WO2014104071A1 - Modified titanium oxide fine particle powder for molded bodies, composition for molded bodies, and molded body - Google Patents
Modified titanium oxide fine particle powder for molded bodies, composition for molded bodies, and molded body Download PDFInfo
- Publication number
- WO2014104071A1 WO2014104071A1 PCT/JP2013/084607 JP2013084607W WO2014104071A1 WO 2014104071 A1 WO2014104071 A1 WO 2014104071A1 JP 2013084607 W JP2013084607 W JP 2013084607W WO 2014104071 A1 WO2014104071 A1 WO 2014104071A1
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- WO
- WIPO (PCT)
- Prior art keywords
- titanium oxide
- molded body
- fine particle
- particle powder
- content
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- 239000010419 fine particle Substances 0.000 title claims abstract description 178
- 239000000843 powder Substances 0.000 title claims abstract description 151
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 239000000203 mixture Substances 0.000 title claims description 142
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 72
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 72
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- 229960002969 oleic acid Drugs 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
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- 238000002407 reforming Methods 0.000 description 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
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Images
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- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
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Definitions
- the present invention relates to a modified titanium oxide fine particle powder for a molded body, a composition for a molded body using the fine powder, and a molded body.
- the ceramic molded body is formed by molding a ceramic molding composition containing ceramic powder by a molding method such as extrusion molding, casting molding, and compression molding (also referred to as tableting molding), followed by a drying step and further firing. It is manufactured through a process.
- Various shapes such as tablet shape, ring shape, pipe shape, honeycomb (honeycomb) shape, etc. are known as the shape of the extrusion molding, and it is used as a catalyst carrier or a catalyst.
- pollutants particularly NO x
- a honeycomb catalyst as a selective reduction type NO x catalyst (hereinafter referred to as SCR catalyst).
- a honeycomb formed body is manufactured by extruding a ceramic powder and a composition containing a catalyst component source through a die, drying, and then firing.
- a ceramic powder and a composition containing a catalyst component source are used to extrusion a honeycomb formed body.
- extrusion is difficult or exfoliation may occur during extrusion molding, and then there is a problem of significant shrinkage or cracking during drying and firing.
- Patent Document 1 JP 2009-226583 A
- Patent Document 2 contains (a) a polyalkylene glycol fatty acid ester and (b) a linear unsaturated fatty acid having 12 to 22 carbon atoms, the ratio of which is expressed by mass ratio.
- Patent Document 2 there is no particular limitation on the method for adding and using the ceramic extrusion additive, and the addition method may be added to the ceramic raw material powder or may be added during kneading.
- Honeycomb catalysts are required to increase the number of pitches for further performance improvement or economic improvement, as well as to improve moldability, crack suppression, strength, wear resistance, etc., and catalyst performance. There is a need for weight reduction and thinning.
- the present inventors have intensively studied. As a result, when a predetermined amount of a specific modifier is supported in advance on the titanium oxide-based fine particle powder, the moldability is improved and cracks are improved. It has been found that effects such as suppression, strength, wear resistance, etc. can be obtained, and on the other hand, by improving the moldability, it can be made thinner and the number of pitches can be increased without lowering strength, wear resistance, etc.
- the present invention has been completed.
- Titanium oxide-based fine particles are modified with a modifying agent composed of a fatty acid and / or a fatty acid ester, and the content of the modifying agent is 0.01 to 1
- a modified titanium oxide fine particle powder for molded bodies characterized by being in the range of 5% by weight.
- Titanium oxide fine particles contain at least one oxide selected from tungsten oxide (WO 3 ), molybdenum oxide (MoO 3 ), silicon oxide (SiO 2 ), and zirconium oxide (ZrO 2 ) together with titanium oxide.
- W (%) The weight reduction rate (W (%)) when the temperature was raised from 30 ° C. to 100 ° C. in the suggested thermal analysis of the titanium oxide fine particles with the water adjusted to 15% by weight, and the water adjusted to 15% by weight and said producing molded modified titanium oxide-based fine powder weight loss when heated to 100 ° C. from 30 ° C.
- the content of the active ingredient precursor compound is in the range of 0.0006 to 12.8% by weight in terms of oxide,
- a molding composition wherein the total solid concentration is in the range of 60 to 85% by weight.
- the active component precursor compound is at least one selected from the group consisting of V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, and Ir.
- [11] (i) Modified titanium oxide-based fine particle powder for molded article according to the above [1] to [6], (ii) reinforcement, (iii) containing an active ingredient (i) the content of the modified titanium oxide fine particle powder for molding is in the range of 55 to 95% by weight, and (ii) the content of the reinforcing material is in the range of 3 to 15% by weight (Iii) A molded product characterized in that the content of the active ingredient is in the range of 0.001 to 15% by weight as an oxide.
- the molded body is a honeycomb molded body, the honeycomb has an outer diameter in the range of 30 to 400 mm, a length in the range of 3 to 1500 mm, a pitch in the range of 6 to 500 cpsi, and a wall thickness Is in the range of 0.1 to 1.5 mm, [11] or [12].
- the active component is a metal of at least one element selected from V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, Ir, or The molded article according to [11] to [13], which is a metal oxide.
- the molded article according to [13] wherein the thickness is in the range of 0.1 to 0.3 mm.
- the moldability is improved, and even if the number of pitches is increased, it is possible to reduce the thickness and weight.
- the weight reduction curve of the sample of Example 1, Example 6, the comparative example 1, and the comparative example 4 is shown.
- the endothermic curves of the samples of Example 1, Example 6, Comparative Example 1 and Comparative Example 4 are shown.
- the modified titanium oxide fine particle powder for a molded body of the present invention is composed of titanium oxide-based fine particles, and the titanium oxide-based fine particles are modified with a modifier composed of a fatty acid and / or a fatty acid ester.
- Titanium oxide fine particles Titanium oxide fine particles are used as the titanium oxide fine particles used in the present invention. Further, composite titanium oxide-based fine particles containing at least one oxide selected from tungsten oxide (WO 3 ), molybdenum oxide (MO 3 ), silicon oxide (SiO 2 ), and zirconium oxide (ZrO 2 ) can be used. . When tungsten oxide (WO 3 ), molybdenum oxide (MO 3 ), silicon oxide (SiO 2 ), zirconium oxide (ZrO 2 ), etc. are contained, the content of oxide other than titanium oxide is 40 wt% or less as an oxide, Furthermore, it is preferable that it exists in the range of 30 weight% or less.
- Modifiers As the modifiers used in the present invention, fatty acids and / or fatty acid esters are used.
- the fatty acid is preferably a saturated fatty acid represented by the following formula (1) and / or an unsaturated fatty acid represented by the following formula (2).
- saturated fatty acid examples include stearic acid, lauric acid, myristic acid, behenic acid, arachidic acid, lignoceric acid, palmitic acid and the like, and mixtures thereof.
- examples of unsaturated fatty acids include oleic acid, arachidonic acid, linoleic acid, linolenic acid, icosapentaenoic acid, docosahexaenoic acid, and the like, and mixtures thereof.
- glycerin fatty acid ester is preferable and represented by the following formula.
- Specific examples include stearic acid monoglyceride, palmitic acid monoglyceride, oleic acid monoglyceride, stearic acid diglyceride, oleic acid diglyceride, behenic acid monoglyceride, caprylic acid monoglyceride, caprylic acid diglyceride, caprylic acid triglyceride, and the like.
- the content of the modifier in the modified titanium oxide fine particle powder for molded bodies is preferably in the range of 0.01 to 1.5% by weight, more preferably 0.02 to 1.0% by weight.
- the content of the modifying agent in the modified titanium oxide fine particle powder for molded bodies is small, the moldability, particularly the moldability improvement effect during extrusion molding may not be sufficiently obtained.
- the content of the modifier is too large, the pore volume of the molded body obtained when a molded body described later is prepared tends to be large, and the compression strength may be insufficient.
- a molded product having excellent moldability and excellent compressive strength, abrasion resistance, crack resistance, etc. is prepared. Can do.
- it is excellent in moldability it is possible to prepare a molded body having a complicated structure such as a honeycomb molded body. For this reason, it is possible to prepare a lightweight honeycomb molded body having a small thickness.
- the modified titanium oxide fine particle powder for a molded product is an aggregate of modified titanium oxide fine particles, and the average particle diameter of the modified titanium oxide fine particles before modification is 0.03 to 2.0 ⁇ m, and more preferably, 0.0. It is preferably in the range of 30 to 1.50 ⁇ m.
- the average particle size of the modified titanium oxide fine particles is preferably in the range of 0.03 to 2.5 ⁇ m, more preferably 0.30 to 2.0 ⁇ m.
- the surface of the titanium oxide fine particles is coated when the modifier is large, or the surface of the titanium oxide fine particles is coated when the modifier is small. It is adsorbed on the part.
- the moldability is improved by the presence of the modifier on the surface of the titanium oxide-based fine particles.
- the average particle diameter of the modified titanium oxide fine particles is in the above range, the moldability is excellent, and the resulting molded article is excellent in compressive strength, wear resistance, crack resistance, and the like.
- Such a modified titanium oxide fine particle powder for a molded body is produced as follows.
- a modified titanium oxide-based fine particle powder for a molded product can be prepared by mixing a predetermined amount of a modifier with the titanium oxide-based fine particles having the predetermined average particle diameter.
- the mixing method is not particularly limited as long as it can be uniformly mixed with the titanium oxide-based fine particles as much as possible, and a conventionally known mixing method can be employed.
- a kneader for example, a blender, a mixer, etc. are mentioned.
- the heating temperature is generally in the range of 40 to 120 ° C., although it varies depending on the type of modifier (melting point, etc.). Further, a volatile solvent such as ethanol may be used at the time of reforming.
- the mixing time varies depending on the temperature, but is generally 0.25 to 5 hours.
- W (%) weight reduction rate accompanying water desorption when the temperature is raised from 30 ° C. to 100 ° C. in the suggested thermal analysis of the titanium oxide fine particles adjusted to 15% by weight of water
- Weight reduction rate (W ST (%)) due to desorption of water when the temperature is raised from 30 ° C. to 100 ° C. in the suggested thermal analysis of the modified titanium oxide fine particle powder for molded bodies adjusted to 15% by weight
- the ratio (W ST (%)) / (W (%)) is 1.02 to 1.20, preferably 1.03 to 1.15.
- the weight reduction ratio in the suggested thermal analysis of the modified titanium oxide fine particle powder for molded bodies increases is not clear, if the weight reduction ratio ratio is in the above range, the composition for molded bodies described later Even when the raw material mixture has the same water content during kneading and kneading at the time of kneading around 100 ° C., the apparent water content is high due to the water desorbed by heating around 100 ° C. It is assumed that the composition for kneading and kneading is enhanced and a composition for a molded body having excellent moldability can be prepared.
- the modified titanium oxide fine particle powder for molded bodies according to the present invention not only has a large amount of water desorption when the temperature is raised from 30 ° C. to 100 ° C. There is a tendency for the bottom temperature to shift to higher temperatures.
- the weight reduction rate was measured by a suggested thermal analyzer (manufactured by Rigaku Corporation: differential differential thermal balance: TG8120 high-temperature type, high-sensitivity differential scanning calorimeter: DSC8230 standard type).
- the weight loss rate from 30 ° C. to 100 ° C. was determined by measuring at 5.0 ° C./min under an air atmosphere.
- the molding composition according to the present invention is a composition comprising (i) the modified titanium oxide fine particle powder for molding, (ii) a reinforcing material, and (iii) an active ingredient precursor compound.
- Modified titanium oxide-based fine particle powder for molded body The modified titanium oxide-based fine particle powder for molded body is used as the modified titanium oxide-based fine particle powder for molded body.
- the content of the modified titanium oxide fine particle powder for molded body in the molded body composition is preferably in the range of 33 to 80.8% by weight, more preferably 40 to 75% by weight as the solid content.
- the content of the modified titanium oxide fine particle powder for molded body in the molded body composition is small, molding becomes difficult and the catalyst performance, for example, the NO x removal rate of the selective reduction type NO x catalyst is insufficient. It may become.
- a fibrous reinforcing material such as glass fiber or ceramic fiber can be used.
- the content of the reinforcing material in the molding composition is preferably in the range of 1.8 to 12.8% by weight, more preferably 3 to 10% by weight as the solid content.
- the content of the reinforcing material in the molding composition is small, cracks due to shrinkage may occur during drying after extrusion molding. Even if the content of the reinforcing material in the molded body composition is too large, the reinforcing material may be clogged in the molding die during extrusion molding, which may impair the moldability.
- the active component precursor compound is selected from the group consisting of V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, and Ir. A compound of at least one element is used. Since the active component functions as a catalyst, it is appropriately selected according to the purpose.
- the content of the active ingredient precursor compound in the molding composition is preferably 0.0006 to 12.8% by weight, more preferably 0.3 to 10% by weight.
- the NO x removal rate may be insufficient when used as a selective reduction type NO x catalyst.
- the content of the active component precursor compound is large as an oxide, the moldability is lowered, and the compression strength and crack resistance of the resulting molded article are insufficient.
- a filler may be included. When such a filler is contained, it is possible to continuously perform extrusion molding and to prepare a molded body having excellent compressive strength and wear resistance.
- ceramic powder such as cordierite, alumina, zirconia, silicon nitride, silicon carbide, clay mineral can be used.
- the filler content in the molding composition is preferably in the range of 0.6 to 12.8% by weight, more preferably 3 to 10% by weight as the solid content.
- the content of the filler in the molded body composition is small, the continuous extrusion moldability is lowered, and it may be difficult to mold a long-sized molded body, particularly a long-sized honeycomb molded body.
- the mold may be frequently cleaned or replaced, which may reduce productivity and economy. Even if there is too much content of the filler in the composition for shaping
- composition for molded bodies of the present invention may contain an organic additive other than the modifier.
- organic additive examples include carboxymethyl cellulose, methyl cellulose, hydroxypropyl cellulose, hydroxymethyl cellulose, crystalline cellulose, polyethylene glycol, polypropylene glycol, polyethylene oxide and the like.
- the content of the organic additive in the molding composition is preferably in the range of 0.03 to 4.3% by weight, more preferably 0.5 to 2% by weight in the molding composition.
- the content of the organic additive in the molded body composition is small, the moldability becomes insufficient, and if it is too much, the pore volume of the resulting molded body catalyst becomes large and the compressive strength becomes insufficient. In some cases, cracks may occur during firing of the molded body.
- composition molded composition contains a solvent in addition to the above components.
- the solvent is appropriately selected depending on the purpose of use and the molding method.
- volatile solvents such as water, methanol, ethanol, propanol, and methyl ethyl ketone.
- water is preferable.
- the total solid content concentration of such a molding composition is in the range of 60 to 85% by weight, more preferably 65 to 75% by weight.
- the shape retention of the molded body before drying after the extrusion molding is weak and may be deformed.
- the molded body composition according to the present invention can be prepared in the same manner as in the prior art except that the above-described modified titanium oxide-based fine particle powder is used.
- Kneading and kneading are preferably performed under heating.
- the temperature at this time is preferably in the range of about 80 to 140 ° C., more preferably 90 to 130 ° C.
- By performing kneading and kneading in such a temperature range it is possible to prepare a molded article composition having excellent moldability.
- the molded body according to the present invention includes (i) the modified titanium oxide-based fine particle powder for molded body, (ii) a reinforcing material, and (iii) an active ingredient.
- the content of the modified titanium oxide fine particle powder for molded body in the molded body is preferably 55 to 95% by weight, more preferably 70 to 80% by weight.
- the content of the modified titanium oxide fine particle powder for the molded body in the molded body is small, molding may become difficult and the catalyst performance, for example, the NOx removal rate of the selective reduction type NOx catalyst may be insufficient. .
- the content of the reinforcing material in the molded body is preferably 3 to 15% by weight, more preferably 3 to 10% by weight as a solid content.
- the content of the reinforcing material in the molded body is small, the strength is low, and even if it is increased, the productivity is poor, and the active ingredient that functions as a catalyst decreases.
- the filler content in the molded body is preferably in the range of 1 to 15% by weight, more preferably 3 to 10% by weight as the solid content. If the filler content in the molded body is small, the strength is low, and even if the filler content is too large, the catalyst performance may be insufficient.
- the active component is derived from the precursor and is selected from V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, and Ir. At least one elemental metal or metal oxide is included.
- metals such as V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, Ir, and / or V 2 O 5 , WO 3 , MO 3 , Cr 2 O 3 , MnO 2 , Mn 2 O 3 , Fe 2 O 3 , NiO, CuO, Ag 2 O, AuO, PdO, Y 2 O 3 , CeO 2 , Nd 2 O 5 , In 2 O 3 And oxides such as IrO and mixtures thereof.
