WO2013099253A1 - Poudre granulée contenant du titane et son procédé de production, et catalyseur de traitement de gaz d'échappement utilisant celle-ci et son procédé de production - Google Patents

Poudre granulée contenant du titane et son procédé de production, et catalyseur de traitement de gaz d'échappement utilisant celle-ci et son procédé de production Download PDF

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WO2013099253A1
WO2013099253A1 PCT/JP2012/008353 JP2012008353W WO2013099253A1 WO 2013099253 A1 WO2013099253 A1 WO 2013099253A1 JP 2012008353 W JP2012008353 W JP 2012008353W WO 2013099253 A1 WO2013099253 A1 WO 2013099253A1
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titanium
granular powder
honeycomb
tungsten
exhaust gas
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PCT/JP2012/008353
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English (en)
Japanese (ja)
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究 瀬戸
足立　健太郎
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日揮触媒化成株式会社
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Priority to CN201280064415.4A priority Critical patent/CN104023840B/zh
Priority to KR1020147017326A priority patent/KR101667863B1/ko
Publication of WO2013099253A1 publication Critical patent/WO2013099253A1/fr

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    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
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    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
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    • B01J23/24—Chromium, molybdenum or tungsten
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/615—100-500 m2/g
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C01G41/006—Compounds containing, besides tungsten, two or more other elements, with the exception of oxygen or hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2255/00—Catalysts
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    • B01D2255/207—Transition metals
    • B01D2255/20707—Titanium
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • C—CHEMISTRY; METALLURGY
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    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area

Definitions

  • the present invention relates to a titanium-containing granular powder for producing an exhaust gas treatment catalyst having good moldability to a honeycomb structure, an exhaust gas treatment catalyst using the same, and a production method thereof.
  • SCR selective catalytic reduction
  • a catalyst in which an active component such as vanadium oxide or tungsten oxide is supported on a titanium oxide carrier is used.
  • a denitration catalyst of the SCR method is disposed in the flue and advances the denitration reaction by contacting with the exhaust gas.
  • the denitration catalyst Is used, for example, formed into a honeycomb shape.
  • a honeycomb-shaped denitration catalyst is formed by extruding a powdery carrier component into a honeycomb shape, then impregnating and supporting the active component, or kneading the carrier component and active component together with a molding aid etc. and extruding into a honeycomb shape. It is manufactured by a molding method or the like. For this reason, it is preferable that the titanium oxide powder as the carrier component has high extrudability.
  • the titanium oxide powder baked at a relatively high temperature has good extrudability, but since crystallization proceeds, the specific surface area may be reduced, and the denitration performance may be reduced.
  • titanium oxide powder fired at a relatively low temperature has a small decrease in specific surface area, but has a problem that it is difficult to form into a honeycomb shape due to poor extrudability.
  • Patent Document 1 describes a technique for preparing composite oxide particles of titanium dioxide and tungsten oxide by adding ammonium paratungstate to a titanium dioxide precursor and firing at 500 ° C. for 3 hours.
  • ammonium paratungstate and ammonium metavanadate are added to a titanium dioxide precursor and calcined at 550 ° C. for 2 hours to obtain a titanium-containing powder for producing a denitration catalyst.
  • ammonium paratungstate is known to decompose at a temperature of about 450 ° C. to release ammonia, resulting in tungsten oxide.
  • the titanium-containing powder for producing a denitration catalyst described in Patent Documents 1 and 2 does not contain an ammonium salt, when producing a honeycomb structure using these powders, the moldability at the time of extrusion molding was not good.
  • the exhaust gas denitration catalyst described in Patent Document 3 is obtained by adding ammonium metatungstate to titanium dioxide powder calcined at 600 to 1000 ° C., then forming into a honeycomb shape, and further at a temperature of 500 to 600 ° C. A technique for obtaining a denitration catalyst by calcination is described. However, when the titanium dioxide powder is calcined at 600 to 1000 ° C., crystallization proceeds and the specific surface area of the powder decreases, resulting in a decrease in the denitration catalyst activity.
  • the present invention has been made in view of the above-described circumstances, and the object thereof is titanium-containing granular powder having good moldability and low specific surface area after firing, a method for producing the same, and further this titanium-containing granular powder. And a method for producing the same.
  • the first invention is a composite oxide (X) of a metal element containing at least one of tungsten and molybdenum and titanium, (i) a tungsten-containing nitrogen compound, (ii) a tungsten-containing sulfur compound, and (iii) tungsten-containing
  • a honeycomb-shaped exhaust gas treatment catalyst comprising a chlorine compound, (iv) a molybdenum-containing nitrogen compound, (v) a molybdenum-containing sulfur compound, and (vi) an additive (Y) selected from molybdenum-containing chlorine compounds.
  • a titanium-containing granular powder (1)
  • the additive (Y) includes (i) a tungsten-containing nitrogen compound or (iv) a molybdenum-containing nitrogen compound
  • A represents the number of moles of titanium atoms contained in the titanium-containing granular powder.
  • B the number of moles of nitrogen atoms contained in the titanium-containing granular powder is represented by B
  • the molar ratio (B / A) is in the range of 8.70 ⁇ 10 ⁇ 4 to 2.78 ⁇ 10 ⁇ 1 .
  • the additive (Y) contains (ii) a tungsten-containing sulfur compound or (v) a molybdenum-containing sulfur compound
  • A represents the number of moles of titanium atoms contained in the titanium-containing granular powder.
  • the molar ratio (C / A) is in the range of 6.96 ⁇ 10 ⁇ 3 to 5.55 ⁇ 10 ⁇ 1 .
  • 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.
  • the first invention has the following requirements.
  • the titanium oxide contained in the titanium-containing granular powder has an anatase type crystal structure, and the (101) plane of the anatase type crystal the peak intensity and P 1, and when representing the peak intensity of (101) plane of anatase-type crystal in the reference powder (Ishihara Sangyo Kaisha Ltd. MC-90) of titanium dioxide P 0, the ratio of the peak intensity ( (P 1 / P 0 ) is in the range of 0.30 to 1.3, and the specific surface area of the titanium-containing granular powder is in the range of 40 to 300 m 2 / g.
  • the titanium-containing granular powder is a particulate material in which 99.9% by weight or more of the total amount has a particle diameter of 45 ⁇ m or less.
  • the (i) tungsten-containing nitrogen compound is at least one selected from ammonium paratungstate, ammonium metatungstate, ammonium phosphotungstate and ammonium tetrathiotungstate, and (iv) molybdenum-containing The nitrogen compound is at least one selected from ammonium molybdate, ammonium phosphomolybdate and ammonium tetrathiomolybdate.
  • the (ii) tungsten-containing sulfur compound is tungsten disulfide, and the (v) molybdenum-containing sulfur compound is molybdenum disulfide.
  • the (iii) tungsten-containing chlorine compound is tungsten hexachloride, and the (vi) molybdenum-containing chlorine compound is molybdenum pentachloride.
  • a second invention is a honeycomb-shaped exhaust gas treatment catalyst characterized in that it contains a titanium-containing granular powder and an active ingredient, and the content ratio of the titanium-containing granular powder is 60% by weight or more. Furthermore, the second invention preferably has the following requirements.
  • the active ingredient is vanadium oxide.
