure and the peak intensity ratio (P ¹ (x)) of the composite oxide was measured by X-ray diffraction as described above, / P ⁰ ) was 0.95. The specific surface area of the particulate powder of the composite oxide was measured by the above-mentioned method and found to be 86 m ² / g.

(2) Honeycomb  The shape exhaust gas treating catalyst (X)

Subsequently, honeycomb-shaped exhaust gas treatment including the honeycomb structured body was carried out in the same manner as in Example 1, except that the particulate powder (x) of the composite oxide was used in place of the titanium-containing particulate powder (a) Catalyst (X) was prepared. The weight composition ratios of the metal elements contained in the honeycomb structure on the basis of oxides were TiO ₂ / WO ₃ / MoO ₃ / V ₂ O ₅ /GF = 89.8 / 2.84 / 1.89 / 0.500 / 5.00.

[Comparative Example 9]

&Lt; Particulate powder (y) of complex oxide and honeycomb-shaped exhaust gas treating catalyst (Y)

(1) Particulate phase of composite oxide Powder (y)

(E ') of the composite oxide of Example 5, except that 3.07 kg of ammonium molybdate was added simultaneously with ammonium paratungstate in the preparation of the granular powder (e') of the composite oxide obtained in Example 5 To obtain a particulate powder (y) of a composite oxide.

When the titanium oxide contained in the granular powder of the composite oxide had an anatase crystal structure and the peak intensity ratio (P ¹ (x)) of the composite oxide was measured by X-ray diffraction as described above, / P ⁰ ) was 0.87. The specific surface area of the particulate powder of the composite oxide was measured by the above-mentioned method and found to be 77 m ² / g.

(2) Honeycomb  The shape exhaust gas treating catalyst (Y)

Subsequently, a honeycomb type exhaust gas treating catalyst (1) containing a honeycomb structured body was obtained in the same manner as in Example 1, except that the particulate powder (y) of the composite oxide was used in place of the titanium-containing particulate powder (Y). The weight composition ratios of the metal elements contained in the honeycomb structure on the basis of oxides were TiO ₂ / WO ₃ / MoO ₃ / V ₂ O ₅ /GF = 75.6 / 9.45 / 9.45/0.500/5.00.

[Comparative Example 10]

&Lt; Titanium-containing particulate powder (z) and honeycomb-shaped exhaust gas treating catalyst (Z)

(1) The titanium-containing granular powder (z)

The procedure of Example 1 was repeated except that 15.0 kg of the metatitanic acid slurry in terms of titanium dioxide and the amount of ammonium paratungstate added were changed to 0.845 kg in preparing the granular powder (a ') of the complex oxide obtained in Example 1 To obtain a granular powder (z ') of the composite oxide.

The titanium-containing particulate powder (z) was prepared in the same manner as in Example 1 except that 11.3 kg of ammonium molybdate was used as an additive to be added to the particulate powder (z ') of the composite oxide.

Subsequently, a value A obtained by dividing the mass of the titanium atom, which is a metallic element constituting the composite oxide, contained in the thus obtained titanium-containing particulate powder (z) by its atomic weight was determined, and the additive (ammonium molybdate) The value B obtained by dividing the nitrogen atom as the constituent element by the atomic amount thereof was obtained. As a result, the above-mentioned values A and B were 188 and 55.1, respectively, and the ratio (B / A) thereof was 2.93 × 10 ^-1 .

The titanium oxide contained in the granular powder of the complex oxide had an anatase crystal structure and the peak intensity ratio (P ¹ (z)) of the composite oxide was measured by X-ray diffraction as described above, / P ⁰ ) was 0.75. The specific surface area of the particulate powder of the composite oxide was measured by the above method and found to be 70 m ² / g.

(2) Honeycomb  The shape exhaust gas treating catalyst (Z)

Subsequently, a honeycomb type exhaust gas treating catalyst (1) containing a honeycomb structured body was obtained in the same manner as in Example 1, except that the titanium-containing particulate powder (z) was used in place of the titanium-containing particulate powder (Z). The weight composition ratios of the metal elements contained in the honeycomb structure on the basis of oxides were TiO ₂ / WO ₃ / MoO ₃ / V ₂ O ₅ /GF = 56.7 / 2.84 / 35.0/0.500/5.00.

The values of the above A to F relating to the titanium-containing granular powder, the composite oxide, and the mixture of the titanium powder and the ammonium paratungstate (hereinafter collectively referred to as &quot; titanium-containing granular powder &quot; 1, the specific surface area SA of the titanium-containing particulate powder (a) to (z), the peak intensity ratio (P ¹ / P ⁰ ) of the anatase type crystal surface (101), the honeycomb- (101) face peak intensity ratio (P ^{1 '} ) of the anatase type crystal before and after the test (A 1) to (Z), the fine pore volume (PV), the moldability test result, the denitration rate, / P ¹ ) are shown in Table 2.