- the content of the active ingredient in the molded body is preferably in the range of 0.001 to 15% by weight, more preferably 0.3 to 12% by weight as an oxide. If the content of the active component is small, the NO x removal rate may be insufficient when used as a selective reduction type NO x catalyst. Even if there is too much content of an active ingredient, the compressive strength and crack resistance of a molded object will become inadequate.
- the moldability is high, and the obtained honeycomb molded body is excellent in strength and wear resistance.
- a molded product having a large number of pitches can be obtained.
- the outer diameter of the honeycomb molded body is preferably in the range of 30 to 400 mm.
- the external shape of the honeycomb is not particularly limited, such as a quadrangle, a hexagon, an octagon or more polygon, a circle, an ellipse, and the like, and can be appropriately selected depending on the application and usage.
- the length of the honeycomb molded body is preferably 3 to 1500 mm, more preferably 50 to 1300 mm.
- the length of the honeycomb molded body is less than 3 mm, it is difficult to manufacture.
- the pitch of the honeycomb molded body is preferably in the range of 6 to 500 cpsi, more preferably 15 to 200 cpsi.
- the pitch of the honeycomb molded body is less than 6 cpsi, the opening is large and the shape retaining property is weak, which makes it difficult to manufacture.
- the thickness of the honeycomb molded body is preferably in the range of 0.1 to 1.5 mm, more preferably 0.1 to 0.3 mm.
- a honeycomb molded body having a wall thickness of less than 0.1 mm is difficult to obtain even if the above-described modified titanium oxide-based fine particles are used.
- the thickness of the honeycomb molded body exceeds 1.5 mm, it can be formed by a conventionally known method without using the modified titanium oxide fine particles.
- the thickness of the honeycomb molded body is particularly preferably in the range of 0.1 to 0.3 mm.
- the present invention can be suitably used as a honeycomb that is thin and lightweight, has a large number of pitches, is excellent in strength, wear resistance, and compressive strength, is lightweight, and is economical.
- the molded body according to the present invention can be prepared by a conventionally known method using the aforementioned molded body composition.
- the shape of the molded body can be obtained by obtaining a conventionally known molded body such as pellets, beads, rings, and honeycombs, and by appropriately selecting a mold for extrusion molding at the time of molding.
- Example 1 Preparation of Modified Titanium Oxide Fine Particle Powder (1) for Molded Body 78.3 kg of metatitanic acid slurry (manufactured by Ishihara Sangyo Co., Ltd.) was charged into a stirring tank equipped with a heating reflux, and 2.82 kg of ammonium paratungstate was added.
- aqueous ammonia was added to adjust the pH to 9.5, and the mixture was aged with stirring at 95 ° C. for 1 hour. Then, this mixed slurry was cooled to 40 ° C., then filtered, and washed with water to prepare a washed cake having a solid content concentration (TiO 2 ⁇ WO 3 ) of 49% by weight.
- the washed cake contained 3.0 wt% SO 4 and 0.03 wt% Na 2 O on a dry basis.
- the average particle diameter of the titanium oxide fine particle powder (1) was measured by the following method, and the results are shown in the table.
- the composition (preparation standard) is shown in the table.
- the average particle size and particle size distribution were measured using a laser diffraction / scattering particle size distribution measuring apparatus (Horiba, Ltd .: LA-300). The conditions at this time were dispersed in an aqueous dispersion medium, irradiated with ultrasonic waves for 3 minutes, and the concentration was adjusted so that the laser light transmittance was 85%.
- Titanium oxide fine particle powder (1) was prepared.
- the average particle size and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (1) for molded bodies were measured, the results are shown in the table, the weight loss curve is shown in FIG. An endothermic curve is shown. At this time, the content of the modifying agent in the modified titanium oxide fine particle powder (1) for a molded body is 0.1% by weight based on the amount used.
- the average particle size was measured in the same manner as the titanium oxide fine particle powder (1).
- composition for molded body 1.28 kg of ammonium metavanadate as V 2 O 5 dissolved in 0.375 kg of monoethanolamine in 23.5 kg of modified titanium oxide fine particle powder (1) for molded body The solution was added, then ammonia water and water were added to adjust the pH of the mixed slurry to 9, and the mixture was kneaded for 0.5 hours while heating to 120 ° C. with a kneader. Thereafter, glass fiber (made by Owens Corning Co., Ltd .: chopped strand 03 DE, length 3 mm, fiber diameter 5 ⁇ m) 1.25 kg as a reinforcing material, acid clay 1.25 kg as a filler, and polyethylene oxide 0. 5 kg was added and the mixture was further kneaded for 1.5 hours to prepare a molding composition (1).
- glass fiber made by Owens Corning Co., Ltd .: chopped strand 03 DE, length 3 mm, fiber diameter 5 ⁇ m
- the content (usage standard) of each component in the molding composition (1) is shown in the table.
- the moisture content was measured with an infrared moisture meter (manufactured by Kett Chemical Laboratory: FD-610).
- a honeycomb structure (1) was prepared by extruding the composition for molded body (1) into a honeycomb shape with a vacuum extruder.
- the honeycomb structure (1) was dried at 60 ° C. for 48 hours, and then fired at 530 ° C. for 3 hours to prepare a honeycomb structure molded body (1).
- Each dimension of the molded body (1) was measured, and the results are shown in the table.
- the content (usage standard) of each component in the molded body (1) is shown in the table.
- the weight ratio of TiO 2 / WO 3 / V 2 O 5 / GF / acid clay is 77.4 / 8.6 / 4/5/5.
- the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (1) were measured by the following methods, and the results are shown in the table.
- the specific surface area of the honeycomb-shaped exhaust gas treatment catalyst is 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.
- ⁇ Pore volume> The pore volume was measured with a mercury intrusion method pore distribution measuring device (manufactured by QANTA CROME: PM-33GT1LP). The pressure range is 32 to 32200 psi.
- a (cm) and c (cm) indicate the dimensions of the two sides of the pressing surface of the sample.
- W (N) indicates the maximum load until the sample is completely destroyed by applying a load gradually.
- ⁇ Denitration catalyst performance test> The molded body (1) was cut into a honeycomb sample having 5 ⁇ 5 honeycomb holes and a length of 200 mm to obtain a test sample, and this test sample was filled in a flow reactor. A model gas having the following composition was passed through this flow reactor, and the denitration rate was measured. The denitration rate of nitrogen oxides (NO x ) in the gas before and after contact with the catalyst was determined by the following equation (5). At this time, the concentration of NO x was measured with a chemiluminescent nitrogen oxide analyzer.
- Denitration rate (%) ⁇ (NO x in non-contact gas (mass ppm) ⁇ NO x in gas after contact (mass ppm)) / NO x in non-contact gas (mass ppm) ⁇ ⁇ 100 ⁇ (5)
- Test conditions Catalyst shape: Honeycomb pore number 5 ⁇ 5, length 200mm Reaction temperature: 350 ° C., SV 40,000 hr ⁇ 1
- Modified titanium oxide-based fine particle powder (2) for molded body was the same as in Example 1 except that 4.7 g of stearic acid was used as a modifier.
- Example 2 Preparation of Modified Titanium Oxide Fine Particle Powder (2) for Molded Body Modified titanium oxide-based fine
- the average particle diameter and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (2) for molded bodies were measured, and the results are shown in the table.
- the content of the modifier is shown in the table.
- molding composition (2) was prepared in the same manner as in Example 1 except that the modified titanium oxide fine particle powder (2) for molding was used.
- the content of each component in the molding composition (2) is shown in the table.
- molded body (2) was prepared in the same manner as in Example 1 except that the molded body composition (2) was used.
- Example 3 Preparation of Modified Titanium Oxide Fine Particle Powder (3) for Molded Body Modified titanium oxide fine particle powder (3) for molded body was the same as in Example 1 except that 11.8 g of stearic acid was used as a modifier. was prepared.
- the average particle diameter and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (3) for molded bodies were measured, and the results are shown in the table.
- the content of the modifier is shown in the table.
- molding composition (3) was prepared in the same manner as in Example 1, except that the modified titanium oxide fine particle powder (3) for molding was used.
- molded body (3) was prepared in the same manner as in Example 1 except that the molded body composition (3) was used.
- Example 4 Preparation of Modified Titanium Oxide Fine Particle Powder (4) for Molded Body Modified Titanium Oxide Fine Particle Powder (4) for Molded Body in the same manner as in Example 1 except that 47.0 g of stearic acid was used as a modifier. Was prepared.
- the average particle diameter and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (4) for molded bodies were measured, and the results are shown in the table.
- the content of the modifier is shown in the table.
- molding composition (4) was prepared in the same manner as in Example 1, except that the modified titanium oxide fine particle powder (4) for molding was used.
- molded body (4) was prepared in the same manner as in Example 1, except that the molded body composition (4) was used.
- Example 5 Preparation of Modified Titanium Oxide Fine Particle Powder (5) for Molded Body Modified titanium oxide-based fine particle powder (5) for molded body was the same as in Example 1 except that 117.5 g of stearic acid was used as a modifier. Was prepared.
- the average particle diameter and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (5) for molded bodies were measured, and the results are shown in the table.
- the content of the modifier is shown in the table.
- molding composition (5) was prepared in the same manner as in Example 1 except that the modified titanium oxide fine particle powder (5) for molding was used.
- molded body (5) was prepared in the same manner as in Example 1 except that the molded body composition (5) was used.
- Example 6 Preparation of Modified Titanium Oxide Fine Particle Powder (6) for Molded Body
- modified titanium oxide fine particle powder (6) for molded body was prepared in the same manner except that 188 g of stearic acid was used as a modifier. did.
- the average particle diameter and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (6) for molded bodies were measured. The results are shown in the table, the weight loss curve is shown in FIG. 1, and the endotherm is shown in FIG. A curve is shown. Moreover, a composition (usage amount reference
- molding composition (6) was prepared in the same manner as in Example 1 except that the modified titanium oxide fine particle powder (6) for molding was used.
- the content (usage standard) of each component in the molding composition (6) is shown in the table.
- molded body (6) was prepared in the same manner as in Example 1 except that the molded body composition (6) was used.
- Example 7 Preparation of Modified Titanium Oxide Fine Particle Powder (7) for Molded Body Titanium oxide fine particle powder (7) was obtained in the same manner as in Example 1. In a thermostatic bath adjusted to 40 ⁇ 5 ° C. after mixing for 20 minutes with 23.5 kg of the resulting titanium oxide fine particle powder (7) and 100 ml of a solution of 23.5 g of stearic acid dissolved in ethanol as a modifier. Was dried to prepare a modified titanium oxide fine particle powder (7) for a molded body.
- the average particle diameter and water desorption rate (W ST %) of the modified titanium oxide fine particle powder (7) for molded bodies were measured, and the results are shown in the table.
- the content of the modifier is shown in the table.
- molding composition (7) was prepared in the same manner as in Example 1, except that the modified titanium oxide fine particle powder (7) for molding was used.
- molded body (7) was prepared in the same manner as in Example 1 except that the molded body composition (7) was used.
- Example 8 Preparation of Modified Titanium Oxide Fine Particle Powder (8) for Molded Body
- modified titanium oxide fine particle powder (8) for molded body was prepared in the same manner except that 23.5 g of lauric acid was used as a modifier. Prepared.
- the average particle diameter and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (8) for molded bodies were measured, and the results are shown in the table.
- the content of the modifier is shown in the table.
- molding composition (8) was prepared in the same manner as in Example 1, except that the modified titanium oxide fine particle powder (8) for molding was used.
- molded body (8) was prepared in the same manner as in Example 1, except that the molded body composition (8) was used.
- Example 9 Preparation of Modified Titanium Oxide Fine Particle Powder (9) for Molded Body
- modified titanium oxide fine particle powder (9) for molded body was prepared in the same manner except that 23.5 g of myristic acid was used as a modifier. Prepared.
- the average particle diameter and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (9) for molded bodies were measured, and the results are shown in the table.
- the content of the modifier is shown in the table.
- molding composition (9) was prepared in the same manner as in Example 1 except that the modified titanium oxide fine particle powder (9) for molding was used.
- the content of each component in the molding composition (9) is shown in the table.
- molded body (9) was prepared in the same manner as in Example 1 except that the molded body composition (9) was used.
- Example 10 Preparation of Modified Titanium Oxide Fine Particle Powder (10) for Molded Body
- modified titanium oxide fine particle powder (10) for molded body was prepared in the same manner except that 23.5 g of palmitic acid was used as a modifier. Prepared.
- the average particle diameter and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (10) for molded bodies were measured, and the results are shown in the table.
- the content of the modifier is shown in the table.
- molding composition (10) was prepared in the same manner as in Example 1 except that the modified titanium oxide fine particle powder (10) for molding was used.
- the content of each component in the molding composition (10) is shown in the table.
- molded body (10) was prepared in the same manner as in Example 1 except that the molded body composition (10) was used.
- Example 11 Preparation of Modified Titanium Oxide Fine Particle Powder (11) for Molded Body
- modified titanium oxide fine particle powder (11) for molded body was prepared in the same manner except that 23.5 g of oleic acid was used as a modifier. Prepared.
- the average particle diameter and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (11) for molded bodies were measured, and the results are shown in the table.
- the content of the modifier is shown in the table.
- molding composition (11) A molding composition (11) was prepared in the same manner as in Example 1 except that the modified titanium oxide fine particle powder (11) for molding was used. The content of each component in the molding composition (11) is shown in the table.
- molded body (11) was prepared in the same manner as in Example 1 except that the molded body composition (11) was used.
- Example 12 Preparation of Modified Titanium Oxide Fine Particle Powder (12) for Molded Body
- the modified titanium oxide fine particle powder (12) for molded body was the same as in Example 1 except that 23.5 g of stearic acid monoglyceride was used as a modifier. Was prepared.
- the average particle diameter and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (12) for molded bodies were measured, and the results are shown in the table.
- the content of the modifier is shown in the table.
- molding composition (12) A molding composition (12) was prepared in the same manner as in Example 1 except that the modified titanium oxide fine particle powder (12) for molding was used.
- the content of each component in the molding composition (12) is shown in the table.
- molded body (12) was prepared in the same manner as in Example 1 except that the molded body composition (12) was used.
- Example 13 Preparation of Modified Titanium Oxide Fine Particle Powder (13) for Molded Body 78.3 kg of metatitanic acid slurry (manufactured by Ishihara Sangyo Co., Ltd.) was charged into a stirring tank equipped with a heating reflux, and 1.97 kg of ammonium paratungstate and water After adding 18.8 kg of acid silicate solution having a SiO 2 concentration of 4.0 wt% prepared by dealkalizing the glass solution with a cation exchange resin, 30.5 kg of ammonia water having a concentration of 15 wt% was added.
- metatitanic acid slurry manufactured by Ishihara Sangyo Co., Ltd.
- the pH was adjusted to 9.5, and the mixture was further aged with stirring at 95 ° C. for 1 hour. Then, this mixed slurry was cooled to 40 ° C., then filtered, and washed with water to prepare a washing cake having a solid content concentration (TiO 2 ⁇ WO 3 ⁇ SiO 2 ) of 50% by weight.
- the washed cake contained 3.0 wt% SO 4 and 0.03 wt% Na 2 O on a dry basis.
- the average particle diameter of the titanium oxide fine particle powder (13) was measured, and the results are shown in the table.
- the composition (preparation standard) is shown in the table. Further, the moisture desorption rate (W%) was measured, and the results are shown in the table.
- a modified titanium oxide fine particle powder (13) for a molded body was prepared in the same manner except that the titanium oxide fine particle powder (13) was used in Example 1.
- the average particle diameter and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (13) for molded bodies were measured, and the results are shown in the table.
- the content of the modifier is shown in the table.
- molding composition (13) was prepared in the same manner as in Example 1, except that the modified titanium oxide fine particle powder (13) for molding was used.
- the content of each component in the molding composition (13) is shown in the table.
- molded body (13) was prepared in the same manner as in Example 1, except that the molded body composition (13) was used.
- the average particle diameter of the titanium oxide fine particle powder (R1) for molded bodies for molded bodies was measured, and the results are shown in the table.
- molding composition (R1) A molding composition (R1) was prepared in the same manner as in Example 1 except that the titanium oxide fine particle powder (R1) for molding was used.
- the content of each component in the molding composition (R1) is shown in the table.
- the average particle diameter of the titanium oxide fine particle powder (R2) for molding was measured, and the results are shown in the table.
- molded body composition (R2) was prepared in the same manner as in Example 1, except that the molded body titanium oxide fine particle powder (R2) was used.
- the content of each component in the molding composition (R2) is shown in the table.