  • the honeycomb-shaped exhaust gas treatment catalyst is a nitrogen oxide removal catalyst.
  • the third invention is a composite oxide (X) of a metal element containing at least one of tungsten and molybdenum and titanium, (i) a tungsten-containing nitrogen compound, (ii) a tungsten-containing sulfur compound, and (iii) tungsten-containing Honeycomb including a step of mixing a chlorine compound, (iv) a molybdenum-containing nitrogen compound, (v) a molybdenum-containing sulfur compound, and (vi) an additive (Y) selected from the molybdenum-containing chlorine compound at a ratio shown below:
  • a method for producing titanium-containing granular powder for producing a flue gas treatment catalyst (1) When (i) tungsten-containing nitrogen compound or (iv) molybdenum-containing nitrogen compound is used as the additive (Y), the number of moles of titanium atoms contained in the titanium-containing granular powder is represented by A.
  • the molar ratio (B / A) is from 8.70 ⁇ 10 ⁇ 4 to 2.78 ⁇ 10 ⁇ 1 .
  • the step of mixing the composite oxide and the additive in a proportion that falls within a range (2)
  • the number of moles of titanium atoms contained in the titanium-containing granular powder is A.
  • the molar ratio ( D / A) is 6 96 ⁇ 10 -3 ⁇ 6.94 ⁇ 10 the composite oxide at a rate in the range of -1 and titanium-containing particulate honeycomb exhaust gas treatment catalyst for the production, characterized by comprising the step of mixing the additive It is a manufacturing method of powder. Furthermore, it is preferable that the third invention has the following requirements.
  • the titanium-containing granular powder comprises the composite oxide (X) of the metal element, (i) a tungsten-containing nitrogen compound, (ii) a tungsten-containing sulfur compound, (iii) a tungsten-containing chlorine compound, and (iv) molybdenum. It is obtained by mixing at least one additive (Y) selected from a nitrogen-containing compound, (v) a molybdenum-containing sulfur compound, and (vi) a molybdenum-containing chlorine compound.
  • the fourth invention is (1) mixing water and vanadium oxide or a precursor thereof with titanium-containing granular powder for producing a honeycomb-shaped exhaust gas treatment catalyst produced by the production method according to the third invention, Obtaining a slurry liquid containing these components, (2) adding a structural reinforcing material to the slurry and kneading to obtain a mixture containing the components; (3) including a step of obtaining the honeycomb structure by extruding the admixture, and (4) further comprising firing at a temperature of 400 to 700 ° C. after drying the honeycomb structure.
  • This is a method for manufacturing a honeycomb-shaped exhaust gas treatment catalyst.
  • the titanium-containing granular powder of the present invention since a composite oxide of at least one of tungsten and molybdenum and titanium is contained, the progress of crystallization during firing of the exhaust gas treatment catalyst after honeycomb formation is suppressed, High catalytic activity can be maintained by suppressing a decrease in specific surface area.
  • the additives because it contains nitrogen compounds, sulfur compounds, and chlorine compounds containing tungsten and molybdenum as additives, these additives play a role in improving the formability of titanium-containing granular powders, resulting in extrusion molding. It is possible to obtain a honeycomb structure with little or very few defects in the honeycomb shape.
  • FIG. 1 is a conceptual diagram of a honeycomb structure according to the present invention, and more specifically, shows a plan view seen from one end side in a penetration direction of a honeycomb hole.
  • titanium-containing granular powder for manufacturing a honeycomb-shaped exhaust gas treatment catalyst in the present invention (hereinafter sometimes simply referred to as “titanium-containing granular powder”) is a composite oxidation of a metal element containing at least one of tungsten and molybdenum and titanium. Contains things.
  • the composite oxide is a compound of at least one metal element of tungsten (W) and molybdenum (Mo), a metal element of titanium (Ti), and oxygen (O).
  • this composite oxide includes a crystal structure portion corresponding to anatase-type titanium dioxide.
  • specific examples of the composite oxide include a composite oxide containing titanium and tungsten (for convenience, TiO 4/2 -WO 4/2 ), a composite oxide containing titanium and molybdenum (for convenience).
  • a binary composite oxide such as TiO 4/2 -MoO 4/2
  • a composite oxide containing titanium, tungsten, and molybdenum for convenience, TiO 4/2 -WO 4 / 2- TiO 4/2 -MoO 4/2
  • binary and ternary complex oxides as shown in the above general chemical formula (I), are those in which TiO 4/2 titanium oxide molecules are dispersed in a highly dispersed state such as WO 4/2 and MoO 4/2. It is conceivable to have an incorporated structure.
  • TiO 4/2 and MoO 4/2 incorporated into the titanium oxide molecule TiO 4/2 are titanium dioxide during heating and firing of the honeycomb structure obtained from the titanium-containing granular powder containing the composite oxide. It is considered to play a role of suppressing the metastasis of the crystallization proceeds and rutile titanium dioxide (TiO 2) (TiO 2) .
  • TiO 2 rutile titanium dioxide
  • the honeycomb-shaped exhaust gas treatment using the honeycomb structure obtained from the titanium-containing granular powder containing the composite oxide In a catalyst, particularly a nitrogen oxide removal catalyst, excellent effects such as resistance to sulfur compounds contained in exhaust gas and wear resistance may not be obtained.
  • the specific surface area (SA) and anatase of titanium oxide when the titanium-containing granular powder is measured by X-ray diffraction The peak intensity of the (101) plane of the mold crystal is preferably within a predetermined range.
  • the specific surface area of the titanium-containing granular powder is preferably in the range of 40 to 300 m 2 / g, more preferably in the range of 50 to 120 m 2 / g.
  • the specific surface area after firing the honeycomb structure formed using the titanium-containing granular powder also becomes small, and sufficient catalytic activity as an exhaust gas treatment catalyst is obtained.
  • the specific surface area of the said titanium containing granular powder can be adjusted in the above-mentioned range by heating or baking this granular powder.
  • the temperature at which the additive used here decomposes and releases gaseous nitrogen compounds (eg NH 4 ), gaseous sulfur compounds (eg SO 2 ), gaseous chlorine compounds (eg ClO 2 ), etc. Do not heat up to.
  • this compound decomposes at a temperature of about 450 ° C.
  • the ratio of the peak intensity (P 1 / P 0 ) is preferably in the range of 0.30 to 1.3, and more preferably in the range of 0.6 to 1.2.
  • the peak intensity ratio exceeds 1.3, it indicates that crystallization of titanium dioxide is in progress, leading to a decrease in specific surface area and catalyst performance.
  • a more preferable range is 0.9 to 1.1. In this range, the effect of adding the additive is maximized in improving the moldability.
  • the peak intensity ratio (P 1 / P 0 ) can be adjusted within the above-mentioned range by heating or firing the titanium-containing granular powder.
  • the additive used here decomposes to form a gaseous nitrogen compound (for example, NH 4 ), a gaseous sulfur compound (for example, SO 2 ) or a gaseous chlorine compound (for example, ClO). 2 ) Do not heat to such a temperature as to release. The reason is as described above.
  • the titanium-containing granular powder according to the embodiment is added with an additive for improving the formability at the time of forming into a honeycomb structure.