The results shown in Table 2 show that the titanium-containing granulated powders (a) to (p) according to the examples and the composite of titanium and tungsten used as the raw materials of the titanium-containing granular powders (q) to (z) The specific surface area (SA) of the oxide is 70 to 95 m ² / g, all of which are in the range of 40 to 300 m ² / g. The titanium-containing granular powder has a peak intensity ratio (P ¹ / P ⁰ ) of (101) plane of the anatase type crystal to the reference powder of titanium dioxide within the range of 0.75 to 0.98, all within the range of 0.30 to 1.3 have.

The honeycomb type exhaust gas treating catalysts (A) to (P) relating to Examples 1 to 16 were produced using these titanium-containing particulate powders (a) to (p) as raw materials. Among the twenty, the honeycomb structure was the tenth or the fastest, and in Examples 2 to 5, 15 and 16, the honeycomb defect did not occur. Examples 1 to 3 in which the addition amount of ammonium paratungstate was changed, Examples 4 and 5 and Examples 15 and 16 in which both of the content of titanium and the amount of additive were changed were changed, and the content of tungsten disulfide in Example 6 (Or C / A, D / A) of each of Examples 9 to 11, in which the addition amount of tungsten hexachloride was changed, the honeycomb defect was less likely to occur Tendency.

On the other hand, all of the denitration rate, wear rate and heat resistance of the honeycomb-shaped exhaust gas treating catalyst were found to be practically free from problems. As to the evaluation items, the larger the value of B / A (or C / A, D / A) is, the more the abrasion strength is improved and the heat resistance is lowered.

On the other hand, the honeycomb-shaped exhaust gas treating catalysts of Comparative Examples 1, 3, 5, and 7 to 9 using composite oxides (q), (s), (u) , Honeycomb defects occurred in the honeycomb structure at the early stage of the fourth to ninth. Thus, it was confirmed that when additives of tungsten compound or molybdenum compound were added to the composite oxide, the effect of improving the moldability in extrusion molding was obtained.

The honeycomb-shaped exhaust gas treating catalysts of Comparative Examples 2, 4 and 6 in which a mixture of titanium dioxide (r), (t) and (v) The honeycomb defect did not occur in the molding test, and the moldability at the time of extrusion molding was good, but the heat resistance was lower than those of the other examples and the comparative example. In this respect, by adding an additive of a nitrogen compound, a sulfur compound and a chlorine compound containing tungsten or molybdenum to a composite oxide containing tungsten or molybdenum, it is possible to provide a honeycomb structure having good moldability during extrusion molding, An exhaust gas treating catalyst was obtained.

In addition, in the results of Comparative Example 10 in which the B / A value was 6.34 x 10 ^-1 and the B / A value greatly exceeded the upper limit value (2.78 x 10 ^-1 ), honeycomb defect occurred in 20 extrusion molding tests , The moldability at the time of extrusion molding was good, but the test result that the denitration rate and the heat resistance were the lowest was obtained.

Claims (12)