- composition for molding (R3) 1. 23.5 kg of titanium oxide fine particle powder (1) prepared in the same manner as in Example 1, 0.375 kg of monoethanolamine, and ammonium metavanadate as V 2 O 5 . A solution in which 28 kg was dissolved was added, then 23.5 g of stearic acid was added, then ammonia water and water were added to adjust the pH of the mixed slurry to 9, and kneaded while heating to 110 ° C. with a kneader.
- the content of each component in the molding composition (R3) is shown in the table.
- molded body (R3) was prepared in the same manner as in Example 1 except that the molded body composition (R3) was used.
- the average particle diameter and moisture desorption rate (W ST %) of the titanium oxide fine particle powder (R5) for molded bodies were measured, and the results are shown in the table.
- the content of the modifier is shown in the table.
- Preparation of molding composition (R5) A molding composition (R5) was prepared in the same manner as in Example 1 except that the titanium oxide fine particle powder (R5) for molding was used.
- Example 14 Preparation of Modified Titanium Oxide Fine Particle Powder (14) for Molded Body 87.0 kg of metatitanic acid slurry (manufactured by Ishihara Sangyo Co., Ltd.) was charged into a stirring tank equipped with a heating reflux, and 20.5 kg of 15% by weight ammonia water In addition, the pH was adjusted to 9.5, and the mixture was further aged with stirring at 95 ° C. for 1 hour.
- metatitanic acid slurry manufactured by Ishihara Sangyo Co., Ltd.
- the mixed slurry was cooled to 40 ° C., then filtered and washed with water to prepare a washing cake having a solid content concentration (TiO 2 ) of 49% by weight.
- the washed cake contained 3.0 wt% SO 4 and 0.03 wt% Na 2 O on a dry basis.
- the average particle diameter of the titanium oxide fine particle powder (14) was measured, and the results are shown in the table.
- the composition (formulation standard) is shown in the table.
- the moisture desorption rate (W%) was measured, and the results are shown in the table.
- a modified titanium oxide fine particle powder (14) for a molded body was prepared in the same manner except that the titanium oxide fine particle powder (14) was used in Example 1.
- the average particle diameter and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (14) for molded bodies were measured, and the results are shown in the table.
- the content of the modifier is shown in the table.
- Preparation of molding composition (14) A molding composition (14) was prepared in the same manner as in Example 1, except that the modified titanium oxide fine particle powder (14) for molding was used. The content of each component in the molding composition (14) is shown in the table.
- Preparation of molded body (14) A molded body (14) was prepared in the same manner as in Example 1 except that the molded body composition (14) was used.
Abstract
[Problem] To provide a modified titanium oxide powder which is capable of producing a honeycomb molded body that can be reduced in thickness and weight even if the number of pitches is increased, while having excellent moldability, strength, wear resistance, cracking resistance and the like.
[Solution] A modified titanium oxide fine particle powder which is composed of fine titanium oxide particles and is characterized in that: the fine titanium oxide particles are modified with a modifying agent that is composed of a fatty acid and/or a fatty acid ester; and the content of the modifying agent is within the range of 0.01-1.0% by weight. A modified titanium oxide fine particle powder wherein the fatty acid is a saturated fatty acid represented by formula (1) and/or an unsaturated fatty acid represented by formula (2).
CnH2n-CO2H (1)
Cn'H2n'-2m+1-CO2H (2)
(In the formulae, n represents an integer of 4-23; n' represents an integer of 13-23; and m represents an integer of 1-6 that is the number of double bonds.)
Description
本発明は、成型体用改質酸化チタン系微粒子粉末および該微粉末を用いた成型体用組成物ならびに成型体に関する。
The present invention relates to a modified titanium oxide fine particle powder for a molded body, a composition for a molded body using the fine powder, and a molded body.
セラミックス成形体は、セラミックス粉体を含むセラミックス成型用組成物を、例えば、押出成型、鋳込み成型、及び圧縮成型（打錠成型ともいう）等の成型方法により成型した後、乾燥工程、更には焼成工程を経て製造されている。
The ceramic molded body is formed by molding a ceramic molding composition containing ceramic powder by a molding method such as extrusion molding, casting molding, and compression molding (also referred to as tableting molding), followed by a drying step and further firing. It is manufactured through a process.
押出成型体の形状としては、タブレット状、リング状、パイプ状、ハニカム（蜂の巣）状等種々の形状が知られており、触媒担体あるいは触媒等として用いられている。
Various shapes such as tablet shape, ring shape, pipe shape, honeycomb (honeycomb) shape, etc. are known as the shape of the extrusion molding, and it is used as a catalyst carrier or a catalyst.
例えば、発電所等の固定発生源、自動車等の移動発生源から排出される汚染物質とくにＮＯxは、選択還元型ＮＯx触媒（以下、ＳＣＲ触媒という）としてハニカム触媒を用いて処理されている。
For example, pollutants, particularly NO x , emitted from fixed sources such as power plants and mobile sources such as automobiles are treated using a honeycomb catalyst as a selective reduction type NO x catalyst (hereinafter referred to as SCR catalyst). .
従来、ハニカム成型体は、セラミックス粉末に、触媒成分源を配合した組成物を、ダイスを通して押出成型し、乾燥し、次いで焼成して製造している。しかしながら、押出成型する際に押出が困難であったり、剥離を生じたりする場合があり、ついで乾燥、焼成する際に大きく収縮したり、クラックを生じる問題があった。
Conventionally, a honeycomb formed body is manufactured by extruding a ceramic powder and a composition containing a catalyst component source through a die, drying, and then firing. However, there are cases where extrusion is difficult or exfoliation may occur during extrusion molding, and then there is a problem of significant shrinkage or cracking during drying and firing.
このため、本願出願人はハニカム成型用組成物に飽和脂肪酸を配合することによって乾燥時の収縮が低減できることを開示している。（特許文献１：特開２００９－２２６５８３号公報）
また、特開2011-240618号公報（特許文献２）には、（ａ）ポリアルキレングリコール脂肪酸エステルと（ｂ）炭素数１２～２２の直鎖不飽和脂肪酸を含有し、その比率が質量比で（ａ）：（ｂ）＝９６：４～９９：１である、セラミックス押出成形用添加剤が開示されている。特許文献２には、セラミックス押出成形用添加剤の添加方法及び使用形態について、特に制限はなく、添加方法としては、セラミックス原料粉体に添加してもよいし、混練中に添加してもよく、また杯土調製後に添加してもよい旨が開示されている。しかしながら、セラミックス原料粉体としてコージェライトを使用した実施例が開示されているだけであり、酸化チタン粒子を用いることについて、特にあらかじめ酸化チタン微粒子に押出成型用添加剤を添加した場合の効果についての記載も示唆もない。加えて、どのような粒子径のセラミックス原料粉体を用いるかについての記載もない。 For this reason, the applicant of the present application discloses that shrinkage during drying can be reduced by blending a saturated fatty acid into the honeycomb molding composition. (Patent Document 1: JP 2009-226583 A)
JP-A-2011-240618 (Patent Document 2) contains (a) a polyalkylene glycol fatty acid ester and (b) a linear unsaturated fatty acid having 12 to 22 carbon atoms, the ratio of which is expressed by mass ratio. A ceramic extrusion additive is disclosed wherein (a) :( b) = 96: 4 to 99: 1. InPatent Document 2, there is no particular limitation on the method for adding and using the ceramic extrusion additive, and the addition method may be added to the ceramic raw material powder or may be added during kneading. In addition, it is disclosed that it may be added after the preparation of the clay. However, only an example using cordierite as a ceramic raw material powder is disclosed. Regarding the use of titanium oxide particles, particularly the effect when an additive for extrusion molding is added to titanium oxide fine particles in advance. There is no description or suggestion. In addition, there is no description as to what particle size ceramic raw material powder is used.
また、特開2011-240618号公報（特許文献２）には、（ａ）ポリアルキレングリコール脂肪酸エステルと（ｂ）炭素数１２～２２の直鎖不飽和脂肪酸を含有し、その比率が質量比で（ａ）：（ｂ）＝９６：４～９９：１である、セラミックス押出成形用添加剤が開示されている。特許文献２には、セラミックス押出成形用添加剤の添加方法及び使用形態について、特に制限はなく、添加方法としては、セラミックス原料粉体に添加してもよいし、混練中に添加してもよく、また杯土調製後に添加してもよい旨が開示されている。しかしながら、セラミックス原料粉体としてコージェライトを使用した実施例が開示されているだけであり、酸化チタン粒子を用いることについて、特にあらかじめ酸化チタン微粒子に押出成型用添加剤を添加した場合の効果についての記載も示唆もない。加えて、どのような粒子径のセラミックス原料粉体を用いるかについての記載もない。 For this reason, the applicant of the present application discloses that shrinkage during drying can be reduced by blending a saturated fatty acid into the honeycomb molding composition. (Patent Document 1: JP 2009-226583 A)
JP-A-2011-240618 (Patent Document 2) contains (a) a polyalkylene glycol fatty acid ester and (b) a linear unsaturated fatty acid having 12 to 22 carbon atoms, the ratio of which is expressed by mass ratio. A ceramic extrusion additive is disclosed wherein (a) :( b) = 96: 4 to 99: 1. In
ハニカム触媒には、さらなる性能向上あるいは経済性の向上のためにピッチ数を増加させるとともに、成型性、クラックの抑制、強度、耐摩耗性等の向上、触媒性能向上が求められており、加えて、軽量化、薄肉化が求められている。
Honeycomb catalysts are required to increase the number of pitches for further performance improvement or economic improvement, as well as to improve moldability, crack suppression, strength, wear resistance, etc., and catalyst performance. There is a need for weight reduction and thinning.
そこで、このような課題を解決するために、本発明者らは鋭意検討した結果、酸化チタン系微粒子粉末にあらかじめ特定の改質剤を所定量担持して用いると、成型性が向上し、クラックの抑制、強度、耐摩耗性等の効果が得られ、他方、成型性の向上によって強度、耐摩耗性等を低下させることなく従来より薄肉化でき、ピッチ数を増加することができることを見出して本発明を完成するに至った。
［１］酸化チタン系微粒子からなり、かつ該酸化チタン系微粒子が、脂肪酸および／または脂肪酸エステルからなる改質剤で改質されてなり、かつ該改質剤の含有量が０．０１～１．５重量％の範囲にあることを特徴とする成型体用改質酸化チタン系微粒子粉末。
［２］前記脂肪酸が下記式(1)で表される飽和脂肪酸および／または下記式(2)で表される不飽和脂肪酸であることを特徴とする［１］の成型体用改質酸化チタン系微粒子粉末。 Therefore, in order to solve such problems, the present inventors have intensively studied. As a result, when a predetermined amount of a specific modifier is supported in advance on the titanium oxide-based fine particle powder, the moldability is improved and cracks are improved. It has been found that effects such as suppression, strength, wear resistance, etc. can be obtained, and on the other hand, by improving the moldability, it can be made thinner and the number of pitches can be increased without lowering strength, wear resistance, etc. The present invention has been completed.
[1] Titanium oxide-based fine particles, the titanium oxide-based fine particles are modified with a modifying agent composed of a fatty acid and / or a fatty acid ester, and the content of the modifying agent is 0.01 to 1 A modified titanium oxide fine particle powder for molded bodies, characterized by being in the range of 5% by weight.
[2] The modified titanium oxide for molded articles according to [1], wherein the fatty acid is a saturated fatty acid represented by the following formula (1) and / or an unsaturated fatty acid represented by the following formula (2): Fine particle powder.
［１］酸化チタン系微粒子からなり、かつ該酸化チタン系微粒子が、脂肪酸および／または脂肪酸エステルからなる改質剤で改質されてなり、かつ該改質剤の含有量が０．０１～１．５重量％の範囲にあることを特徴とする成型体用改質酸化チタン系微粒子粉末。
［２］前記脂肪酸が下記式(1)で表される飽和脂肪酸および／または下記式(2)で表される不飽和脂肪酸であることを特徴とする［１］の成型体用改質酸化チタン系微粒子粉末。 Therefore, in order to solve such problems, the present inventors have intensively studied. As a result, when a predetermined amount of a specific modifier is supported in advance on the titanium oxide-based fine particle powder, the moldability is improved and cracks are improved. It has been found that effects such as suppression, strength, wear resistance, etc. can be obtained, and on the other hand, by improving the moldability, it can be made thinner and the number of pitches can be increased without lowering strength, wear resistance, etc. The present invention has been completed.
[1] Titanium oxide-based fine particles, the titanium oxide-based fine particles are modified with a modifying agent composed of a fatty acid and / or a fatty acid ester, and the content of the modifying agent is 0.01 to 1 A modified titanium oxide fine particle powder for molded bodies, characterized by being in the range of 5% by weight.
[2] The modified titanium oxide for molded articles according to [1], wherein the fatty acid is a saturated fatty acid represented by the following formula (1) and / or an unsaturated fatty acid represented by the following formula (2): Fine particle powder.
ＣnＨ2n－ＣＯ2Ｈ・・・・・・・・・・・・・・・・（１）
（但し、ｎは４～２３の整数）
Ｃn'Ｈ2n'-2m+1－ＣＯ2Ｈ・・・・・・（２）
（但し、ｎ'は１３～２３の整数、ｍは２重結合の数を表す１～６の整数）
［３］前記改質酸化チタン系微粒子の平均粒子径が０．０３～２．５μｍの範囲にあることを特徴とする［１］の成型体用改質酸化チタン系微粒子粉末。
［４］前記酸化チタン系微粒子の平均粒子径が０．０３～２．０μｍの範囲にあることを特徴とする［１］の成型体用改質酸化チタン系微粒子粉末。
［５］酸化チタン系微粒子が、酸化チタンとともに、酸化タングステン（ＷＯ3）、酸化モリブデン（ＭoＯ3）、酸化珪素（ＳiＯ2）、酸化ジルコニウム（ＺrＯ2）から選ばれる酸化物の少なくとも１種を含み、酸化チタン系微粒子中の含有量が酸化物として０．５～４０重量％の範囲にあることを特徴とする［１］の成型体用改質酸化チタン系微粒子粉末。
［６］水分を１５重量％に調整した前記酸化チタン系微粒子の示唆熱分析における３０℃から１００℃に昇温した際の重量減少率（Ｗ（％））と、水分を１５重量％に調整した前記成型体用改質酸化チタン系微粒子粉末の示唆熱分析における３０℃から１００℃に昇温した際の重量減少率（ＷST（％））との重量減少率比（ＷST（％））／（Ｗ（％））が１．０２～１．２０の範囲にあることを特徴とする［１］～［５］の成型体用改質酸化チタン系微粒子粉末。
［７］(i)前記［１］～［６］の成型体用改質酸化チタン系微粒子粉末、
(ii)補強材、
(iii)活性成分前駆体化合物 を含む組成物であり、
該組成物中の(i) 成型体用改質酸化チタン系微粒子粉末の含有量が、３３～８０．８重量％の範囲にあり、(ii)補強材の含有量が１．８～１２．８重量％の範囲にあり、(iii)活性成分前駆体化合物の含有量が酸化物換算して０．０００６～１２．８重量％の範囲にあり、
全固形分濃度が６０～８５重量％の範囲にあることを特徴とする成型体用組成物。
［８］さらに、フィラーを含んでなり、該フィラーの含有量が固形分として０．６～１２．８重量％の範囲にあることを特徴とする［７］の成型体用組成物。
［９］さらに、前記改質剤以外の有機添加剤を０．０３～４．５重量％の範囲で含んでなることを特徴とする［７］の成型体用組成物。
［１０］前記活性成分前駆体化合物が、Ｖ、Ｗ、Ｍｏ、Ｃｒ、Ｍｎ、Ｆｅ、Ｎｉ、Ｃｕ、Ａｇ、Ａｕ、Ｐｄ、Ｙ、Ｃｅ、Ｎｄ、Ｉｎ、Ｉｒからなる群から選ばれる少なくとも１種の元素の化合物であることを特徴とする［７］の成型体用組成物。
［１１］(i)前記［１］～［６］の成型体用改質酸化チタン系微粒子粉末、
(ii)補強材、
(iii)活性成分 を含み
(i)成型体用改質酸化チタン系微粒子粉末の含有量が５５～９５重量％の範囲にあり、(ii)補強材の含有量が３～１５重量％の範囲にあり、(iii)活性成分の含有量が酸化物として０．００１～１５重量％の範囲にあることを特徴とする成型体。
［１２］さらに、フィラーを含み、該フィラーの含有量が１～１５重量％の範囲にあることを特徴とする［１１］の成型体。
［１３］前記成型体がハニカム成型体であり、該ハニカムの外径が３０～４００ｍｍの範囲にあり、長さが３～１５００ｍｍの範囲にあり、ピッチが６～５００ｃｐｓｉの範囲にあり、肉厚が０．１～１．５ｍｍの範囲にあることを特徴とする［１１］または［１２］の成型体。
［１４］前記活性成分が、Ｖ、Ｗ、Ｍｏ、Ｃｒ、Ｍｎ、Ｆｅ、Ｎｉ、Ｃｕ、Ａｇ、Ａｕ、Ｐｄ、Ｙ、Ｃｅ、Ｎｄ、Ｉｎ、Ｉｒから選ばれる少なくとも１種の元素の金属または金属酸化物であることを特徴とする［１１］～［１３］の成型体。
［１５］前記肉厚が０．１～０．３ｍｍの範囲にあることを特徴とする［１３］の成型体。 C n H 2n -CO 2 H (1)
(Where n is an integer from 4 to 23)
C n ′ H 2n′-2m + 1 —CO 2 H (2)
(Where n ′ is an integer from 13 to 23, m is an integer from 1 to 6 representing the number of double bonds)
[3] The modified titanium oxide fine particle powder for molding according to [1], wherein the average particle diameter of the modified titanium oxide fine particles is in the range of 0.03 to 2.5 μm.