  • An additive plays the role which gives moderate viscosity to the kneaded material of the titanium containing granular powder prepared for extrusion molding.
  • the kneaded product supplied to a die of a vacuum extrusion molding machine or the like becomes difficult to be interrupted, and there is little or no honeycomb part of the honeycomb shape.
  • the structure can be formed.
  • the “honeycomb-shaped partial defect” means that, for example, as shown in FIG. 1, a part of the partition walls forming the honeycomb structure is chipped. In some cases.
  • the specific surface area of the honeycomb structure may be reduced, or the mechanical strength of the honeycomb structure may be reduced.
  • 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 an additive group 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.
  • a tungsten-containing nitrogen compound include ammonium tungstate salts such as ammonium paratungstate, ammonium metatungstate, ammonium phosphotungstate, and tetrathiotungstate
  • tungsten-containing sulfur compounds include tungsten disulfide, Examples include tungsten trisulfide.
  • examples of the tungsten-containing chlorine compound include tungsten hexachloride, tungsten dichloride, tungsten trichloride, tungsten tetrachloride, tungsten pentachloride, tungsten dichloride dioxide, and tungsten tetrachloride oxide.
  • examples of the molybdenum-containing nitrogen compound include ammonium molybdate such as ammonium molybdate, ammonium phosphomolybdate, and ammonium tetrathiomolybdate
  • examples of the molybdenum-containing sulfur compound include molybdenum disulfide, molybdenum trisulfide, Examples thereof include molybdenum tetrasulfide.
  • examples of the molybdenum-containing chlorine compound include molybdenum pentachloride, molybdenum dichloride, molybdenum trichloride, molybdenum tetrachloride, and molybdenum pentachloride.
  • these additives are oxidized to become tungsten oxide (WO 3 ) or molybdenum oxide (MoO 3 ) when the honeycomb structure after being formed is fired to obtain an exhaust gas treatment catalyst.
  • the tungsten oxide and molybdenum oxide obtained here are contained in the composite oxide and are combined with the above-mentioned WO 4/2 and MoO 4/2 incorporated into titanium dioxide (TiO 4/2 ). The form is different.
  • the titanium-containing granular powder in the present invention contains the above-mentioned additives in the proportions shown below.
  • the additive contains a tungsten-containing nitrogen compound or a molybdenum-containing nitrogen compound
  • a value obtained by dividing the mass of titanium atoms contained in the titanium-containing granular powder by its atomic weight is represented by A
  • B the value obtained by dividing the mass of nitrogen atoms contained in the titanium-containing granular powder by the atomic weight
  • the ratio (B / A) is 8.70 ⁇ 10 ⁇ 4 to 2.78 ⁇ . it is preferably in the range of 10 -1.
  • the additive contains a tungsten-containing sulfur compound or a molybdenum-containing sulfur compound
  • the value obtained by dividing the mass of titanium atoms contained in the titanium-containing granular powder by its atomic weight is represented by A
  • a value obtained by dividing the mass of sulfur atoms contained in the titanium-containing granular powder by the atomic weight is represented by C
  • the ratio (C / A) is 6.96 ⁇ 10 ⁇ 3 to 5. It is preferably in the range of 55 ⁇ 10 ⁇ 1 .
  • the additive contains a tungsten-containing chlorine compound or a molybdenum-containing chlorine compound
  • the value obtained by dividing the mass of titanium atoms contained in the titanium-containing granular powder by the atomic weight is represented by A.
  • the value obtained by dividing the mass of chlorine atoms contained in the titanium-containing granular powder by the atomic weight is represented by D
  • the ratio (D / A) is 6.96 ⁇ 10 ⁇ 3 to 6 It is preferably in the range of .94 ⁇ 10 ⁇ 1 . If the content of the additive is below the above range, the occurrence of the above-mentioned honeycomb defects may not be sufficiently suppressed.
  • the amount of the additive exceeds the above range, the heat generated when the additive is oxidized becomes large, which may cause cracks and cracks when the honeycomb structure is fired. is there.
  • the titanium-containing granular powder according to the present invention is a particulate material having a particle size of 45 ⁇ m or less. Extrusion was performed when particles in this particle size range were less than 99.9% by mass of the total weight, that is, when more than 0.1% by mass of particulate matter having a particle size greater than 45 ⁇ m was included. In some cases, some or many of the partition walls may be lost, and a desired honeycomb structure may not be obtained.
  • tungsten-containing nitrogen compounds such as ammonium paratungstate, ammonium metatungstate, ammonium phosphotungstate and ammonium tetrathiotungstate
  • tungsten-containing sulfur compounds such as tungsten disulfide and tungsten trisulfide
  • tungsten hexachloride Tungsten-containing chlorinated compounds such as tungsten dichloride, tungsten trichloride, tungsten tetrachloride, tungsten pentachloride, tungsten dichloride dioxide, tungsten tetrachloride oxide
  • molybdenum such as ammonium molybdate, ammonium phosphomolybdate, and ammonium tetrathiomolybdate
  • Molybdenum-containing sulfur compounds such as nitrogen compounds, molybdenum disulfide, molybdenum trisulfide, and molybdenum tetrasulfide, molybdenum pentachloride, molybden
  • the amount of the raw materials, due to preliminary experiments, dehydration, titanium-containing particulate powder was calcined, more particularly WO 3 and MoO and WO 4/2 and MoO 4/2 contained in the composite oxide It can be determined by grasping in advance the relationship between the content of tungsten or molybdenum converted to the oxide standard of 3 and the amount of each raw material added. Moreover, it is preferable to use the titanium sulfate solution obtained from the manufacturing process of the titanium dioxide by a sulfuric acid method as a raw material of metatitanic acid, and also hydrolyze this 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, so that the pH of the solution is in the range of 2 to 10.5 in advance. It is preferable to adjust to the set value.
  • the slurry solution is, for example, at a temperature range of 50 to 100 ° C. for 0.5 to 24 hours. Aged by heating.
  • the slurry solution after heat aging is dehydrated, and the obtained dehydrated cake is washed with distilled water or the like, and then dehydrated again to obtain a dehydrated cake.
  • the dried product obtained by drying the moisture in the obtained dehydrated cake is baked in a temperature range of, for example, 400 to 700 ° C. for 0.5 to 20 hours in an air atmosphere kiln, etc. Can be obtained.
  • it is desirable that the composite oxide is further pulverized by a ball mill or the like, if necessary, to obtain a composite oxide having a particle size of not less than 99.9% by mass of 45 ⁇ m or less.
  • a tungsten-containing nitrogen compound, tungsten-containing sulfur compound, tungsten-containing chlorine compound, molybdenum-containing nitrogen compound, molybdenum-containing sulfur is added to a composite oxide of a metal element containing at least one of tungsten and molybdenum and titanium manufactured by the above method.
  • the titanium-containing granular powder according to the present invention is produced by mixing an additive selected from the group consisting of a compound and a molybdenum-containing chlorine compound.
  • the value obtained by dividing the mass of titanium atoms contained in the titanium-containing granular powder by the atomic weight is represented by A.
  • the value obtained by dividing the mass of nitrogen atoms contained in the titanium-containing granular powder by the atomic weight is represented by B
  • the ratio (B / A) is 8.70 ⁇ 10 ⁇ 4 to 2
  • the composite oxide and the additive are mixed at a ratio in the range of .78 ⁇ 10 ⁇ 1 .