(I) a tungsten-containing nitrogen compound, (ii) a tungsten-containing sulfur compound, (iii) a tungsten-containing chlorine compound, (iv) a molybdenum-containing tungsten compound containing at least one of tungsten and molybdenum, Containing particulate powder for producing a honeycomb-shaped exhaust gas treating catalyst comprising an additive (Y) selected from a nitrogen compound, (v) a sulfur compound containing molybdenum and (vi) a molybdenum-containing chlorine compound,
(1) When the additive (Y) contains (i) a tungsten-containing nitrogen compound or (iv) a molybdenum-containing nitrogen compound, the number of moles of titanium atoms contained in the titanium- Containing granular powder has a molar ratio (B / A) in the range of 8.70 x 10 &lt; ^-4 &gt; to 2.78 x 10 &lt; ^-1 &
(2) When the additive (Y) contains (ii) a sulfur-containing tungsten compound or (v) a sulfur compound containing molybdenum, the number of moles of titanium atoms contained in the titanium- Containing granular powder is represented by C, the molar ratio (C / A) thereof is in the range of 6.96 × 10 ^-3 to 5.55 × 10 ^-1 ,
(3) When the additive (Y) contains (iii) a tungsten-containing chlorine compound or (vi) a molybdenum-containing chlorine compound, the number of moles of titanium atoms contained in the titanium- Containing granular powder is represented by D, the molar ratio (D / A) of the chlorine atom contained in the granular powder is in the range of 6.96 x 10 ^-3 to 6.94 x 10 ^-1
Wherein the titanium-containing granular powder for producing a honeycomb-shaped exhaust gas treating catalyst is a titanium-containing granular powder. The method of producing a titanium-containing granular powder according to claim 1, wherein the titanium-containing granular powder has an anatase-type crystal structure as measured by X-ray diffraction, wherein the titanium oxide contained in the titanium-containing granular powder has an anatase- when in P ^1, and the reference powder (Ishihara Sangyo whether or sikki manufactured Preparation MC-90) in 101 of the anatase type crystal of titanium dioxide revealed the surface peak intensity P ^0, ratio (P ¹ / P his peak intensity ⁰ ) is in the range of 0.30 to 1.3,
The titanium-containing particulate powder for producing a honeycomb-shaped exhaust gas treating catalyst according to claim ¹ , wherein the specific surface area of the titanium-containing particulate powder is in the range of 40 to 300 m ² / g. The titanium-containing granular powder for producing a honeycomb-shaped exhaust gas treating catalyst according to claim 1, wherein the titanium-containing granular powder is a particulate material having a particle diameter of not less than 45 탆 in a total amount of not less than 99.9% by weight. The method according to claim 1, wherein the (i) tungsten-containing nitrogen compound is at least one member selected from the group consisting of ammonium paratungstate, ammonium metatungstate, ammonium tungstate and ammonium tetratothiotungstate, Is at least one member selected from the group consisting of ammonium molybdate, ammonium phosphomolybdate and ammonium tetrathiomolybdate. The titanium-containing granular powder for producing a honeycomb-shaped exhaust gas treating catalyst according to claim 1, wherein (ii) the tungsten-containing sulfur compound is tungsten disulfide, and (v) the molybdenum-containing sulfur compound is molybdenum disulfide. The titanium-containing granular powder for producing a honeycomb-shaped exhaust gas treating catalyst according to claim 1, wherein (iii) the tungsten-containing chlorine compound is tungsten hexachloride, and (vi) the molybdenum-containing chlorine compound is molybdenum contaminated. A honeycomb-shaped exhaust gas treating catalyst comprising the titanium-containing particulate powder according to claim 1 and an active ingredient, wherein the content of the titanium-containing particulate powder is 60% by weight or more. The honeycomb-type exhaust gas treatment catalyst according to claim 7, wherein the active component is vanadium oxide. The honeycomb-shaped exhaust gas treating catalyst according to claim 7, wherein the honeycomb-shaped exhaust gas treating catalyst is a nitrogen oxide removing catalyst. (I) a tungsten-containing nitrogen compound, (ii) a tungsten-containing sulfur compound, (iii) a tungsten-containing chlorine compound, (iv) a molybdenum-containing tungsten compound containing at least one of tungsten and molybdenum, Containing granular powder for producing a honeycomb-shaped exhaust gas treating catalyst, which comprises the step of mixing the additives (Y) selected from nitrogen compounds, (v) sulfur compounds containing molybdenum and (vi) molybdenum- / RTI &gt;
(1) In the case where (i) a tungsten-containing nitrogen compound or (iv) a molybdenum-containing nitrogen compound is used as the additive (Y), the number of moles of titanium atoms contained in the titanium- (B / A) of 8.70 x 10 &lt; ^-4 &gt; to 2.78 x 10 &lt; ^-1 &gt; when the number of moles of nitrogen atoms contained in the granular powder Comprising:
(2) In the case of using (ii) a sulfur-containing tungsten compound or (v) a sulfur compound containing molybdenum as the additive (Y), the number of moles of titanium atoms contained in the titanium- Containing granular powder is mixed with the additive in such a ratio that the molar ratio (C / A) thereof is in the range of 6.96 × 10 ^-3 to 5.55 × 10 ^-1 , , And further comprises
(3) In the case of using (iii) a tungsten-containing chlorine compound or (vi) a molybdenum-containing chlorine compound as the additive (Y), the number of moles of titanium atoms contained in the titanium- when revealed the molar number of chlorine atoms contained in the granulated powder containing a D, its molar ratio (D / a) is 6.96 × 10 ^-3 to mixing the composite oxide and the additive at a ratio in the range of 6.94 × 10 ^-1 Including the steps of
Containing particulate powder for producing a honeycomb-shaped exhaust gas treating catalyst. The method according to claim 10, wherein the titanium-containing granular powder is a mixture of the composite oxide (X) of the metal element, (i) a tungsten-containing nitrogen compound, (ii) a tungsten-containing sulfur compound, (iii) a tungsten- ) Containing at least one additive (Y) selected from a molybdenum-containing nitrogen compound, a molybdenum-containing nitrogen compound, a molybdenum-containing sulfur compound and a molybdenum-containing chlorine compound. Gt; (1) A process for producing a honeycomb-shaped exhaust gas treating catalyst, comprising the steps of: mixing water and vanadium oxide or a precursor thereof with titanium-containing granular powder for producing a honeycomb-shaped exhaust gas treating catalyst according to claim 10 to obtain a slurry liquid containing these components;
(2) a step of adding a structural reinforcement to the slurry liquid and kneading the mixture to obtain a mixture containing the above components,
(3) a step of extruding and forming the mixture to obtain a honeycomb structure and
(4) drying the honeycomb structured body, and further calcining the honeycomb structured body under a temperature condition of 400 to 700 ° C.

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