[4] The modified titanium oxide fine particle powder for molding according to [1], wherein an average particle size of the titanium oxide fine particles is in the range of 0.03 to 2.0 μm.
[5] Titanium oxide fine particles contain at least one oxide selected from tungsten oxide (WO 3 ), molybdenum oxide (MoO 3 ), silicon oxide (SiO 2 ), and zirconium oxide (ZrO 2 ) together with titanium oxide. The modified titanium oxide fine particle powder for molding according to [1], wherein the content in the titanium oxide fine particles is in the range of 0.5 to 40% by weight as an oxide.
[6] The weight reduction rate (W (%)) when the temperature was raised from 30 ° C. to 100 ° C. in the suggested thermal analysis of the titanium oxide fine particles with the water adjusted to 15% by weight, and the water adjusted to 15% by weight and said producing molded modified titanium oxide-based fine powder weight loss when heated to 100 ° C. from 30 ° C. in differential thermal analysis (W ST (%)) weight loss ratio of (W ST (%) ) / (W (%)) is in the range of 1.02 to 1.20. [1] to [5] The modified titanium oxide fine particle powder for molded bodies according to [1] to [5].
[7] (i) Modified titanium oxide fine particle powders for molded bodies according to the above [1] to [6],
(ii) reinforcement,
(iii) a composition containing an active ingredient precursor compound,
In the composition, the content of (i) the modified titanium oxide fine particle powder for molded bodies is in the range of 33 to 80.8% by weight, and (ii) the content of the reinforcing material is 1.8 to 12. (Iii) the content of the active ingredient precursor compound is in the range of 0.0006 to 12.8% by weight in terms of oxide,
A molding composition, wherein the total solid concentration is in the range of 60 to 85% by weight.
[8] The molded article composition according to [7], further comprising a filler, wherein the filler content is in the range of 0.6 to 12.8 wt% as a solid content.
[9] The molding composition according to [7], further comprising an organic additive other than the modifier in an amount of 0.03 to 4.5% by weight.
[10] The active component precursor compound is at least one selected from the group consisting of V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, and Ir. [7] The molding composition according to [7], which is a compound of a seed element.
[11] (i) Modified titanium oxide-based fine particle powder for molded article according to the above [1] to [6],
(ii) reinforcement,
(iii) containing an active ingredient (i) the content of the modified titanium oxide fine particle powder for molding is in the range of 55 to 95% by weight, and (ii) the content of the reinforcing material is in the range of 3 to 15% by weight (Iii) A molded product characterized in that the content of the active ingredient is in the range of 0.001 to 15% by weight as an oxide.
[12] The molded article according to [11], further comprising a filler, wherein the filler content is in the range of 1 to 15% by weight.
[13] The molded body is a honeycomb molded body, the honeycomb has an outer diameter in the range of 30 to 400 mm, a length in the range of 3 to 1500 mm, a pitch in the range of 6 to 500 cpsi, and a wall thickness Is in the range of 0.1 to 1.5 mm, [11] or [12].
[14] The active component is a metal of at least one element selected from V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, Ir, or The molded article according to [11] to [13], which is a metal oxide.
[15] The molded article according to [13], wherein the thickness is in the range of 0.1 to 0.3 mm.
（但し、ｎは４～２３の整数）
Ｃn'Ｈ2n'-2m+1－ＣＯ2Ｈ・・・・・・（２）
（但し、ｎ'は１３～２３の整数、ｍは２重結合の数を表す１～６の整数）
［３］前記改質酸化チタン系微粒子の平均粒子径が０．０３～２．５μｍの範囲にあることを特徴とする［１］の成型体用改質酸化チタン系微粒子粉末。
［４］前記酸化チタン系微粒子の平均粒子径が０．０３～２．０μｍの範囲にあることを特徴とする［１］の成型体用改質酸化チタン系微粒子粉末。
［５］酸化チタン系微粒子が、酸化チタンとともに、酸化タングステン（ＷＯ3）、酸化モリブデン（ＭoＯ3）、酸化珪素（ＳiＯ2）、酸化ジルコニウム（ＺrＯ2）から選ばれる酸化物の少なくとも１種を含み、酸化チタン系微粒子中の含有量が酸化物として０．５～４０重量％の範囲にあることを特徴とする［１］の成型体用改質酸化チタン系微粒子粉末。
［６］水分を１５重量％に調整した前記酸化チタン系微粒子の示唆熱分析における３０℃から１００℃に昇温した際の重量減少率（Ｗ（％））と、水分を１５重量％に調整した前記成型体用改質酸化チタン系微粒子粉末の示唆熱分析における３０℃から１００℃に昇温した際の重量減少率（ＷST（％））との重量減少率比（ＷST（％））／（Ｗ（％））が１．０２～１．２０の範囲にあることを特徴とする［１］～［５］の成型体用改質酸化チタン系微粒子粉末。
［７］(i)前記［１］～［６］の成型体用改質酸化チタン系微粒子粉末、
(ii)補強材、
(iii)活性成分前駆体化合物 を含む組成物であり、
該組成物中の(i) 成型体用改質酸化チタン系微粒子粉末の含有量が、３３～８０．８重量％の範囲にあり、(ii)補強材の含有量が１．８～１２．８重量％の範囲にあり、(iii)活性成分前駆体化合物の含有量が酸化物換算して０．０００６～１２．８重量％の範囲にあり、
全固形分濃度が６０～８５重量％の範囲にあることを特徴とする成型体用組成物。
［８］さらに、フィラーを含んでなり、該フィラーの含有量が固形分として０．６～１２．８重量％の範囲にあることを特徴とする［７］の成型体用組成物。
［９］さらに、前記改質剤以外の有機添加剤を０．０３～４．５重量％の範囲で含んでなることを特徴とする［７］の成型体用組成物。
［１０］前記活性成分前駆体化合物が、Ｖ、Ｗ、Ｍｏ、Ｃｒ、Ｍｎ、Ｆｅ、Ｎｉ、Ｃｕ、Ａｇ、Ａｕ、Ｐｄ、Ｙ、Ｃｅ、Ｎｄ、Ｉｎ、Ｉｒからなる群から選ばれる少なくとも１種の元素の化合物であることを特徴とする［７］の成型体用組成物。
［１１］(i)前記［１］～［６］の成型体用改質酸化チタン系微粒子粉末、
(ii)補強材、
(iii)活性成分 を含み
(i)成型体用改質酸化チタン系微粒子粉末の含有量が５５～９５重量％の範囲にあり、(ii)補強材の含有量が３～１５重量％の範囲にあり、(iii)活性成分の含有量が酸化物として０．００１～１５重量％の範囲にあることを特徴とする成型体。
［１２］さらに、フィラーを含み、該フィラーの含有量が１～１５重量％の範囲にあることを特徴とする［１１］の成型体。
［１３］前記成型体がハニカム成型体であり、該ハニカムの外径が３０～４００ｍｍの範囲にあり、長さが３～１５００ｍｍの範囲にあり、ピッチが６～５００ｃｐｓｉの範囲にあり、肉厚が０．１～１．５ｍｍの範囲にあることを特徴とする［１１］または［１２］の成型体。
［１４］前記活性成分が、Ｖ、Ｗ、Ｍｏ、Ｃｒ、Ｍｎ、Ｆｅ、Ｎｉ、Ｃｕ、Ａｇ、Ａｕ、Ｐｄ、Ｙ、Ｃｅ、Ｎｄ、Ｉｎ、Ｉｒから選ばれる少なくとも１種の元素の金属または金属酸化物であることを特徴とする［１１］～［１３］の成型体。
［１５］前記肉厚が０．１～０．３ｍｍの範囲にあることを特徴とする［１３］の成型体。 C n H 2n -CO 2 H (1)
(Where n is an integer from 4 to 23)
C n ′ H 2n′-2m + 1 —CO 2 H (2)
(Where n ′ is an integer from 13 to 23, m is an integer from 1 to 6 representing the number of double bonds)
[3] The modified titanium oxide fine particle powder for molding according to [1], wherein the average particle diameter of the modified titanium oxide fine particles is in the range of 0.03 to 2.5 μm.
[4] The modified titanium oxide fine particle powder for molding according to [1], wherein an average particle size of the titanium oxide fine particles is in the range of 0.03 to 2.0 μm.
[5] Titanium oxide fine particles contain at least one oxide selected from tungsten oxide (WO 3 ), molybdenum oxide (MoO 3 ), silicon oxide (SiO 2 ), and zirconium oxide (ZrO 2 ) together with titanium oxide. The modified titanium oxide fine particle powder for molding according to [1], wherein the content in the titanium oxide fine particles is in the range of 0.5 to 40% by weight as an oxide.
[6] The weight reduction rate (W (%)) when the temperature was raised from 30 ° C. to 100 ° C. in the suggested thermal analysis of the titanium oxide fine particles with the water adjusted to 15% by weight, and the water adjusted to 15% by weight and said producing molded modified titanium oxide-based fine powder weight loss when heated to 100 ° C. from 30 ° C. in differential thermal analysis (W ST (%)) weight loss ratio of (W ST (%) ) / (W (%)) is in the range of 1.02 to 1.20. [1] to [5] The modified titanium oxide fine particle powder for molded bodies according to [1] to [5].
[7] (i) Modified titanium oxide fine particle powders for molded bodies according to the above [1] to [6],
(ii) reinforcement,
(iii) a composition containing an active ingredient precursor compound,
In the composition, the content of (i) the modified titanium oxide fine particle powder for molded bodies is in the range of 33 to 80.8% by weight, and (ii) the content of the reinforcing material is 1.8 to 12. (Iii) the content of the active ingredient precursor compound is in the range of 0.0006 to 12.8% by weight in terms of oxide,
A molding composition, wherein the total solid concentration is in the range of 60 to 85% by weight.
[8] The molded article composition according to [7], further comprising a filler, wherein the filler content is in the range of 0.6 to 12.8 wt% as a solid content.
[9] The molding composition according to [7], further comprising an organic additive other than the modifier in an amount of 0.03 to 4.5% by weight.
[10] The active component precursor compound is at least one selected from the group consisting of V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, and Ir. [7] The molding composition according to [7], which is a compound of a seed element.
[11] (i) Modified titanium oxide-based fine particle powder for molded article according to the above [1] to [6],
(ii) reinforcement,
(iii) containing an active ingredient (i) the content of the modified titanium oxide fine particle powder for molding is in the range of 55 to 95% by weight, and (ii) the content of the reinforcing material is in the range of 3 to 15% by weight (Iii) A molded product characterized in that the content of the active ingredient is in the range of 0.001 to 15% by weight as an oxide.
[12] The molded article according to [11], further comprising a filler, wherein the filler content is in the range of 1 to 15% by weight.
[13] The molded body is a honeycomb molded body, the honeycomb has an outer diameter in the range of 30 to 400 mm, a length in the range of 3 to 1500 mm, a pitch in the range of 6 to 500 cpsi, and a wall thickness Is in the range of 0.1 to 1.5 mm, [11] or [12].
[14] The active component is a metal of at least one element selected from V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, Ir, or The molded article according to [11] to [13], which is a metal oxide.
[15] The molded article according to [13], wherein the thickness is in the range of 0.1 to 0.3 mm.
本発明によれば、酸化チタン系微粒子粉末にあらかじめ特定の改質剤を所定量担持して用いているので、成型性が向上し、ピッチ数を多くしても、薄肉化・軽量化が可能であり、強度、耐摩耗性、耐クラック性等に優れたハニカム成型体を製造することが可能となる。
According to the present invention, since a predetermined amount of a specific modifier is supported in advance on the titanium oxide fine particle powder, the moldability is improved, and even if the number of pitches is increased, it is possible to reduce the thickness and weight. Thus, it becomes possible to manufacture a honeycomb molded body excellent in strength, wear resistance, crack resistance and the like.
以下、先ず、本発明の成型体用改質酸化チタン系微粒子粉末について具体的に説明する。
［成型体用改質酸化チタン系微粒子粉末］
本発明に係る成型体用改質酸化チタン系微粒子粉末は、酸化チタン系微粒子からなり、かつ該酸化チタン系微粒子が、脂肪酸および／または脂肪酸エステルからなる改質剤で改質されている。 Hereinafter, first, the modified titanium oxide fine particle powder for a molded body of the present invention will be specifically described.
[Modified titanium oxide fine particles for moldings]
The modified titanium oxide-based fine particle powder for molded bodies according to the present invention is composed of titanium oxide-based fine particles, and the titanium oxide-based fine particles are modified with a modifier composed of a fatty acid and / or a fatty acid ester.
［成型体用改質酸化チタン系微粒子粉末］
本発明に係る成型体用改質酸化チタン系微粒子粉末は、酸化チタン系微粒子からなり、かつ該酸化チタン系微粒子が、脂肪酸および／または脂肪酸エステルからなる改質剤で改質されている。 Hereinafter, first, the modified titanium oxide fine particle powder for a molded body of the present invention will be specifically described.
[Modified titanium oxide fine particles for moldings]
The modified titanium oxide-based fine particle powder for molded bodies according to the present invention is composed of titanium oxide-based fine particles, and the titanium oxide-based fine particles are modified with a modifier composed of a fatty acid and / or a fatty acid ester.
酸化チタン系微粒子
本発明に用いる酸化チタン系微粒子としては、酸化チタン微粒子が使用される。また、酸化タングステン（ＷＯ3）、酸化モリブデン（ＭＯ3）、酸化珪素（ＳｉＯ2）、酸化ジルコニウム（ＺｒＯ2）から選ばれる酸化物の少なくとも１種を含む複合酸化チタン系微粒子を用いることができる。 酸化タングステン（ＷＯ3）、酸化モリブデン（ＭＯ3）、酸化珪素（ＳｉＯ2）、酸化ジルコニウム（ＺｒＯ2）等を含む場合の酸化チタン以外の酸化物の含有量は酸化物として４０重量％以下、さらには３０重量％以下の範囲にあることが好ましい。 Titanium oxide fine particles Titanium oxide fine particles are used as the titanium oxide fine particles used in the present invention. Further, composite titanium oxide-based fine particles containing at least one oxide selected from tungsten oxide (WO 3 ), molybdenum oxide (MO 3 ), silicon oxide (SiO 2 ), and zirconium oxide (ZrO 2 ) can be used. . When tungsten oxide (WO 3 ), molybdenum oxide (MO 3 ), silicon oxide (SiO 2 ), zirconium oxide (ZrO 2 ), etc. are contained, the content of oxide other than titanium oxide is 40 wt% or less as an oxide, Furthermore, it is preferable that it exists in the range of 30 weight% or less.
本発明に用いる酸化チタン系微粒子としては、酸化チタン微粒子が使用される。また、酸化タングステン（ＷＯ3）、酸化モリブデン（ＭＯ3）、酸化珪素（ＳｉＯ2）、酸化ジルコニウム（ＺｒＯ2）から選ばれる酸化物の少なくとも１種を含む複合酸化チタン系微粒子を用いることができる。 酸化タングステン（ＷＯ3）、酸化モリブデン（ＭＯ3）、酸化珪素（ＳｉＯ2）、酸化ジルコニウム（ＺｒＯ2）等を含む場合の酸化チタン以外の酸化物の含有量は酸化物として４０重量％以下、さらには３０重量％以下の範囲にあることが好ましい。 Titanium oxide fine particles Titanium oxide fine particles are used as the titanium oxide fine particles used in the present invention. Further, composite titanium oxide-based fine particles containing at least one oxide selected from tungsten oxide (WO 3 ), molybdenum oxide (MO 3 ), silicon oxide (SiO 2 ), and zirconium oxide (ZrO 2 ) can be used. . When tungsten oxide (WO 3 ), molybdenum oxide (MO 3 ), silicon oxide (SiO 2 ), zirconium oxide (ZrO 2 ), etc. are contained, the content of oxide other than titanium oxide is 40 wt% or less as an oxide, Furthermore, it is preferable that it exists in the range of 30 weight% or less.