  • the mixing amount of the additive formulates the relationship of the B / A ratio of the composite oxide and the titanium-containing granular powder to the mixing amount of the additive, and the required mixing amount of the additive is determined from the design value of B / A. It can be obtained by reverse calculation.
  • the value obtained by dividing the mass of titanium atoms contained in the titanium-containing granular powder by the atomic weight is represented by A.
  • the value obtained by dividing the mass of sulfur atoms contained in the titanium-containing granular powder by the atomic weight is represented by C
  • the ratio (C / A) is 6.96 ⁇ 10 ⁇ 3 to 5
  • the composite oxide and the additive are mixed at a ratio in the range of .55 ⁇ 10 ⁇ 1 .
  • the mixing amount of the additive in this case can also be determined from the relational expression between the mixing amount of the additive and the C / A ratio between the composite oxide and the titanium-containing granular powder.
  • the value obtained by dividing the mass of titanium atoms contained in the titanium-containing granular powder by the atomic weight is represented by A.
  • the value obtained by dividing the mass of chlorine atoms contained in the titanium-containing granular powder by the atomic weight is represented by D
  • the ratio (D / A) is 6.96 ⁇ 10 ⁇ 3 to 6
  • the composite oxide and the additive are mixed at a ratio in the range of 94 ⁇ 10 ⁇ 1 .
  • the mixing amount of the additive in this case can also be determined from the relational expression between the mixing amount of the additive and the D / A ratio between the composite oxide and the titanium-containing granular powder.
  • the additive used in preparing the titanium-containing granular powder one type may be selected from the aforementioned additive group, or two or more types may be selected. Further, the timing of adding the additive to the composite oxide is not limited to the stage after the composite oxide is pulverized. For example, the additive may be added to the ball mill together with the composite oxide and pulverized simultaneously.
  • the titanium-containing granular powder thus obtained is preferably a particulate material having a total amount of 99.9% by mass or more and a particle diameter of 45 ⁇ m or less.
  • a composite that has been previously pulverized by a ball mill or the like so that 99.9% by mass or more becomes a particulate material having a particle size of 45 ⁇ m or less The oxide and the additive may be mixed, or the mixed oxide and the additive may be mixed and then pulverized to adjust the particle diameter within the above range.
  • a honeycomb-shaped exhaust gas treatment catalyst according to the present invention is an exhaust gas treatment catalyst comprising the above-described honeycomb structure, and the titanium-containing granular powder is 60% by mass or more, preferably in the range of 70 to 99.9% by mass. It is desirable to contain. When the content ratio of the titanium-containing granular powder is less than 60% by mass, desired denitration activity may not be obtained.
  • the titanium-containing granular powder of the present invention is contained in an amount of 60% by mass or more, for example, the granular powder outside the technical scope of the present invention does not include the complex oxide and additive referred to in the present invention. (For example, titanium dioxide powder etc.) may be contained in less than 40% by mass.
  • the honeycomb-shaped exhaust gas treatment catalyst further includes an active component for removing nitrogen oxides.
  • the active component include vanadium (V), tungsten (W), molybdenum (Mo), chromium (Cr), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), silver ( Metal components such as Ag), iron (Au), palladium (Pd), yttrium (Y), cerium (Ce), neodymium (Nd), indium (In), and iridium (Ir) can be given.
  • vanadium oxide (V 2 O 5 ) is particularly suitable because it is relatively inexpensive and has a high removal rate of nitrogen oxides.
  • the content of the active component used in the exhaust gas treatment catalyst for removing nitrogen oxides is preferably in the range of 0.1 to 30% by mass of the total catalyst weight as metal oxide.
  • the honeycomb-shaped exhaust gas treatment catalyst formed so as to contain at least 60% by mass of the titanium-containing granular powder containing the composite oxide is a titanium dioxide at the time of firing the honeycomb structure containing the active component. Not only is the progress of crystallization suppressed, but when exhaust gas treatment is performed using this, a high nitrogen oxide removal rate can be achieved.
  • titanium oxide (TiO 4/2 ) contained in the granular powder forms a composite oxide with WO 4/2 and / or MoO 4/2 . Therefore, even if calcination is performed at the above temperature, crystallization of titanium dioxide can be suppressed. Furthermore, the titanium-containing granular powder not only contains tungsten such as WO 4/2 and molybdenum such as MoO 4/2 in the composite oxide, but also for improving moldability during extrusion molding. The additive used also includes a raw material that is finally fired to become an oxide such as WO 3 or MoO 3 .
  • honeycomb-shaped exhaust gas treatment catalyst that suppresses the progress of crystallization of titanium dioxide is less likely to reduce its specific surface area, and can maintain denitration activity close to the initial activity for a long period of time.
  • the additive used in the present invention can improve the formability when the honeycomb structure is extruded, it is possible to suppress the occurrence of the above-mentioned honeycomb defects.
  • the honeycomb-shaped exhaust gas treatment catalyst according to the present invention is obtained by (a) kneading the titanium-containing granular powder of the present invention and an active component or its precursor together with a molding aid or the like into a kneaded product, and then forming a desired honeycomb shape.
  • the titanium-containing granular powder of the present invention is kneaded with a molding aid or the like to obtain a kneaded product, and then extruded into a desired honeycomb shape, It is produced by a method of impregnating a dried and calcined carrier with an aqueous solution containing an active ingredient, followed by drying and calcining (impregnation method).
  • the catalyst produced by the kneading method (a) is said to be a solid type catalyst, and since high denitration activity can be obtained, a honeycomb-shaped exhaust gas treatment catalyst containing vanadium oxide as an active substance by the kneading method An example of manufacturing the case will be described.
  • the titanium-containing granular powder of the present invention is dispersed in a solvent such as water to form a slurry solution, and a vanadium oxide precursor, such as ammonium metavanadate, and a monoethanolamine as a dissolving agent are added to the slurry solution. .
  • a reinforcing material such as glass fiber or acid clay and a lubricant such as polyethylene oxide are added to the slurry solution, and kneaded and kneaded with a kneader such as a kneader to prepare a kneaded product suitable for extrusion molding.
  • the admixture thus obtained is extruded using, for example, a vacuum extruder to obtain a honeycomb structure.
  • the additive contained in the kneaded product gives an appropriate viscosity to the kneaded product, which makes it difficult for the kneaded product supplied to the die of the vacuum extrusion machine to be cut off, and partially destroys the honeycomb shape.
  • a honeycomb structure with little or the like is formed. Thereafter, the obtained honeycomb structure is dried, and the dried honeycomb structure is fired in a kiln in an atmospheric atmosphere, for example, at a temperature range of 400 to 700 ° C. for 0.5 to 24 hours to be glass fiber or acidic.
  • a honeycomb-shaped exhaust gas treatment catalyst containing vanadium oxide as an active metal in titanium oxide with white clay added is obtained.
  • honeycomb-shaped exhaust gas treatment catalyst honeycomb structure
  • the shape of the honeycomb-shaped exhaust gas treatment catalyst (honeycomb structure) obtained in this way is not particularly limited, but is composed of a square quadrangular prism, a rectangular quadrangular prism, etc.
  • a plurality of rectangular honeycomb holes for example, 4 to 2500 as shown in FIG. 1 are formed.
  • the honeycomb holes may have a honeycomb shape instead of a square shape.
  • the external dimensions of the honeycomb structure are as follows: (1) The length of the plane from one end in the penetration direction of the honeycomb holes (hereinafter sometimes referred to as “the length of one side of the plane”) is about 30 to 300 mm, preferably Is about 50 to 200 mm (ii) the length in the penetration direction of the honeycomb holes (hereinafter sometimes referred to as “the length in the penetration direction”) is about 100 to 3000 mm, preferably about 300 to 1500 mm, (iii) the honeycomb holes The length of one side of the opening that forms (square) (hereinafter sometimes referred to as “opening”) is about 1 to 15 mm, preferably about 2 to 10 mm, and (iv) is formed between the honeycomb holes.
  • partition wall thickness (hereinafter sometimes referred to as “partition wall thickness”) is about 0.1 to 2 mm, preferably about 0.1 to 1.5 mm, and (v) the honeycomb structure has an aperture ratio of 60 to 85%, preferably in the range of 70-85% It is desirable to be.
  • the strength of the honeycomb structure becomes weak, or denitration per unit volume. In some cases, the activity and the activity of decomposing organic halogen compounds may be lowered.
  • Honeycomb exhaust gas treatment catalyst of the present invention the exhaust gas containing NO X, in particular NO X, such as boiler exhaust gas, in addition heavy metal containing SO X, the exhaust gas containing dust, adding a reducing agent such as ammonia
  • NO X such as boiler exhaust gas
  • a reducing agent such as ammonia
  • the catalyst is used under normal denitration treatment conditions.
  • the reaction temperature is in the range of 150 to 600 ° C., preferably 300 to 400 ° C., and the space velocity (superficial velocity). Is preferably in the range of 1000 to 100,000 hr ⁇ 1 .
  • the evaluation method of the honeycomb-shaped exhaust gas treatment catalyst manufactured using the titanium-containing granular powder of each example is described below.
  • Formability test generation of honeycomb defects
  • the criteria for determining the formability of the honeycomb structure is a vacuum type extrusion molding machine, in which 20 honeycomb structures each having a length of 500 mm in the penetrating direction are formed continuously (the length of one side of the plane).
  • the length of one side of the honeycomb hole is about 6.7 mm
  • the thickness of the partition wall of the honeycomb hole is about 0.75 mm
  • some of the honeycomb-shaped defects are generated in the subsequent honeycomb structures. I confirmed.
  • a honeycomb-shaped exhaust gas treatment catalyst having a honeycomb structure having a honeycomb hole number of 9 ⁇ 9 and a length of 100 mm in the penetration direction (the other dimensions are cut out and adjusted) is used as a test sample, and this test sample is used as a flow reaction.
  • the vessel was filled.
  • a gas containing sand was passed through the flow reactor under the following conditions, and the wear rate was measured based on the following formula (1) from the amount of decrease in the catalyst weight.
  • the amount of sand passing through the flow reactor was determined by providing a cyclone in the rear stage of the flow reactor, and measuring the weight of the sand collected in the cyclone after the wear test.
  • Abrasion rate (% / kg) ⁇ [catalyst weight before starting wear test (g) ⁇ catalyst weight after finishing wear test (g)] / catalyst weight before starting wear test (g) ⁇ ⁇ 100 / sand passing amount (Kg)
  • Test conditions Catalyst shape: Honeycomb pores 9 ⁇ 9, 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 sand Average particle size 500 ⁇ m [3] Heat resistance test The peak intensity (P 1 ) of the (101) plane of the anatase type crystal contained in the honeycomb-shaped exhaust gas treatment catalyst, and the (101) ) plane was confirmed thermostable than 'ratio (peak intensity after heat resistance test P 1 with)' / heat resistance test prior to the peak intensity P 1) peak intensity (P 1 of. The smaller the value of the peak intensity ratio
  • Specific surface area The specific surface area of the titanium-containing granular powder or honeycomb-shaped exhaust gas treatment catalyst was determined by a specific surface area measuring device based on the BET method using a mixed gas of 30% nitrogen and 70% helium as an adsorbed gas (Macsorb HM model-1220, manufactured by Mountec Co., Ltd.). Asked.
  • Pore volume Using a porosimeter (manufactured by Quantachrome, Poremster 33), the total pore volume of the honeycomb-shaped exhaust gas treatment catalyst was determined by a mercury intrusion method.
  • the peak intensity P 0 (measured value storage) of the plane and the peak intensity P 1 of the (101) plane of the anatase type crystal of titanium oxide contained in the titanium-containing granular powder prepared in the present invention are the X-rays shown above. Each was measured by diffraction, and the peak intensity ratio (P 1 / P 0 ) was determined.
  • Denitration rate (%) ⁇ [NO X (mass ppm) of the non-contact gas - NO X in the gas after contacting (mass ppm)] / NO X untouched gas (mass ppm) ⁇ ⁇ 100 ⁇ (2 )
  • Titanium-containing granular powder (a) and honeycomb-shaped exhaust gas treatment catalyst (A)> Titanium-containing granular powder (a)
  • the titanium sulfate solution obtained from the manufacturing process of titanium dioxide by the sulfuric acid method was hydrolyzed to obtain a metatitanic acid slurry.
  • the mixture was aged by heating with sufficient stirring.
  • the slurry after heat aging was cooled and taken out from the stirring vessel, and the solid content was filtered and dehydrated to obtain a washed cake.
  • the washed cake was dried at a temperature of 110 ° C. for 20 hours and then calcined at a temperature of 550 ° C. for 5 hours. Thereby, the nitrogen atom contained in the added raw material etc. was discharge
  • the fired product is previously pulverized by a ball mill, and a composite oxide granular powder (a ′) containing a metal element of titanium and tungsten having a particle diameter of 45 ⁇ m or less of 99.9% by mass of the whole.
  • a ′ composite oxide granular powder
  • 0.282 kg of ammonium paratungstate as an additive was added to the granular powder (a ′) of the composite oxide, and mixed so as to be uniform with 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) in which 99.9% by mass or more of the total amount had a particle diameter of 45 ⁇ m or less.
  • a value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (a) thus obtained by the atomic weight is obtained.
  • a value B obtained by dividing a nitrogen atom which is an element constituting the additive (ammonium paratungstate) by its atomic weight was determined.
  • the values A and B were 297 and 0.90, respectively, and the ratio (B / A) was 3.03 ⁇ 10 ⁇ 3 .
  • the titanium-containing granular powder (a) was measured by the X-ray diffraction shown above, the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure, and the anatase type crystal of the peak intensity of (101) plane and P 1, and when representing the peak intensity of (101) plane of anatase-type crystal in the reference powder (Ishihara Sangyo Kaisha Ltd.
  • the value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (b) thus obtained by the atomic weight is obtained.
  • a value B obtained by dividing a nitrogen atom which is an element constituting the additive (ammonium paratungstate) by its atomic weight was determined.
  • the values A and B were 297 and 1.80, respectively, and the ratio (B / A) was 6.05 ⁇ 10 ⁇ 3 .