酸化チタン系微粒子中の前記酸化チタン以外の酸化物の含有量が多すぎると、改質酸化チタン系微粒子粉末を用いても成型が困難となる場合がある。
If the content of oxides other than the titanium oxide in the titanium oxide-based fine particles is too large, molding may be difficult even if the modified titanium oxide-based fine particle powder is used.
改質剤
本発明に用いる改質剤としては、脂肪酸および／または脂肪酸エステルが用いられる。 Modifiers As the modifiers used in the present invention, fatty acids and / or fatty acid esters are used.
本発明に用いる改質剤としては、脂肪酸および／または脂肪酸エステルが用いられる。 Modifiers As the modifiers used in the present invention, fatty acids and / or fatty acid esters are used.
前記脂肪酸は、下記式(1)で表される飽和脂肪酸および／または下記式(2)で表される不飽和脂肪酸であることが好ましい。
The fatty acid is preferably a saturated fatty acid represented by the following formula (1) and / or an unsaturated fatty acid represented by the following formula (2).
ＣnＨ2n－ＣＯ2Ｈ・・・・・・・・・・・・・・・・（１）
（但し、ｎは４～２３の整数）
Ｃn'Ｈ2n'-2m+1－ＣＯ2Ｈ・・・・・・（２）
（但し、ｎ'は１３～２３の整数、ｍは２重結合の数を表す１～６の整数）
飽和脂肪酸としては、具体的には、ステアリン酸、ラウリン酸、ミリスチン酸、ベヘン酸、アラキジン酸、リグノセリン酸、パルミチン酸等およびこれらの混合物が挙げられる。 C n H 2n -CO 2 H (1)
(Where n is an integer from 4 to 23)
C n ′ H 2n′-2m + 1 —CO 2 H (2)
(Where n ′ is an integer from 13 to 23, m is an integer from 1 to 6 representing the number of double bonds)
Specific examples of the saturated fatty acid include stearic acid, lauric acid, myristic acid, behenic acid, arachidic acid, lignoceric acid, palmitic acid and the like, and mixtures thereof.
（但し、ｎは４～２３の整数）
Ｃn'Ｈ2n'-2m+1－ＣＯ2Ｈ・・・・・・（２）
（但し、ｎ'は１３～２３の整数、ｍは２重結合の数を表す１～６の整数）
飽和脂肪酸としては、具体的には、ステアリン酸、ラウリン酸、ミリスチン酸、ベヘン酸、アラキジン酸、リグノセリン酸、パルミチン酸等およびこれらの混合物が挙げられる。 C n H 2n -CO 2 H (1)
(Where n is an integer from 4 to 23)
C n ′ H 2n′-2m + 1 —CO 2 H (2)
(Where n ′ is an integer from 13 to 23, m is an integer from 1 to 6 representing the number of double bonds)
Specific examples of the saturated fatty acid include stearic acid, lauric acid, myristic acid, behenic acid, arachidic acid, lignoceric acid, palmitic acid and the like, and mixtures thereof.
また、不飽和脂肪酸としては、オレイン酸、アラキドン酸、リノール酸、リノレン酸、イコサペンタエン酸、ドコサヘキサエン酸等およびこれらの混合物が挙げられる。
Also, examples of unsaturated fatty acids include oleic acid, arachidonic acid, linoleic acid, linolenic acid, icosapentaenoic acid, docosahexaenoic acid, and the like, and mixtures thereof.
脂肪酸エステルとしては、グリセリン脂肪酸エステルが好ましく、下記式で表される。
As the fatty acid ester, glycerin fatty acid ester is preferable and represented by the following formula.
成型体用改質酸化チタン系微粒子粉末中の前記改質剤の含有量は０．０１～１．５重量％、さらには０．０２～１．０重量％の範囲にあることが好ましい。
The content of the modifier in the modified titanium oxide fine particle powder for molded bodies is preferably in the range of 0.01 to 1.5% by weight, more preferably 0.02 to 1.0% by weight.
成型体用改質酸化チタン系微粒子粉末中の改質剤の含有量が少ないと、成型性、特に押出成型の際の成型性向上効果が充分得られない場合がある。改質剤の含有量が多すぎると、後述する成型体を調製した場合に得られる成型体の細孔容積が大きくなる傾向があり、圧縮強度が不充分となる場合がある。
If the content of the modifying agent in the modified titanium oxide fine particle powder for molded bodies is small, the moldability, particularly the moldability improvement effect during extrusion molding may not be sufficiently obtained. When the content of the modifier is too large, the pore volume of the molded body obtained when a molded body described later is prepared tends to be large, and the compression strength may be insufficient.
成型体用改質酸化チタン系微粒子粉末中の改質剤の含有量が前記範囲にあれば、成型性に優れ、圧縮強度、耐摩耗性、耐クラック性等に優れた成型体を調製することができる。特に、成型性に優れるためにハニカム成型体のような複雑な構造を有する成型体の調製が可能であり、このため、肉厚が薄い、軽量ハニカム成型体の調製が可能である。
If the content of the modifier in the modified titanium oxide fine particle powder for molded products is within the above range, a molded product having excellent moldability and excellent compressive strength, abrasion resistance, crack resistance, etc. is prepared. Can do. In particular, since it is excellent in moldability, it is possible to prepare a molded body having a complicated structure such as a honeycomb molded body. For this reason, it is possible to prepare a lightweight honeycomb molded body having a small thickness.
成型体用改質酸化チタン系微粒子粉末は改質酸化チタン系微粒子の凝集体であり、改質酸化チタン系微粒子の改質前の平均粒子径は０．０３～２．０μｍ、さらには０．３０～１．５０μｍの範囲にあることが好ましい。
The modified titanium oxide fine particle powder for a molded product is an aggregate of modified titanium oxide fine particles, and the average particle diameter of the modified titanium oxide fine particles before modification is 0.03 to 2.0 μm, and more preferably, 0.0. It is preferably in the range of 30 to 1.50 μm.
また、改質酸化チタン系微粒子の平均粒子径は０．０３～２．５μｍ、さらには０．３０～２．０μｍの範囲にあることが好ましい。
改質剤の含有量、酸化チタン微粒子の平均粒子径によっても異なるが、改質剤が多い場合は酸化チタン微粒子の表面を被覆したり、改質剤が少ない場合は酸化チタン微粒子の表面の一部に吸着等して存在している。このように、酸化チタン系微粒子の表面に改質剤が存在することによって成型性が向上する。 The average particle size of the modified titanium oxide fine particles is preferably in the range of 0.03 to 2.5 μm, more preferably 0.30 to 2.0 μm.
Depending on the content of the modifier and the average particle diameter of the titanium oxide fine particles, the surface of the titanium oxide fine particles is coated when the modifier is large, or the surface of the titanium oxide fine particles is coated when the modifier is small. It is adsorbed on the part. Thus, the moldability is improved by the presence of the modifier on the surface of the titanium oxide-based fine particles.
改質剤の含有量、酸化チタン微粒子の平均粒子径によっても異なるが、改質剤が多い場合は酸化チタン微粒子の表面を被覆したり、改質剤が少ない場合は酸化チタン微粒子の表面の一部に吸着等して存在している。このように、酸化チタン系微粒子の表面に改質剤が存在することによって成型性が向上する。 The average particle size of the modified titanium oxide fine particles is preferably in the range of 0.03 to 2.5 μm, more preferably 0.30 to 2.0 μm.
Depending on the content of the modifier and the average particle diameter of the titanium oxide fine particles, the surface of the titanium oxide fine particles is coated when the modifier is large, or the surface of the titanium oxide fine particles is coated when the modifier is small. It is adsorbed on the part. Thus, the moldability is improved by the presence of the modifier on the surface of the titanium oxide-based fine particles.
改質酸化チタン系微粒子の平均粒子径が前記範囲にあれば、成型性に優れ、得られる成型体は圧縮強度、耐摩耗性、耐クラック性等に優れている。
If the average particle diameter of the modified titanium oxide fine particles is in the above range, the moldability is excellent, and the resulting molded article is excellent in compressive strength, wear resistance, crack resistance, and the like.
このような成型体用改質酸化チタン系微粒子粉末は以下のようにして製造される。
Such a modified titanium oxide fine particle powder for a molded body is produced as follows.
前記した所定の平均粒子径を有する酸化チタン系微粒子に所定量の改質剤を混合することによって成型体用改質酸化チタン系微粒子粉末を調製することができる。
A modified titanium oxide-based fine particle powder for a molded product can be prepared by mixing a predetermined amount of a modifier with the titanium oxide-based fine particles having the predetermined average particle diameter.
混合方法としては、酸化チタン系微粒子に可能な範囲で均一に混合できれば特に制限はなく、従来公知の混合方法を採用することができる。
The mixing method is not particularly limited as long as it can be uniformly mixed with the titanium oxide-based fine particles as much as possible, and a conventionally known mixing method can be employed.
例えば、ニーダー、ブレンダー、ミキサー等が挙げられる。
For example, a kneader, a blender, a mixer, etc. are mentioned.
混合する際は加熱することが好ましく、加熱温度は改質剤の種類（融点等）によっても異なるが、概ね４０～１２０℃の範囲である。また改質時にエタノールなどの揮発性溶媒を用いてもよい。
When mixing, it is preferable to heat, and the heating temperature is generally in the range of 40 to 120 ° C., although it varies depending on the type of modifier (melting point, etc.). Further, a volatile solvent such as ethanol may be used at the time of reforming.
また、混合時間は、温度によっても異なるが、概ね０．２５～５時間である。
つぎに、水分を１５重量％に調整した前記酸化チタン系微粒子の示唆熱分析における３０℃から１００℃に昇温した際の水の脱離に伴う重量減少率（Ｗ（％））と、水分を１５重量％に調整した前記成型体用改質酸化チタン系微粒子粉末の示唆熱分析における３０℃から１００℃に昇温した際の水の脱離に伴う重量減少率（ＷST（％））との重量減少率比（ＷST（％））／（Ｗ（％））が１．０２～１．２０、好ましくは１．０３～１．１５の範囲にあることが好ましい。 The mixing time varies depending on the temperature, but is generally 0.25 to 5 hours.
Next, the weight reduction rate (W (%)) accompanying water desorption when the temperature is raised from 30 ° C. to 100 ° C. in the suggested thermal analysis of the titanium oxide fine particles adjusted to 15% by weight of water, Weight reduction rate (W ST (%)) due to desorption of water when the temperature is raised from 30 ° C. to 100 ° C. in the suggested thermal analysis of the modified titanium oxide fine particle powder for molded bodies adjusted to 15% by weight It is preferable that the ratio (W ST (%)) / (W (%)) is 1.02 to 1.20, preferably 1.03 to 1.15.
つぎに、水分を１５重量％に調整した前記酸化チタン系微粒子の示唆熱分析における３０℃から１００℃に昇温した際の水の脱離に伴う重量減少率（Ｗ（％））と、水分を１５重量％に調整した前記成型体用改質酸化チタン系微粒子粉末の示唆熱分析における３０℃から１００℃に昇温した際の水の脱離に伴う重量減少率（ＷST（％））との重量減少率比（ＷST（％））／（Ｗ（％））が１．０２～１．２０、好ましくは１．０３～１．１５の範囲にあることが好ましい。 The mixing time varies depending on the temperature, but is generally 0.25 to 5 hours.
Next, the weight reduction rate (W (%)) accompanying water desorption when the temperature is raised from 30 ° C. to 100 ° C. in the suggested thermal analysis of the titanium oxide fine particles adjusted to 15% by weight of water, Weight reduction rate (W ST (%)) due to desorption of water when the temperature is raised from 30 ° C. to 100 ° C. in the suggested thermal analysis of the modified titanium oxide fine particle powder for molded bodies adjusted to 15% by weight It is preferable that the ratio (W ST (%)) / (W (%)) is 1.02 to 1.20, preferably 1.03 to 1.15.
ここで、成型体用改質酸化チタン系微粒子粉末の示唆熱分析における重量減少割合が多くなる理由については明らかではないが、重量減少割合比が前記範囲にあれば、後述する成型体用組成物を調製する際に１００℃近辺の加温下での混練、捏和時に原料混合物の水分が同じであっても、１００℃近辺の加温で脱離する水分により、見掛上水分が多い状態を呈し、混練、捏和の効果が高まり、成型性に優れた成型体用組成物が調製できるものと推察される。
Here, although the reason why the weight reduction ratio in the suggested thermal analysis of the modified titanium oxide fine particle powder for molded bodies increases is not clear, if the weight reduction ratio ratio is in the above range, the composition for molded bodies described later Even when the raw material mixture has the same water content during kneading and kneading at the time of kneading around 100 ° C., the apparent water content is high due to the water desorbed by heating around 100 ° C. It is assumed that the composition for kneading and kneading is enhanced and a composition for a molded body having excellent moldability can be prepared.
また、本発明に係る成型体用改質酸化チタン系微粒子粉末は、前記３０℃から１００℃に昇温した際の水の脱離量が多いだけでなく、水の脱離に伴う吸熱ピークのボトム温度が高温にシフトする傾向が認められる。
前記重量減少率は、示唆熱分析計（リガク(株)製：差動型示差熱天秤：TG8120高温型、高感度示差走査熱量計：DSC8230標準型）により、サンプル量を約１０ｍｇ、昇温速度５．０℃／ｍｉｎ、空気雰囲気下の条件で測定し、３０℃～１００℃までの重量減少率を求めた。
［成型体用組成物］
本発明に係る成型体用組成物は、(i)前記成型体用改質酸化チタン系微粒子粉末、(ii)補強材、(iii)活性成分前駆体化合物 を含む組成物である。 In addition, the modified titanium oxide fine particle powder for molded bodies according to the present invention not only has a large amount of water desorption when the temperature is raised from 30 ° C. to 100 ° C. There is a tendency for the bottom temperature to shift to higher temperatures.
The weight reduction rate was measured by a suggested thermal analyzer (manufactured by Rigaku Corporation: differential differential thermal balance: TG8120 high-temperature type, high-sensitivity differential scanning calorimeter: DSC8230 standard type). The weight loss rate from 30 ° C. to 100 ° C. was determined by measuring at 5.0 ° C./min under an air atmosphere.
[Composite composition]
The molding composition according to the present invention is a composition comprising (i) the modified titanium oxide fine particle powder for molding, (ii) a reinforcing material, and (iii) an active ingredient precursor compound.
前記重量減少率は、示唆熱分析計（リガク(株)製：差動型示差熱天秤：TG8120高温型、高感度示差走査熱量計：DSC8230標準型）により、サンプル量を約１０ｍｇ、昇温速度５．０℃／ｍｉｎ、空気雰囲気下の条件で測定し、３０℃～１００℃までの重量減少率を求めた。
［成型体用組成物］
本発明に係る成型体用組成物は、(i)前記成型体用改質酸化チタン系微粒子粉末、(ii)補強材、(iii)活性成分前駆体化合物 を含む組成物である。 In addition, the modified titanium oxide fine particle powder for molded bodies according to the present invention not only has a large amount of water desorption when the temperature is raised from 30 ° C. to 100 ° C. There is a tendency for the bottom temperature to shift to higher temperatures.
The weight reduction rate was measured by a suggested thermal analyzer (manufactured by Rigaku Corporation: differential differential thermal balance: TG8120 high-temperature type, high-sensitivity differential scanning calorimeter: DSC8230 standard type). The weight loss rate from 30 ° C. to 100 ° C. was determined by measuring at 5.0 ° C./min under an air atmosphere.
[Composite composition]
The molding composition according to the present invention is a composition comprising (i) the modified titanium oxide fine particle powder for molding, (ii) a reinforcing material, and (iii) an active ingredient precursor compound.
成型体用改質酸化チタン系微粒子粉末
成型体用改質酸化チタン系微粒子粉末としては、前記した成型体用改質酸化チタン系微粒子粉末を用いる。 Modified titanium oxide-based fine particle powder for molded body The modified titanium oxide-based fine particle powder for molded body is used as the modified titanium oxide-based fine particle powder for molded body.
成型体用改質酸化チタン系微粒子粉末としては、前記した成型体用改質酸化チタン系微粒子粉末を用いる。 Modified titanium oxide-based fine particle powder for molded body The modified titanium oxide-based fine particle powder for molded body is used as the modified titanium oxide-based fine particle powder for molded body.
成型体用組成物中の成型体用改質酸化チタン系微粒子粉末の含有量は固形分として３３～８０．８重量％、さらには４０～７５重量％の範囲にあることが好ましい。
The content of the modified titanium oxide fine particle powder for molded body in the molded body composition is preferably in the range of 33 to 80.8% by weight, more preferably 40 to 75% by weight as the solid content.
成型体用組成物中の成型体用改質酸化チタン系微粒子粉末の含有量が少ないと、成形が困難となるとともに、触媒性能、例えば選択還元型ＮＯx触媒のＮＯxの除去率が不充分となる場合がある。
If the content of the modified titanium oxide fine particle powder for molded body in the molded body composition is small, molding becomes difficult and the catalyst performance, for example, the NO x removal rate of the selective reduction type NO x catalyst is insufficient. It may become.
成型体用組成物中の成型体用改質酸化チタン系微粒子粉末の含有量が多すぎても、後述する他の補強材、フィラー、活性成分前駆体の使用量が制限されるため、成型性、圧縮強度、耐クラック性および触媒性能が不充分となる場合がある。
Even if the content of the modified titanium oxide fine particle powder for molded body in the molded body composition is too large, the amount of other reinforcing materials, fillers, and active ingredient precursors described later is limited, so the moldability , Compressive strength, crack resistance and catalyst performance may be insufficient.
補強材
補強材としては、グラスファイバー、セラミックファイバー等の繊維状補強材を用いることができる。 As the reinforcing material reinforcing material, a fibrous reinforcing material such as glass fiber or ceramic fiber can be used.
補強材としては、グラスファイバー、セラミックファイバー等の繊維状補強材を用いることができる。 As the reinforcing material reinforcing material, a fibrous reinforcing material such as glass fiber or ceramic fiber can be used.
このような補強材を含んでいると、押出し成型した後の乾燥時の収縮による亀裂の発生を抑制することができ、圧縮強度、耐摩耗性に優れた成型体を調製することができる。
When such a reinforcing material is included, it is possible to suppress the generation of cracks due to shrinkage during drying after extrusion molding, and it is possible to prepare a molded body having excellent compressive strength and wear resistance.
成型体用組成物中の補強材の含有量は、固形分として１．８～１２．８重量％、さらには３～１０重量％の範囲にあることが好ましい。
The content of the reinforcing material in the molding composition is preferably in the range of 1.8 to 12.8% by weight, more preferably 3 to 10% by weight as the solid content.
成型体用組成物中の補強材の含有量が少ないと、押出し成型した後の乾燥時に収縮による亀裂が発生する場合がある。成型体用組成物中の補強材の含有量が多すぎても、押出し成型時に成形用金型に補強材が詰まり、成形性を阻害する場合がある。
If the content of the reinforcing material in the molding composition is small, cracks due to shrinkage may occur during drying after extrusion molding. Even if the content of the reinforcing material in the molded body composition is too large, the reinforcing material may be clogged in the molding die during extrusion molding, which may impair the moldability.
活性成分前駆体化合物
活性成分前駆体化合物としては、Ｖ、Ｗ、Ｍｏ、Ｃｒ、Ｍｎ、Ｆｅ、Ｎｉ、Ｃｕ、Ａｇ、Ａｕ、Ｐｄ、Ｙ、Ｃｅ、Ｎｄ、Ｉｎ、Ｉｒからなる群から選ばれる少なくとも１種の元素の化合物が用いられる。活性成分は触媒として機能するため、目的に応じて適宜選択される。 Active component precursor compound The active component precursor compound is selected from the group consisting of V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, and Ir. A compound of at least one element is used. Since the active component functions as a catalyst, it is appropriately selected according to the purpose.
活性成分前駆体化合物としては、Ｖ、Ｗ、Ｍｏ、Ｃｒ、Ｍｎ、Ｆｅ、Ｎｉ、Ｃｕ、Ａｇ、Ａｕ、Ｐｄ、Ｙ、Ｃｅ、Ｎｄ、Ｉｎ、Ｉｒからなる群から選ばれる少なくとも１種の元素の化合物が用いられる。活性成分は触媒として機能するため、目的に応じて適宜選択される。 Active component precursor compound The active component precursor compound is selected from the group consisting of V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, and Ir. A compound of at least one element is used. Since the active component functions as a catalyst, it is appropriately selected according to the purpose.
具体的には、メタバナジン酸アンモニウム、硫酸バナジル、パラタングステン酸アンモニウム、メタタングステン酸アンモニウム、タングステン酸、モリブデン酸アンモニウム、硝酸クロム、酢酸クロム、硝酸マンガン、酢酸マンガン、硝酸パラジウム、硫酸鉄、硝酸ニッケル、硝酸銅、硝酸銀、硝酸イットリウム、硝酸セリウム、塩化金、塩化イリジウムなどが挙げられる。
Specifically, ammonium metavanadate, vanadyl sulfate, ammonium paratungstate, ammonium metatungstate, tungstic acid, ammonium molybdate, chromium nitrate, chromium acetate, manganese nitrate, manganese acetate, palladium nitrate, iron sulfate, nickel nitrate, Examples thereof include copper nitrate, silver nitrate, yttrium nitrate, cerium nitrate, gold chloride, and iridium chloride.
成型体用組成物中の活性成分前駆体化合物の含有量は、０．０００６～１２．８重量％、さらには０．３～１０重量％の範囲にあることが好ましい。
The content of the active ingredient precursor compound in the molding composition is preferably 0.0006 to 12.8% by weight, more preferably 0.3 to 10% by weight.
活性成分前駆体化合物の含有量が少ないと、選択還元型ＮＯx触媒として用いた場合にＮＯxの除去率が不充分となる場合がある。
If the content of the active component precursor compound is small, the NO x removal rate may be insufficient when used as a selective reduction type NO x catalyst.
活性成分前駆体化合物の含有量が酸化物として多いと、成形性が低下し、得られる成型体の圧縮強度、耐クラック性が不充分となる。
If the content of the active component precursor compound is large as an oxide, the moldability is lowered, and the compression strength and crack resistance of the resulting molded article are insufficient.
フィラー
本発明では、フィラーを含んでいても良い。このようなフィラーを含んでいると、連続して押出し成形が可能となるとともに圧縮強度、耐摩耗性に優れた成型体を調製することができる。 Filler In the present invention, a filler may be included. When such a filler is contained, it is possible to continuously perform extrusion molding and to prepare a molded body having excellent compressive strength and wear resistance.
本発明では、フィラーを含んでいても良い。このようなフィラーを含んでいると、連続して押出し成形が可能となるとともに圧縮強度、耐摩耗性に優れた成型体を調製することができる。 Filler In the present invention, a filler may be included. When such a filler is contained, it is possible to continuously perform extrusion molding and to prepare a molded body having excellent compressive strength and wear resistance.
フィラーとしては、コージェライト、アルミナ、ジルコニア、窒化珪素、炭化珪素、粘土鉱物等のセラミックス粉体を用いることができる。
As the filler, ceramic powder such as cordierite, alumina, zirconia, silicon nitride, silicon carbide, clay mineral can be used.
成型体用組成物中のフィラーの含有量は、固形分として０．６～１２．８重量％、さらには３～１０重量％の範囲にあることが好ましい。
The filler content in the molding composition is preferably in the range of 0.6 to 12.8% by weight, more preferably 3 to 10% by weight as the solid content.
成型体用組成物中のフィラーの含有量が少ないと、連続押し出し成形性が低下し、長寸法の成型体、特に長寸法のハニカム成型体の成型が困難となる場合があり、また、成形用金型の清掃あるいは取り換えが頻繁になり、生産性、経済性が低下する場合がある。成型体用組成物中のフィラーの含有量が多すぎても、触媒性能が不充分となる場合がある。
If the content of the filler in the molded body composition is small, the continuous extrusion moldability is lowered, and it may be difficult to mold a long-sized molded body, particularly a long-sized honeycomb molded body. The mold may be frequently cleaned or replaced, which may reduce productivity and economy. Even if there is too much content of the filler in the composition for shaping | molding bodies, catalyst performance may become inadequate.
有機添加剤
本発明の成型体用組成物には、前記改質剤以外の有機添加剤を含んでいてもよい。 Organic additive The composition for molded bodies of the present invention may contain an organic additive other than the modifier.
本発明の成型体用組成物には、前記改質剤以外の有機添加剤を含んでいてもよい。 Organic additive The composition for molded bodies of the present invention may contain an organic additive other than the modifier.
有機添加剤としては、カルボキシメチルセルロース、メチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシメチルセルロース、結晶セルロース、ポリエチレングリコール、ポリプロピレングリコール、ポリエチレンオキサイド等が挙げられる。
Examples of the organic additive include carboxymethyl cellulose, methyl cellulose, hydroxypropyl cellulose, hydroxymethyl cellulose, crystalline cellulose, polyethylene glycol, polypropylene glycol, polyethylene oxide and the like.
このような有機添加材を含んでいると、成形用金型からの剥離性、成型性等が向上する効果が得られる。
When such an organic additive is contained, the effect of improving the releasability from the molding die, moldability, and the like can be obtained.
成型体用組成物中の有機添加剤の含有量は成型体用組成物中に０．０３～４．３重量％、さらには０．５～２重量％の範囲にあることが好ましい。
The content of the organic additive in the molding composition is preferably in the range of 0.03 to 4.3% by weight, more preferably 0.5 to 2% by weight in the molding composition.
成型体用組成物中の有機添加剤の含有量が少ないと、成形性が不充分となり、多すぎても、得られる成型体触媒の細孔容積が大きくなり、圧縮強度が不充分となる他、成形体の焼成時に亀裂が発生する場合がある。
If the content of the organic additive in the molded body composition is small, the moldability becomes insufficient, and if it is too much, the pore volume of the resulting molded body catalyst becomes large and the compressive strength becomes insufficient. In some cases, cracks may occur during firing of the molded body.
組成
成型体用組成物は、上記成分以外に、溶剤を含む。溶剤としては、使用目的や成型方法に応じて適宜選択される。 The composition molded composition contains a solvent in addition to the above components. The solvent is appropriately selected depending on the purpose of use and the molding method.
成型体用組成物は、上記成分以外に、溶剤を含む。溶剤としては、使用目的や成型方法に応じて適宜選択される。 The composition molded composition contains a solvent in addition to the above components. The solvent is appropriately selected depending on the purpose of use and the molding method.
具体的には、水、メタノール、エタノール、プロパノール、メチルエチルケトンなど揮発性溶剤が挙げられ、具体的には水が好ましい。
Specific examples include volatile solvents such as water, methanol, ethanol, propanol, and methyl ethyl ketone. Specifically, water is preferable.
このような成型体用組成物の全固形分濃度は６０～８５重量％、さらには６５～７５重量％の範囲にあることが好ましい。
It is preferable that the total solid content concentration of such a molding composition is in the range of 60 to 85% by weight, more preferably 65 to 75% by weight.
成型体用組成物の全固形分濃度が低すぎると、押出し成型後、乾燥前の成形体の保形性が弱く、変形する場合がある。
If the total solid content concentration of the molded body composition is too low, the shape retention of the molded body before drying after the extrusion molding is weak and may be deformed.
成型体用組成物の全固形分濃度が大きすぎても、成形金型を通過する際のすべり性が小さく、成型性、特に連続成形性が低下する場合がある。
Even if the total solid content concentration of the molding composition is too large, the slipping property when passing through the molding die is small, and the moldability, particularly the continuous moldability may be lowered.
本発明に係る成型体用組成物は、前記した改質酸化チタン系微粒子粉末を用いる以外は従来と同様にして調製することができる。
The molded body composition according to the present invention can be prepared in the same manner as in the prior art except that the above-described modified titanium oxide-based fine particle powder is used.
例えば、選択還元型ＮＯｘ触媒の例では、前記改質酸化チタン系微粒子粉末と補強材と活性成分前駆体化合物と水と、必要に応じて用いるフィラーと、有機添加剤とを前記した所定量の範囲となるように混合し、混練、捏和等することによって調製することができる。
For example, in the example of the selective reduction type NOx catalyst, the modified titanium oxide-based fine particle powder, the reinforcing material, the active component precursor compound, water, the filler to be used as necessary, and the organic additive in a predetermined amount as described above. It can be prepared by mixing, kneading, kneading, etc. so that it may become a range.
混練および捏和は、加温下で行うことが好ましい。このときの温度は概８０～１４０℃、さらには９０～１３０℃の範囲にあることが好ましい。このような温度範囲で混練および捏和を行うことによって、成型性に優れた成型体用組成物を調製することができる。
［成型体］
本発明に係る成型体は、(i)前記成型体用改質酸化チタン系微粒子粉末、(ii)補強材、(iii)活性成分 を含む。 Kneading and kneading are preferably performed under heating. The temperature at this time is preferably in the range of about 80 to 140 ° C., more preferably 90 to 130 ° C. By performing kneading and kneading in such a temperature range, it is possible to prepare a molded article composition having excellent moldability.
[Molded body]
The molded body according to the present invention includes (i) the modified titanium oxide-based fine particle powder for molded body, (ii) a reinforcing material, and (iii) an active ingredient.
［成型体］
本発明に係る成型体は、(i)前記成型体用改質酸化チタン系微粒子粉末、(ii)補強材、(iii)活性成分 を含む。 Kneading and kneading are preferably performed under heating. The temperature at this time is preferably in the range of about 80 to 140 ° C., more preferably 90 to 130 ° C. By performing kneading and kneading in such a temperature range, it is possible to prepare a molded article composition having excellent moldability.
[Molded body]
The molded body according to the present invention includes (i) the modified titanium oxide-based fine particle powder for molded body, (ii) a reinforcing material, and (iii) an active ingredient.
成型体中の成型体用改質酸化チタン系微粒子粉末の含有量は５５～９５重量％、さらには７０～８０重量％の範囲にあることが好ましい。
The content of the modified titanium oxide fine particle powder for molded body in the molded body is preferably 55 to 95% by weight, more preferably 70 to 80% by weight.
成型体中の成型体用改質酸化チタン系微粒子粉末の含有量が少ないと、成形が困難となるとともに、触媒性能、例えば選択還元型ＮＯｘ触媒のＮＯｘの除去率が不充分となる場合がある。
If the content of the modified titanium oxide fine particle powder for the molded body in the molded body is small, molding may become difficult and the catalyst performance, for example, the NOx removal rate of the selective reduction type NOx catalyst may be insufficient. .
成型体中の成型体用改質酸化チタン系微粒子粉末の含有量が多すぎても、他の補強材、フィラー、活性成分前駆体の含有量が制限されるため、成型性、圧縮強度、耐クラック性および触媒性能が不充分となる場合がある。
Even if the content of the modified titanium oxide fine particle powder for the molded product in the molded product is too large, the content of other reinforcing materials, fillers and active ingredient precursors is limited, so that the moldability, compressive strength, Cracking properties and catalyst performance may be insufficient.
成型体中の補強材の含有量は、固形分として３～１５重量％、さらには３～１０重量％の範囲にあることが好ましい。
The content of the reinforcing material in the molded body is preferably 3 to 15% by weight, more preferably 3 to 10% by weight as a solid content.
成型体中の補強材の含有量が少ないと、強度が低く、また多くしても、却って生産性が悪い上に、触媒として機能する有効成分が少なくなる。
If the content of the reinforcing material in the molded body is small, the strength is low, and even if it is increased, the productivity is poor, and the active ingredient that functions as a catalyst decreases.
成型体中のフィラーの含有量は、固形分として１～１５重量％、さらには３～１０重量％の範囲にあることが好ましい。成型体中のフィラーの含有量が少ないと、強度が低く、また、フィラーの含有量が多すぎても、触媒性能が不充分となる場合がある。
The filler content in the molded body is preferably in the range of 1 to 15% by weight, more preferably 3 to 10% by weight as the solid content. If the filler content in the molded body is small, the strength is low, and even if the filler content is too large, the catalyst performance may be insufficient.
活性成分としては、前記前駆体から誘導されるものであり、Ｖ、Ｗ、Ｍｏ、Ｃｒ、Ｍｎ、Ｆｅ、Ｎｉ、Ｃｕ、Ａｇ、Ａｕ、Ｐｄ、Ｙ、Ｃｅ、Ｎｄ、Ｉｎ、Ｉｒから選ばれる少なくとも１種の元素の金属または金属酸化物が含まれている。
The active component is derived from the precursor and is selected from V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, and Ir. At least one elemental metal or metal oxide is included.