  • Titanium-containing granular powder (c) and honeycomb-shaped exhaust gas treatment catalyst (C)> Titanium-containing granular powder (c) In the same manner as in Example 1, except that the amount of ammonium paratungstate added was changed to 0.281 kg when preparing the composite oxide granular powder (a ′) obtained in Example 1. Thus, a composite oxide granular powder (c ′) was obtained. Further, the titanium-containing granular powder was prepared in the same manner as in Example 1 except that the amount of ammonium paratungstate added as an additive to the granular powder (c ′) of this composite oxide was changed to 1.13 kg. (C) was prepared.
  • a value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (c) thus obtained by the atomic weight is obtained.
  • a value B obtained by dividing a nitrogen atom which is an element constituting the additive (ammonium paratungstate) by its atomic weight was determined.
  • the values A and B were 297 and 3.60, respectively, and the ratio (B / A) was 1.21 ⁇ 10 ⁇ 2 .
  • a value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (d) thus obtained by the atomic weight is obtained.
  • a value B obtained by dividing a nitrogen atom which is an element constituting the additive (ammonium paratungstate) by its atomic weight was determined.
  • the values A and B were 282 and 4.49, respectively, and the ratio (B / A) was 1.60 ⁇ 10 ⁇ 2 .
  • (E) was prepared. Next, a value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (e) thus obtained by the atomic weight is obtained. Further, a value B obtained by dividing a nitrogen atom which is an element constituting the additive (ammonium paratungstate) by its atomic weight was determined. As a result, the values A and B were 250 and 8.99, respectively, and the ratio (B / A) was 3.59 ⁇ 10 ⁇ 2 .
  • Titanium-containing granular powder (f) and honeycomb-shaped exhaust gas treatment catalyst (F)> Titanium-containing granular powder (f) Titanium was prepared in the same manner as in Example 1, except that the additive added to the composite oxide granular powder (a ′) obtained in Example 1 was changed to tungsten disulfide (added amount: 0.267 kg). The contained granular powder (f) was obtained. Next, a value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (f) thus obtained by the atomic weight is obtained.
  • a value C obtained by dividing a nitrogen atom which is an element constituting the additive (tungsten disulfide) by its atomic weight was determined.
  • the values A and C were 297 and 2.16, respectively, and the ratio (C / A) was 7.26 ⁇ 10 ⁇ 3 .
  • the titanium-containing granular powder (f) was measured by the X-ray diffraction shown above, the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure, and the ratio of the peak intensities (P 1 / P 0 ) was 0.95. Furthermore, it was 94 m ⁇ 2 > / g when the specific surface area of the said titanium containing granular powder was measured by said method.
  • honeycomb exhaust gas treatment catalyst (F) Next, a honeycomb-shaped exhaust gas composed of a honeycomb structure was produced in the same manner as in Example 1 except that this titanium-containing granular powder (f) was used instead of the titanium-containing granular powder (a) described in Example 1. A treated catalyst (F) was prepared.
  • Titanium-containing granular powder (g) Titanium was prepared 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 tungsten disulfide (added amount: 0.535 kg). The contained granular powder (g) was obtained. Next, a value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (g) thus obtained by the atomic weight is obtained.
  • a value C obtained by dividing a nitrogen atom which is an element constituting the additive (tungsten disulfide) by its atomic weight was determined.
  • the values A and C were 297 and 4.31, respectively, and the ratio (C / A) was 1.45 ⁇ 10 ⁇ 2 .
  • the titanium-containing granular powder (g) was measured by the X-ray diffraction shown above, the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure, and the ratio of the peak intensities (P 1 / P 0 ) was 0.95. Furthermore, it was 94 m ⁇ 2 > / g when the specific surface area of the said titanium containing granular powder was measured by said method.
  • honeycomb exhaust gas treatment catalyst Next, a honeycomb-like exhaust gas comprising a honeycomb structure was produced in the same manner as in Example 1 except that this titanium-containing granular powder (g) was used instead of the titanium-containing granular powder (a) described in Example 1. A treated catalyst (G) was prepared.
  • Titanium-containing granular powder (h) and honeycomb-shaped exhaust gas treatment catalyst (H)> Titanium-containing granular powder (h) Titanium was prepared in the same manner as in Example 1, except that the additive added to the composite oxide granular powder (c ′) obtained in Example 3 was changed to tungsten disulfide (added amount: 1.07 kg). The contained granular powder (h) was obtained. Next, a value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (h) thus obtained by the atomic weight is obtained.
  • a value C obtained by dividing a nitrogen atom which is an element constituting the additive (tungsten disulfide) by its atomic weight was determined.
  • the values A and C were 297 and 8.63, respectively, and the ratio (C / A) was 2.90 ⁇ 10 ⁇ 2 .
  • the titanium-containing granular powder (h) was measured by the X-ray diffraction shown above, the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure, and the ratio of the peak intensities (P 1 / P 0 ) was 0.97. Furthermore, it was 94 m ⁇ 2 > / g when the specific surface area of the said titanium containing granular powder was measured by said method.
  • honeycomb exhaust gas treatment catalyst (H) Next, a honeycomb-like exhaust gas composed of a honeycomb structure was produced in the same manner as in Example 1 except that this titanium-containing granular powder (h) was used instead of the titanium-containing granular powder (a) described in Example 1. A treated catalyst (H) was prepared.
  • a value D obtained by dividing a nitrogen atom which is an element constituting the additive (tungsten hexachloride) by its atomic weight was obtained.
  • the values A and D were 297 and 6.47, respectively, and the ratio (D / A) was 2.18 ⁇ 10 ⁇ 2 .
  • the titanium-containing granular powder (i) was measured by the X-ray diffraction shown above, the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure, and the ratio of the peak intensities (P 1 / P 0 ) was 0.97. Furthermore, it was 91 m ⁇ 2 > / g when the specific surface area of the said titanium containing granular powder was measured by said method.
  • honeycomb exhaust gas treatment catalyst (I) Next, a honeycomb-shaped exhaust gas composed of a honeycomb structure was produced in the same manner as in Example 1 except that this titanium-containing granular powder (i) was used instead of the titanium-containing granular powder (a) described in Example 1. Treated catalyst (I) was prepared.
  • a value D obtained by dividing a nitrogen atom which is an element constituting the additive (tungsten hexachloride) by its atomic weight was obtained.
  • the values A and D were 297 and 12.9, respectively, and the ratio (D / A) was 4.35 ⁇ 10 ⁇ 2 .
  • the titanium-containing granular powder (j) was measured by the X-ray diffraction shown above, the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure, and the ratio of the peak intensities (P 1 / P 0 ) was 0.96. Furthermore, it was 92 m ⁇ 2 > / g when the specific surface area of the said titanium containing granular powder was measured by said method.
  • honeycomb exhaust gas treatment catalyst (J) Next, a honeycomb-like exhaust gas composed of a honeycomb structure was produced in the same manner as in Example 1 except that this titanium-containing granular powder (j) was used instead of the titanium-containing granular powder (a) described in Example 1. A treated catalyst (J) was prepared.
  • Titanium-containing granular powder (k) and honeycomb-shaped exhaust gas treatment catalyst (K)> Titanium-containing granular powder (k) Titanium-containing in the same manner as in Example 1 except that the additive added to the granular powder (c ′) of the composite oxide obtained in Example 3 was changed to tungsten hexachloride (addition amount 1.71 kg). A granular powder (k) was obtained. Next, a value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (k) thus obtained by the atomic weight is obtained.
  • a value D obtained by dividing a nitrogen atom which is an element constituting the additive (tungsten hexachloride) by its atomic weight was obtained.
  • the values A and D were 297 and 25.9, respectively, and the ratio (D / A) was 8.71 ⁇ 10 ⁇ 2 .
  • the titanium-containing granular powder (k) was measured by the X-ray diffraction shown above, the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure, and the ratio of the peak intensities (P 1 / P 0 ) was 0.95.
  • Example 12 ⁇ Titanium-containing granular powder (l) and honeycomb-shaped exhaust gas treatment catalyst (L)> (1) Titanium-containing granular powder (l) Titanium-containing 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 ammonium molybdate (addition amount 0.613 kg). A granular powder (l) was obtained. Next, a value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (l) thus obtained by the atomic weight is obtained.
  • a value B obtained by dividing a nitrogen atom which is an element constituting the additive (ammonium molybdate) by its atomic weight was obtained.
  • the values A and B were 297 and 2.98, respectively, and the ratio (B / A) was 1.00 ⁇ 10 ⁇ 2 .
  • the titanium-containing granular powder (l) was measured by the X-ray diffraction shown above, the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure, and the ratio of the peak intensities (P 1 / P 0 ) was 0.98. Furthermore, it was 93 m ⁇ 2 > / g when the specific surface area of the said titanium containing granular powder was measured by said method.
  • honeycomb exhaust gas treatment catalyst (L) Next, a honeycomb-like exhaust gas composed of a honeycomb structure was produced in the same manner as in Example 1 except that this titanium-containing granular powder (l) was used instead of the titanium-containing granular powder (a) described in Example 1. A treated catalyst (L) was prepared.
  • Example 13 ⁇ Titanium-containing granular powder (m) and honeycomb-shaped exhaust gas treatment catalyst (M)> (1) Titanium-containing granular powder (m) Titanium-containing 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 (added amount: 0.562 kg). A granular powder (m) was obtained. Next, a value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (m) thus obtained by the atomic weight is obtained.
  • a value C obtained by dividing a nitrogen atom which is an element constituting the additive (molybdenum disulfide) by its atomic weight was determined.
  • the values A and C were 297 and 6.95, respectively, and the ratio (C / A) was 2.34 ⁇ 10 ⁇ 2 .
  • the titanium-containing granular powder (m) was measured by the X-ray diffraction shown above, the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure, and the ratio of the peak intensities (P 1 / P 0 ) was 0.97.
  • honeycomb exhaust gas treatment catalyst Next, a honeycomb-shaped exhaust gas composed of a honeycomb structure was produced in the same manner as in Example 1 except that this titanium-containing granular powder (m) was used instead of the titanium-containing granular powder (a) described in Example 1. A treated catalyst (M) was prepared.
  • a value D obtained by dividing a nitrogen atom which is an element constituting the additive (molybdenum pentachloride) by its atomic weight was determined.
  • the values A and D were 297 and 17.4, respectively, and the ratio (D / A) was 5.84 ⁇ 10 ⁇ 2 .
  • the titanium-containing granular powder (n) was measured by the X-ray diffraction shown above, the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure, and the ratio of the peak intensities (P 1 / P 0 ) was 0.98.
  • honeycomb exhaust gas treatment catalyst (N) Next, a honeycomb-like exhaust gas composed of a honeycomb structure was produced in the same manner as in Example 1 except that this titanium-containing granular powder (n) was used instead of the titanium-containing granular powder (a) described in Example 1. A treated catalyst (N) was prepared.
  • a value B obtained by dividing a nitrogen atom which is an element constituting the additive (ammonium molybdate) by its atomic weight was obtained.
  • the values A and B were 282 and 7.45, respectively, and the ratio (B / A) was 2.64 ⁇ 10 ⁇ 2 .
  • the titanium-containing granular powder (o) was measured by the X-ray diffraction shown above, the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure, and the ratio of the peak intensities (P 1 / P 0 ) was 0.90. Furthermore, it was 85 m ⁇ 2 > / g when the specific surface area of the said titanium containing granular powder was measured by said method.
  • honeycomb exhaust gas treatment catalyst (O) Next, a honeycomb-shaped exhaust gas comprising a honeycomb structure was produced in the same manner as in Example 1 except that this titanium-containing granular powder (o) was used instead of the titanium-containing granular powder (a) described in Example 1. A treated catalyst (O) was prepared.
  • Titanium-containing granular powder (p) Titanium was prepared in the same manner as in Example 1 except that the additive added to the granular powder (e ′) of the composite oxide obtained in Example 5 was changed to ammonium molybdate (amount added: 3.07 kg). The contained granular powder (p) was obtained. Next, a value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (p) thus obtained by the atomic weight is obtained.
  • a value B obtained by dividing a nitrogen atom which is an element constituting the additive (ammonium molybdate) by its atomic weight was obtained.
  • the values A and B were 250 and 14.9, respectively, and the ratio (B / A) was 5.95 ⁇ 10 ⁇ 2 .
  • the titanium-containing granular powder (p) was measured by the X-ray diffraction shown above, the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure, and the ratio of the peak intensities (P 1 / P 0 ) was 0.83. Furthermore, it was 78 m ⁇ 2 > / g when the specific surface area of the said titanium containing granular powder was measured by said method.
  • honeycomb exhaust gas treatment catalyst (P) Next, a honeycomb-shaped exhaust gas composed of a honeycomb structure was produced in the same manner as in Example 1 except that this titanium-containing granular powder (p) was used instead of the titanium-containing granular powder (a) described in Example 1. A treated catalyst (P) was prepared.
  • the granular powder of titanium dioxide and ammonium paratungstate prepared in this manner is crushed using a ball mill, and 99.9% by mass or more of the total amount of titanium dioxide and ammonium paratungstate have a particle size of 45 ⁇ m or less.
  • Granular powder (r) was obtained.
  • the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the granular powder (r) of titanium dioxide and ammonium paratungstate thus obtained is divided by the atomic weight.
  • a value A obtained by dividing the nitrogen atom, which is an element constituting the additive (ammonium paratungstate), by its atomic weight was obtained.
  • the values A and B were 297 and 4.49, respectively, and the ratio (B / A) was 1.51 ⁇ 10 ⁇ 2 .
  • the granular powder (r) of titanium dioxide and ammonium paratungstate was measured by the X-ray diffraction shown above, the titanium oxide contained in the granular powder of titanium dioxide and ammonium paratungstate was anatase type.
  • the peak intensity ratio (P 1 / P 0 ) was 0.97. Furthermore, it was 95 m ⁇ 2 > / g when the specific surface area of the granular powder of the said titanium dioxide and ammonium paratungstate was measured by said method.
  • honeycomb exhaust gas treatment catalyst (R) Next, in place of the titanium-containing granular powder (a) described in Example 1, this honeycomb and ammonium paratungstate granular powder (r) was used in the same manner as in Example 1 to obtain a honeycomb structure.
  • a honeycomb-shaped exhaust gas treatment catalyst (R) comprising a body was prepared.