具体的には、Ｖ、Ｗ、Ｍｏ、Ｃｒ、Ｍｎ、Ｆｅ、Ｎｉ、Ｃｕ、Ａｇ、Ａｕ、Ｐｄ、Ｙ、Ｃｅ、Ｎｄ、Ｉｎ、Ｉｒ等の金属および／またはＶ2Ｏ5、ＷＯ3、ＭＯ3、Ｃｒ2Ｏ3、ＭｎＯ2、Ｍｎ2Ｏ3、Ｆｅ2Ｏ3、ＮｉＯ、ＣｕＯ、Ａｇ2Ｏ、ＡｕＯ、ＰｄＯ、Ｙ2Ｏ3、ＣｅＯ2、Ｎｄ2Ｏ5、Ｉｎ2Ｏ3、ＩｒＯ等の酸化物およびこれらの混合物が挙げられる。
Specifically, metals such as V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, Ir, and / or V 2 O 5 , WO 3 , MO 3 , Cr 2 O 3 , MnO 2 , Mn 2 O 3 , Fe 2 O 3 , NiO, CuO, Ag 2 O, AuO, PdO, Y 2 O 3 , CeO 2 , Nd 2 O 5 , In 2 O 3 And oxides such as IrO and mixtures thereof.
成型体中の活性成分の含有量は酸化物として０．００１～１５重量％、さらには０．３～１２重量％の範囲にあることが好ましい。活性成分の含有量が少ないと、選択還元型ＮＯx触媒として用いた場合にＮＯxの除去率が不充分となる場合がある。活性成分の含有量が多すぎても、成型体の圧縮強度、耐クラック性が不充分となる。
The content of the active ingredient in the molded body is preferably in the range of 0.001 to 15% by weight, more preferably 0.3 to 12% by weight as an oxide. If the content of the active component is small, the NO x removal rate may be insufficient when used as a selective reduction type NO x catalyst. Even if there is too much content of an active ingredient, the compressive strength and crack resistance of a molded object will become inadequate.
本発明に係る成型体の形状はペレット、ビード、リング、ハニカム等従来公知の形状を採用することができるが、本発明では、前記した改質酸化チタン系微粒子粉末を用いることにより、成型性が大きく向上することから、従来成型性が困難なハニカム成型体、特に薄肉のハニカム成型体として好適に用いることができる。
Conventionally known shapes such as pellets, beads, rings, and honeycombs can be adopted as the shape of the molded body according to the present invention. However, in the present invention, by using the modified titanium oxide-based fine particle powder, the moldability is improved. Since it is greatly improved, it can be suitably used as a honeycomb molded body that has been difficult to mold in the past, particularly as a thin honeycomb molded body.
本発明では、上記した組成物を用いているため、成型性が高く、得られるハニカム成型体は強度、耐摩耗性に優れているが、一方で、成型性に優れているために薄肉化、ピッチ数の多い成型体を得ることができる。
In the present invention, since the above-described composition is used, the moldability is high, and the obtained honeycomb molded body is excellent in strength and wear resistance. A molded product having a large number of pitches can be obtained.
ハニカム成型体の外径は３０～４００ｍｍの範囲にあることが好ましい。
The outer diameter of the honeycomb molded body is preferably in the range of 30 to 400 mm.
ここで、ハニカムの外観形状は、四角形、六角形、八角形以上の多角形、円形、楕円形等特に制限は無く、用途・用法によって適宜選択することができる。
Here, the external shape of the honeycomb is not particularly limited, such as a quadrangle, a hexagon, an octagon or more polygon, a circle, an ellipse, and the like, and can be appropriately selected depending on the application and usage.
ハニカム成型体の外径が３０ｍｍ未満と小さくする効果がなく、ハニカム型の選択還元型ＮＯｘ触媒として用いる場合に、生産本数が増えるだけで経済的ではない。ハニカム成型体の外径が４００ｍｍを超えて大きくする効果がなく、このため押出成型装置もない。
There is no effect of reducing the outer diameter of the honeycomb molded body to less than 30 mm, and when used as a honeycomb-type selective reduction type NOx catalyst, the number of production increases and it is not economical. There is no effect of increasing the outer diameter of the honeycomb molded body beyond 400 mm, and therefore there is no extrusion molding apparatus.
また、ハニカム成型体の長さは３～１５００ｍｍ、さらには５０～１３００ｍｍの範囲にあることが好ましい。
Further, the length of the honeycomb molded body is preferably 3 to 1500 mm, more preferably 50 to 1300 mm.
ハニカム成型体の長さが３ｍｍ未満の場合は、製造するのが困難となる。
If the length of the honeycomb molded body is less than 3 mm, it is difficult to manufacture.
ハニカム成型体の長さが１５００ｍｍを超えると、用途が少ない。
When the length of the honeycomb molded body exceeds 1500 mm, there are few uses.
ハニカム成型体のピッチは６～５００ｃｐｓｉ、さらには１５～２００ｃｐｓｉの範囲にあることが好ましい。
The pitch of the honeycomb molded body is preferably in the range of 6 to 500 cpsi, more preferably 15 to 200 cpsi.
ハニカム成型体のピッチが６ｃｐｓｉ未満の場合は、目開きが大きく保形性が弱くなり製造が難しくなる。
When the pitch of the honeycomb molded body is less than 6 cpsi, the opening is large and the shape retaining property is weak, which makes it difficult to manufacture.
ハニカム成型体のピッチが５００ｃｐｓｉを超えると、成型時に圧力損失が大きくなり成形が困難となる場合がある。
When the pitch of the honeycomb molded body exceeds 500 cpsi, pressure loss increases during molding, and molding may be difficult.
ハニカム成型体の肉厚は０．１～１．５ｍｍ、さらには０．1～０．３ｍｍの範囲にあることが好ましい。
The thickness of the honeycomb molded body is preferably in the range of 0.1 to 1.5 mm, more preferably 0.1 to 0.3 mm.
ハニカム成型体の肉厚が０．１ｍｍ未満のものは前記した改質酸化チタン系微粒子を用いても得ることが困難である。
A honeycomb molded body having a wall thickness of less than 0.1 mm is difficult to obtain even if the above-described modified titanium oxide-based fine particles are used.
ハニカム成型体の肉厚が１．５ｍｍを超えると、前記した改質酸化チタン系微粒子を用いることなく従来公知の方法で形成することができる。
When the thickness of the honeycomb molded body exceeds 1.5 mm, it can be formed by a conventionally known method without using the modified titanium oxide fine particles.
本発明では、ハニカム成型体の肉厚は特に０．１～０．３ｍｍの範囲にあることが好ましい。
In the present invention, the thickness of the honeycomb molded body is particularly preferably in the range of 0.1 to 0.3 mm.
本発明によれば、肉厚が薄く軽量で、ピッチの数が多く、且つ、強度、耐摩耗性、圧縮強度に優れ、軽量で、経済性に優れたハニカムとして好適に用いることができる。
According to the present invention, it can be suitably used as a honeycomb that is thin and lightweight, has a large number of pitches, is excellent in strength, wear resistance, and compressive strength, is lightweight, and is economical.
本発明に係る成型体は、前記した成型体用組成物を用いて、従来公知の方法で調製することができる。
The molded body according to the present invention can be prepared by a conventionally known method using the aforementioned molded body composition.
成型体の形状はペレット、ビード、リング、ハニカム等従来公知の形状の成型体を得ることができ、成型時の押出し成型用の金型を適宜選択することによって調製することができる。
The shape of the molded body can be obtained by obtaining a conventionally known molded body such as pellets, beads, rings, and honeycombs, and by appropriately selecting a mold for extrusion molding at the time of molding.
なお、本発明では特に強度、耐摩耗性に優れた薄肉のハニカム成型体を得ることができるが、このとき、真空押出成形機を用いるとクラックの無い、より、強度、耐摩耗性に優れた薄肉のハニカム成型体を安定的に得ることができる。
［実施例］
以下、実施例により説明するが、本発明はこれらの実施例により限定されるものではない。
［実施例１］
成型体用改質酸化チタン系微粒子粉末(1)の調製
メタチタン酸スラリー（石原産業(株)製）７８．３ｋｇを加熱還流器付撹拌槽に仕込み、さらにパラタングステン酸アンモニウム２．８２ｋｇを添加して混合した後、濃度１５重量％のアンモニア水３０．５ｋｇを加えてｐＨを９．５に調整し、９５℃で１時間撹拌しながら熟成した。その後、この混合スラリーを４０℃まで冷却し、ついで、濾過し、掛け水により洗浄して、固形分濃度（ＴｉＯ2・ＷＯ3）４９重量％の洗浄ケーキを調製した。洗浄ケーキは、乾燥基準でＳＯ4を３．０重量％、Ｎａ2Ｏを０．０３重量％含有していた。 In the present invention, it is possible to obtain a thin-walled honeycomb molded body particularly excellent in strength and wear resistance, but at this time, if a vacuum extrusion molding machine is used, there is no crack, and the strength and wear resistance are more excellent. A thin honeycomb molded body can be obtained stably.
[Example]
Hereinafter, although an example explains, the present invention is not limited by these examples.
[Example 1]
Preparation of Modified Titanium Oxide Fine Particle Powder (1) for Molded Body 78.3 kg of metatitanic acid slurry (manufactured by Ishihara Sangyo Co., Ltd.) was charged into a stirring tank equipped with a heating reflux, and 2.82 kg of ammonium paratungstate was added. After mixing, 30.5 kg of 15% by weight aqueous ammonia was added to adjust the pH to 9.5, and the mixture was aged with stirring at 95 ° C. for 1 hour. Then, this mixed slurry was cooled to 40 ° C., then filtered, and washed with water to prepare a washed cake having a solid content concentration (TiO 2 · WO 3 ) of 49% by weight. The washed cake contained 3.0 wt% SO 4 and 0.03 wt% Na 2 O on a dry basis.
［実施例］
以下、実施例により説明するが、本発明はこれらの実施例により限定されるものではない。
［実施例１］
成型体用改質酸化チタン系微粒子粉末(1)の調製
メタチタン酸スラリー（石原産業(株)製）７８．３ｋｇを加熱還流器付撹拌槽に仕込み、さらにパラタングステン酸アンモニウム２．８２ｋｇを添加して混合した後、濃度１５重量％のアンモニア水３０．５ｋｇを加えてｐＨを９．５に調整し、９５℃で１時間撹拌しながら熟成した。その後、この混合スラリーを４０℃まで冷却し、ついで、濾過し、掛け水により洗浄して、固形分濃度（ＴｉＯ2・ＷＯ3）４９重量％の洗浄ケーキを調製した。洗浄ケーキは、乾燥基準でＳＯ4を３．０重量％、Ｎａ2Ｏを０．０３重量％含有していた。 In the present invention, it is possible to obtain a thin-walled honeycomb molded body particularly excellent in strength and wear resistance, but at this time, if a vacuum extrusion molding machine is used, there is no crack, and the strength and wear resistance are more excellent. A thin honeycomb molded body can be obtained stably.
[Example]
Hereinafter, although an example explains, the present invention is not limited by these examples.
[Example 1]
Preparation of Modified Titanium Oxide Fine Particle Powder (1) for Molded Body 78.3 kg of metatitanic acid slurry (manufactured by Ishihara Sangyo Co., Ltd.) was charged into a stirring tank equipped with a heating reflux, and 2.82 kg of ammonium paratungstate was added. After mixing, 30.5 kg of 15% by weight aqueous ammonia was added to adjust the pH to 9.5, and the mixture was aged with stirring at 95 ° C. for 1 hour. Then, this mixed slurry was cooled to 40 ° C., then filtered, and washed with water to prepare a washed cake having a solid content concentration (TiO 2 · WO 3 ) of 49% by weight. The washed cake contained 3.0 wt% SO 4 and 0.03 wt% Na 2 O on a dry basis.
ついで、洗浄ケーキを１１０℃で２０時間乾燥し、さらに５５０℃で５時間焼成した後、粉砕機を用いて粉砕し、酸化チタンと酸化タングステンの複合酸化物（ＴｉＯ2－ＷＯ3、重量比ＴｉＯ2／ＷＯ3＝９０／１０）からなる酸化チタン系微粒子粉末(1)を得た。
Next, the washed cake was dried at 110 ° C. for 20 hours, further calcined at 550 ° C. for 5 hours, and then pulverized using a pulverizer to obtain a composite oxide of titanium oxide and tungsten oxide (TiO 2 —WO 3 , weight ratio TiO 2). 2 / WO 3 = 90/10) to obtain a titanium oxide fine particle powder (1).
酸化チタン系微粒子粉末(1)の平均粒子径を以下の方法で測定し、結果を表に示す。また組成（調合基準）を表に示す。
The average particle diameter of the titanium oxide fine particle powder (1) was measured by the following method, and the results are shown in the table. The composition (preparation standard) is shown in the table.
平均粒子径および粒子径分布は、レーザー回折散乱式粒子径分布測定装置（堀場製作所製：ＬＡ－３００）を用いて測定した。このときの条件は、水分散媒に分散させ、超音波を３分間照射し、レーザー光透過率が８５％となるように濃度調整した。
The average particle size and particle size distribution were measured using a laser diffraction / scattering particle size distribution measuring apparatus (Horiba, Ltd .: LA-300). The conditions at this time were dispersed in an aqueous dispersion medium, irradiated with ultrasonic waves for 3 minutes, and the concentration was adjusted so that the laser light transmittance was 85%.
また、水分脱離率（Ｗ％）を測定し、結果を表に示すとともに、図１に重量減少曲線を示し、図２に吸熱曲線を示す（なお改質していないので、後述の比較例１に相当する）。
Further, the moisture desorption rate (W%) was measured, and the results are shown in the table, and the weight loss curve is shown in FIG. 1, and the endothermic curve is shown in FIG. 1).
ついで、得られた酸化チタン系微粒子粉末(1)２３．５ｋｇと、改質剤としてステアリン酸２３．５ｇを混合し、ニーダーにて２０分間、１２０℃に加熱しながら混合して成型体用改質酸化チタン系微粒子粉末(1)を調製した。
Next, 23.5 kg of the obtained titanium oxide-based fine particle powder (1) and 23.5 g of stearic acid as a modifier were mixed and mixed with a kneader for 20 minutes while heating at 120 ° C. Titanium oxide fine particle powder (1) was prepared.
成型体用改質酸化チタン系微粒子粉末(1)の平均粒子径および水分脱離率（ＷST％）を測定し、結果を表に示すとともに、図１に重量減少曲線を示し、図２に吸熱曲線を示す。
このときの、成型体用改質酸化チタン系微粒子粉末(1)中の改質剤の含有量は使用量基準で０．１重量％である。 The average particle size and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (1) for molded bodies were measured, the results are shown in the table, the weight loss curve is shown in FIG. An endothermic curve is shown.
At this time, the content of the modifying agent in the modified titanium oxide fine particle powder (1) for a molded body is 0.1% by weight based on the amount used.
このときの、成型体用改質酸化チタン系微粒子粉末(1)中の改質剤の含有量は使用量基準で０．１重量％である。 The average particle size and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (1) for molded bodies were measured, the results are shown in the table, the weight loss curve is shown in FIG. An endothermic curve is shown.
At this time, the content of the modifying agent in the modified titanium oxide fine particle powder (1) for a molded body is 0.1% by weight based on the amount used.
また、平均粒子径は酸化チタン系微粒子粉末(1)と同様に測定した。
The average particle size was measured in the same manner as the titanium oxide fine particle powder (1).
成型体用組成物(1)の調製
成型体用改質酸化チタン系微粒子粉末(1)２３．５ｋｇに、モノエタノールアミン０．３７５ｋｇにメタバナジン酸アンモニウムをＶ2Ｏ5として１．２８ｋｇを溶解した溶液を加え、次いでアンモニア水と水を加えてこの混合スラリーのｐＨを９とし、ニーダーにて１２０℃に加熱しながら０．５時間捏和した。その後、補強材としてグラスファイバー（オーウェンスコーニング(株)製：チョップドストランド０３ ＤＥ、長さ３ｍｍ、繊維径５μｍ）１．２５ｋｇ、フィラーとして酸性白土１．２５ｋｇ、及び有機添加剤としてポリエチレンオキサイド０．５ｋｇを加えて、さらに１．５時間捏和して、成型体用組成物(1)を調製した。 Preparation of composition for molded body (1) 1.28 kg of ammonium metavanadate as V 2 O 5 dissolved in 0.375 kg of monoethanolamine in 23.5 kg of modified titanium oxide fine particle powder (1) for molded body The solution was added, then ammonia water and water were added to adjust the pH of the mixed slurry to 9, and the mixture was kneaded for 0.5 hours while heating to 120 ° C. with a kneader. Thereafter, glass fiber (made by Owens Corning Co., Ltd .: chopped strand 03 DE, length 3 mm,fiber diameter 5 μm) 1.25 kg as a reinforcing material, acid clay 1.25 kg as a filler, and polyethylene oxide 0. 5 kg was added and the mixture was further kneaded for 1.5 hours to prepare a molding composition (1).