  • the obtained value A was determined, and further the value B obtained by dividing the nitrogen atom, which is an element constituting the additive (ammonium paratungstate), by its atomic weight was determined.
  • the values A and B were 282 and 8.99, respectively, and the ratio (B / A) was 3.19 ⁇ 10 ⁇ 2 .
  • the titanium oxide contained in the granular powder of titanium dioxide and ammonium paratungstate was anatase type.
  • the peak intensity ratio (P 1 / P 0 ) was 0.92.
  • a value A obtained by dividing the nitrogen atom, which is an element constituting the additive (ammonium paratungstate), by its atomic weight was obtained.
  • the values A and B were 250 and 18.0, respectively, and the ratio (B / A) was 7.18 ⁇ 10 ⁇ 2 .
  • the titanium oxide contained in the granular powder of titanium dioxide and ammonium paratungstate was anatase type.
  • the peak intensity ratio (P 1 / P 0 ) was 0.80.
  • honeycomb exhaust gas treatment catalyst (V) Subsequently, in place of the titanium-containing granular powder (a) described in Example 1, this honeycomb and ammonium paratungstate granular powder (v) was used in the same manner as in Example 1 to obtain a honeycomb structure.
  • a honeycomb-shaped exhaust gas treatment catalyst (V) comprising a body was prepared.
  • honeycomb exhaust gas treatment catalyst (W) Next, a honeycomb structure was formed in the same manner as in Example 1 except that this composite oxide granular powder (w) was used instead of the titanium-containing granular powder (a) described in Example 1. A honeycomb-shaped exhaust gas treatment catalyst (W) was prepared.
  • honeycomb exhaust gas treatment catalyst (X) Next, a honeycomb structure was formed in the same manner as in Example 1 except that this composite oxide granular powder (x) was used instead of the titanium-containing granular powder (a) described in Example 1. A honeycomb-shaped exhaust gas treatment catalyst (X) was prepared.
  • honeycomb exhaust gas treatment catalyst (Y) Next, a honeycomb structure was formed by the same method as in Example 1 except that this composite oxide granular powder (y) was used instead of the titanium-containing granular powder (a) described in Example 1. A honeycomb-shaped exhaust gas treatment catalyst (Y) was prepared.
  • Titanium-containing granular powder (z) and honeycomb-shaped exhaust gas treatment catalyst (Z)> Titanium-containing granular powder (z)
  • the metatitanic acid slurry was changed to 15.0 kg in terms of titanium dioxide and the addition amount of ammonium paratungstate was changed to 0.845 kg. Except for the above, a composite oxide granular powder (z ′) was obtained in the same manner as in Example 1.
  • a titanium-containing granular powder (z) was prepared in the same manner as in Example 1 except that the additive added to the granular powder (z ′) of the composite oxide was changed to 11.3 kg of ammonium molybdate. .
  • a value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (z) thus obtained by the atomic weight is obtained.
  • a value B obtained by dividing a nitrogen atom which is an element constituting the additive (ammonium molybdate) by its atomic weight was determined.
  • the values A and B were 188 and 55.1, respectively, and the ratio (B / A) was 2.93 ⁇ 10 ⁇ 1 .
  • Titanium-containing granular powder, composite oxide, and mixture of titanium powder and ammonium paratungstate (hereinafter collectively referred to as “titanium-containing granular powder etc.”) A to F of (A) to (z) above
  • the values are shown in (Table 1), the specific surface area (SA) for the titanium-containing granular powders (a) to (z), the ratio of the peak intensity of the (101) plane of the anatase type crystal (P 1 / P 0 ), Specific surface area (SA), pore volume (PV), and moldability test results of honeycomb-shaped exhaust gas treatment catalysts (A) to (Z), denitration rate, wear rate, heat resistance ((101 The ratio (P 1 ′ / P 1 ) of the peak intensity of the surface) is shown in (Table 2).
  • the specific surface area of the complex oxide of (SA) is 70 ⁇ 95m 2 / g, both of which fall within the range of 40 ⁇ 300m 2 / g.
  • these titanium-containing granular powders have a ratio (P 1 / P 0 ) of the peak intensity of the (101) plane of the anatase type crystal to the reference powder of titanium dioxide within the range of 0.75 to 0.98, All are within the range of 0.30 to 1.3.
  • honeycomb-shaped exhaust gas treatment catalysts (A) to (P) according to Examples 1 to 16 were prepared.
  • the honeycomb structures were the 10th and later, and no honeycomb defects occurred in Examples 2 to 5 and 15 to 16.
  • 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 the content of titanium and the addition amount of the additive were changed, tungsten disulfide
  • B / A or C / A, D / A described above was used.

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Abstract

La présente invention a pour objectif de fournir : une poudre granulée contenant du titane qui possède une bonne aptitude au moulage en structures en nid d'abeilles, présente une résistance élevée à l'abrasion et une faible diminution de la surface spécifique après cuisson ; un procédé pour la production de la poudre granulée ; un catalyseur de type en nid d'abeilles destiné à traiter les gaz d'échappement, ledit catalyseur de type en nid d'abeilles étant obtenu à partir de la poudre granulée ; et un procédé de production du catalyseur de type en nid d'abeilles. Pour ce faire, l'invention concerne une poudre granulée contenant du titane qui comprend, dans un rapport prédéfini, un oxyde composite contenant du titane conjointement avec du tungstène et/ou du molybdène, et au moins un type d'additif choisi parmi un composé azoté contenant du tungstène ou du molybdène, un composé du soufre contenant du tungstène ou du molybdène et un composé chloré contenant du tungstène ou du molybdène. L'invention concerne également un catalyseur de type en nid d'abeilles destiné à traiter des gaz d'échappement qui est obtenu par moulage de la poudre granulée en une structure en nid d'abeilles.
PCT/JP2012/008353 2011-12-27 2012-12-27 Poudre granulée contenant du titane et son procédé de production, et catalyseur de traitement de gaz d'échappement utilisant celle-ci et son procédé de production WO2013099253A1 (fr)

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US20130205743A1 (en) * 2012-02-13 2013-08-15 Anatoly Sobolevskiy SELECTIVE CATALYTIC REDUCTION SYSTEM AND PROCESS FOR CONTROL OF NOx EMISSIONS IN A SULFUR-CONTAINING GAS STREAM
CN105214482A (zh) * 2015-11-14 2016-01-06 华玉叶 一种家用煤炉烟气净化方法

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JP6441140B2 (ja) * 2014-03-28 2018-12-19 日揮触媒化成株式会社 使用済み触媒を用いた酸化チタン系微粉末の製造方法および該粉末を用いた排ガス処理触媒の製造方法
KR102134568B1 (ko) * 2016-02-24 2020-07-16 미쯔비시 케미컬 주식회사 다공형 압출 다이스, 금속 화합물 압출 성형체의 제조 방법, 불포화 알데히드 및/또는 불포화 카르복실산 제조용 촉매 압출 성형체의 제조 방법, 그리고 불포화 알데히드 및/또는 불포화 카르복실산의 제조 방법
CN111229291B (zh) * 2020-03-24 2021-02-09 苏州道一至诚纳米材料技术有限公司 一种复合式非贵金属脱硝催化剂及其制备方法

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