成型体用改質酸化チタン系微粒子粉末(1)２３．５ｋｇに、モノエタノールアミン０．３７５ｋｇにメタバナジン酸アンモニウムをＶ2Ｏ5として１．２８ｋｇを溶解した溶液を加え、次いでアンモニア水と水を加えてこの混合スラリーのｐＨを９とし、ニーダーにて１２０℃に加熱しながら０．５時間捏和した。その後、補強材としてグラスファイバー（オーウェンスコーニング(株)製：チョップドストランド０３ ＤＥ、長さ３ｍｍ、繊維径５μｍ）１．２５ｋｇ、フィラーとして酸性白土１．２５ｋｇ、及び有機添加剤としてポリエチレンオキサイド０．５ｋｇを加えて、さらに１．５時間捏和して、成型体用組成物(1)を調製した。 Preparation of composition for molded body (1) 1.28 kg of ammonium metavanadate as V 2 O 5 dissolved in 0.375 kg of monoethanolamine in 23.5 kg of modified titanium oxide fine particle powder (1) for molded body The solution was added, then ammonia water and water were added to adjust the pH of the mixed slurry to 9, and the mixture was kneaded for 0.5 hours while heating to 120 ° C. with a kneader. Thereafter, glass fiber (made by Owens Corning Co., Ltd .: chopped strand 03 DE, length 3 mm,
成型体用組成物(1)中の各成分の含有量（使用量基準）を表に示す。
The content (usage standard) of each component in the molding composition (1) is shown in the table.
水分量は赤外線水分計（ケツト化学研究所製：ＦＤ－６１０）によって測定した。
The moisture content was measured with an infrared moisture meter (manufactured by Kett Chemical Laboratory: FD-610).
成型体(1)の調製
成型体用組成物(1)を真空押出成形機でハニカム形状に押出成型により、ハニカム構造体(1)を調製した。 Preparation of Molded Body (1) A honeycomb structure (1) was prepared by extruding the composition for molded body (1) into a honeycomb shape with a vacuum extruder.
成型体用組成物(1)を真空押出成形機でハニカム形状に押出成型により、ハニカム構造体(1)を調製した。 Preparation of Molded Body (1) A honeycomb structure (1) was prepared by extruding the composition for molded body (1) into a honeycomb shape with a vacuum extruder.
このとき、以下の基準で成型性を評価し、結果を表に示す。
At this time, moldability was evaluated according to the following criteria, and the results are shown in the table.
＜成形性＞
押出成形時のダイス面からの流れが安定的で、連続１０分間押出成形する間にハニカム触媒内部に欠陥が発生しない場合を◎とした。また、初期の流れが安定的であるが、連続１０分間成形する間にハニカム触媒内部に欠陥が発生した場合を○とした。一方、初期の流れが不安定でハニカム触媒内部に欠陥が発生した場合は△とした。ダイス面から出てこないものを×とした。 <Moldability>
The case where the flow from the die surface during extrusion molding was stable and no defect occurred inside the honeycomb catalyst during extrusion molding for 10 minutes continuously was marked as と し た. In addition, the initial flow was stable, but a case where a defect occurred inside the honeycomb catalyst during the continuous 10-minute molding was marked as ◯. On the other hand, when the initial flow was unstable and a defect was generated inside the honeycomb catalyst, Δ was given. The thing which did not come out from a die surface was set as x.
押出成形時のダイス面からの流れが安定的で、連続１０分間押出成形する間にハニカム触媒内部に欠陥が発生しない場合を◎とした。また、初期の流れが安定的であるが、連続１０分間成形する間にハニカム触媒内部に欠陥が発生した場合を○とした。一方、初期の流れが不安定でハニカム触媒内部に欠陥が発生した場合は△とした。ダイス面から出てこないものを×とした。 <Moldability>
The case where the flow from the die surface during extrusion molding was stable and no defect occurred inside the honeycomb catalyst during extrusion molding for 10 minutes continuously was marked as と し た. In addition, the initial flow was stable, but a case where a defect occurred inside the honeycomb catalyst during the continuous 10-minute molding was marked as ◯. On the other hand, when the initial flow was unstable and a defect was generated inside the honeycomb catalyst, Δ was given. The thing which did not come out from a die surface was set as x.
ついで、ハニカム構造体(1)を６０℃で４８時間乾燥し、ついで、５３０℃で３時間焼成してハニカム構造の成型体(1)を調製した。
Then, the honeycomb structure (1) was dried at 60 ° C. for 48 hours, and then fired at 530 ° C. for 3 hours to prepare a honeycomb structure molded body (1).
成型体(1)の各寸法を測定し、結果を表に示す。また、成型体(1)中の各成分の含有量（使用量基準）を表に示す。（重量比でＴｉＯ2／ＷＯ3／Ｖ2Ｏ5／ＧＦ／酸性白土の割合は、７７．４／８．６／４／５／５である。）
また、成型体(1)の比表面積、細孔容積、圧縮強度および脱硝触媒性能を以下の方法で測定し、結果を表に示す。 Each dimension of the molded body (1) was measured, and the results are shown in the table. In addition, the content (usage standard) of each component in the molded body (1) is shown in the table. (The weight ratio of TiO 2 / WO 3 / V 2 O 5 / GF / acid clay is 77.4 / 8.6 / 4/5/5.)
Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (1) were measured by the following methods, and the results are shown in the table.
また、成型体(1)の比表面積、細孔容積、圧縮強度および脱硝触媒性能を以下の方法で測定し、結果を表に示す。 Each dimension of the molded body (1) was measured, and the results are shown in the table. In addition, the content (usage standard) of each component in the molded body (1) is shown in the table. (The weight ratio of TiO 2 / WO 3 / V 2 O 5 / GF / acid clay is 77.4 / 8.6 / 4/5/5.)
Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (1) were measured by the following methods, and the results are shown in the table.
＜比表面積＞
３０％窒素―７０％ヘリウムの混合ガスを吸着ガスとしたＢＥＴ法に基づく比表面積測定装置によりハニカム状排ガス処理触媒の比表面積を求める。 <Specific surface area>
The specific surface area of the honeycomb-shaped exhaust gas treatment catalyst is 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.
３０％窒素―７０％ヘリウムの混合ガスを吸着ガスとしたＢＥＴ法に基づく比表面積測定装置によりハニカム状排ガス処理触媒の比表面積を求める。 <Specific surface area>
The specific surface area of the honeycomb-shaped exhaust gas treatment catalyst is 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.
＜細孔容積＞
細孔容積は、水銀圧入法細孔分布測定装置（ＱＡＮＴＡ ＣＲＯＭＥ社製：ＰＭ－３３ＧＴ１ＬＰ）で測定した。なお、圧力範囲は３２～３２２００ｐｓｉである。 <Pore volume>
The pore volume was measured with a mercury intrusion method pore distribution measuring device (manufactured by QANTA CROME: PM-33GT1LP). The pressure range is 32 to 32200 psi.
細孔容積は、水銀圧入法細孔分布測定装置（ＱＡＮＴＡ ＣＲＯＭＥ社製：ＰＭ－３３ＧＴ１ＬＰ）で測定した。なお、圧力範囲は３２～３２２００ｐｓｉである。 <Pore volume>
The pore volume was measured with a mercury intrusion method pore distribution measuring device (manufactured by QANTA CROME: PM-33GT1LP). The pressure range is 32 to 32200 psi.
＜圧縮強度＞
圧縮強度機（東京試験機製作所製：型式 ＡＬ／Ｂ３０Ｐ）を用い、成型体(1)を立方体または直方体に切出した試料に対し、ハニカム孔の貫通方向、及びこの方向と直交する方向（以下、単に「直交方向」ともいう）に一定速度で圧縮負荷をかけ、試料が破壊されるまでの最大荷重（Ｎ）を読み取り、下記（４）式より圧縮強度を求める。 <Compressive strength>
Using a compressive strength machine (manufactured by Tokyo Test Machine Manufacturing Co., Ltd .: model AL / B30P), a sample obtained by cutting the molded body (1) into a cube or a rectangular parallelepiped, and the direction through which the honeycomb holes penetrate and perpendicular to this direction (hereinafter, A compressive load is applied at a constant speed to the specimen (also referred to simply as “orthogonal direction”), the maximum load (N) until the sample is broken is read, and the compressive strength is obtained from the following equation (4).
圧縮強度機（東京試験機製作所製：型式 ＡＬ／Ｂ３０Ｐ）を用い、成型体(1)を立方体または直方体に切出した試料に対し、ハニカム孔の貫通方向、及びこの方向と直交する方向（以下、単に「直交方向」ともいう）に一定速度で圧縮負荷をかけ、試料が破壊されるまでの最大荷重（Ｎ）を読み取り、下記（４）式より圧縮強度を求める。 <Compressive strength>
Using a compressive strength machine (manufactured by Tokyo Test Machine Manufacturing Co., Ltd .: model AL / B30P), a sample obtained by cutting the molded body (1) into a cube or a rectangular parallelepiped, and the direction through which the honeycomb holes penetrate and perpendicular to this direction (hereinafter, A compressive load is applied at a constant speed to the specimen (also referred to simply as “orthogonal direction”), the maximum load (N) until the sample is broken is read, and the compressive strength is obtained from the following equation (4).
圧縮強度：（Ｎ／ｃｍ2）＝Ｗ（Ｎ）／｛ａ（ｃｍ）×ｃ（ｃｍ）｝ ・・・（４）
ここで、ａ（ｃｍ）及びｃ（ｃｍ）は試料の加圧面の２辺の寸法を示す。Ｗ（Ｎ）は徐々に負荷をかけ試料が完全に破壊されるまでの最大荷重を示す。 Compressive strength: (N / cm 2 ) = W (N) / {a (cm) × c (cm)} (4)
Here, a (cm) and c (cm) indicate the dimensions of the two sides of the pressing surface of the sample. W (N) indicates the maximum load until the sample is completely destroyed by applying a load gradually.
ここで、ａ（ｃｍ）及びｃ（ｃｍ）は試料の加圧面の２辺の寸法を示す。Ｗ（Ｎ）は徐々に負荷をかけ試料が完全に破壊されるまでの最大荷重を示す。 Compressive strength: (N / cm 2 ) = W (N) / {a (cm) × c (cm)} (4)
Here, a (cm) and c (cm) indicate the dimensions of the two sides of the pressing surface of the sample. W (N) indicates the maximum load until the sample is completely destroyed by applying a load gradually.
＜脱硝触媒性能試験＞
成型体(1)を、ハニカム孔数５×５目、長さ２００ｍｍに切り出して試験試料とし、この試験試料を流通式反応器に充填した。この流通式反応器に下記組成のモデルガスを流通させて脱硝率を測定した。触媒接触前後のガス中の窒素酸化物（ＮＯx）の脱硝率は、下記（５）式により求めた。このときＮＯxの濃度は化学発光式の窒素酸化物分析装置にて測定した。 <Denitration catalyst performance test>
The molded body (1) was cut into a honeycomb sample having 5 × 5 honeycomb holes and a length of 200 mm to obtain a test sample, and this test sample was filled in a flow reactor. A model gas having the following composition was passed through this flow reactor, and the denitration rate was measured. The denitration rate of nitrogen oxides (NO x ) in the gas before and after contact with the catalyst was determined by the following equation (5). At this time, the concentration of NO x was measured with a chemiluminescent nitrogen oxide analyzer.
成型体(1)を、ハニカム孔数５×５目、長さ２００ｍｍに切り出して試験試料とし、この試験試料を流通式反応器に充填した。この流通式反応器に下記組成のモデルガスを流通させて脱硝率を測定した。触媒接触前後のガス中の窒素酸化物（ＮＯx）の脱硝率は、下記（５）式により求めた。このときＮＯxの濃度は化学発光式の窒素酸化物分析装置にて測定した。 <Denitration catalyst performance test>
The molded body (1) was cut into a honeycomb sample having 5 × 5 honeycomb holes and a length of 200 mm to obtain a test sample, and this test sample was filled in a flow reactor. A model gas having the following composition was passed through this flow reactor, and the denitration rate was measured. The denitration rate of nitrogen oxides (NO x ) in the gas before and after contact with the catalyst was determined by the following equation (5). At this time, the concentration of NO x was measured with a chemiluminescent nitrogen oxide analyzer.
脱硝率（％）＝｛（未接触ガス中のＮＯx（質量ｐｐｍ）－接触後のガス中のＮＯx（質量ｐｐｍ））／未接触ガス中のＮＯx（質量ｐｐｍ）｝×１００ ・・・（５）
試験条件
触媒形状：ハニカム孔数５×５目、長さ２００ｍｍ
反応温度：３５０℃、ＳＶ＝４０，０００ｈｒ－１
モデルガス組成：ＮＯｘ＝１００質量ｐｐｍ、ＮＨ3＝１００質量ｐｐｍ、Ｏ2＝ ７重量％、Ｈ2Ｏ＝１０重量％、Ｎ2＝バランス
［実施例２］
成型体用改質酸化チタン系微粒子粉末(2)の調製
実施例１において、改質剤としてステアリン酸４．７ｇを用いた以外は同様にして成型体用改質酸化チタン系微粒子粉末(2)を調製した。 Denitration rate (%) = {(NO x in non-contact gas (mass ppm) −NO x in gas after contact (mass ppm)) / NO x in non-contact gas (mass ppm)} × 100・ (5)
Test conditions Catalyst shape:Honeycomb pore number 5 × 5, length 200mm
Reaction temperature: 350 ° C., SV = 40,000 hr−1
Model gas composition: NOx = 100 mass ppm, NH 3 = 100 mass ppm, O 2 = 7 wt%, H 2 O = 10 wt%, N 2 = balance [Example 2]
Preparation of Modified Titanium Oxide Fine Particle Powder (2) for Molded Body Modified titanium oxide-based fine particle powder (2) for molded body was the same as in Example 1 except that 4.7 g of stearic acid was used as a modifier. Was prepared.
試験条件
触媒形状：ハニカム孔数５×５目、長さ２００ｍｍ
反応温度：３５０℃、ＳＶ＝４０，０００ｈｒ－１
モデルガス組成：ＮＯｘ＝１００質量ｐｐｍ、ＮＨ3＝１００質量ｐｐｍ、Ｏ2＝ ７重量％、Ｈ2Ｏ＝１０重量％、Ｎ2＝バランス
［実施例２］
成型体用改質酸化チタン系微粒子粉末(2)の調製
実施例１において、改質剤としてステアリン酸４．７ｇを用いた以外は同様にして成型体用改質酸化チタン系微粒子粉末(2)を調製した。 Denitration rate (%) = {(NO x in non-contact gas (mass ppm) −NO x in gas after contact (mass ppm)) / NO x in non-contact gas (mass ppm)} × 100・ (5)
Test conditions Catalyst shape:
Reaction temperature: 350 ° C., SV = 40,000 hr−1
Model gas composition: NOx = 100 mass ppm, NH 3 = 100 mass ppm, O 2 = 7 wt%, H 2 O = 10 wt%, N 2 = balance [Example 2]
Preparation of Modified Titanium Oxide Fine Particle Powder (2) for Molded Body Modified titanium oxide-based fine particle powder (2) for molded body was the same as in Example 1 except that 4.7 g of stearic acid was used as a modifier. Was prepared.
成型体用改質酸化チタン系微粒子粉末(2)の平均粒子径および水分脱離率（ＷST％）を測定し、結果を表に示す。また、改質剤の含有量を表に示す。
The average particle diameter and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (2) for molded bodies were measured, and the results are shown in the table. The content of the modifier is shown in the table.
成型体用組成物(2)の調製
実施例１において、成型体用改質酸化チタン系微粒子粉末(2)を用いた以外は同様にして成型体用組成物(2)を調製した。 Preparation of molding composition (2) A molding composition (2) was prepared in the same manner as in Example 1 except that the modified titanium oxide fine particle powder (2) for molding was used.
実施例１において、成型体用改質酸化チタン系微粒子粉末(2)を用いた以外は同様にして成型体用組成物(2)を調製した。 Preparation of molding composition (2) A molding composition (2) was prepared in the same manner as in Example 1 except that the modified titanium oxide fine particle powder (2) for molding was used.
成型体用組成物(2)中の各成分の含有量を表に示す。
The content of each component in the molding composition (2) is shown in the table.
成型体(2)の調製
実施例１において、成型体用組成物(2)を用いた以外は同様にして成型体(2)を調製した。 Preparation of molded body (2) A molded body (2) was prepared in the same manner as in Example 1 except that the molded body composition (2) was used.
実施例１において、成型体用組成物(2)を用いた以外は同様にして成型体(2)を調製した。 Preparation of molded body (2) A molded body (2) was prepared in the same manner as in Example 1 except that the molded body composition (2) was used.
このとき、成型性を評価するとともに、得られた成型体(2)の各寸法を測定し、結果を表に示す。また、成型体(2)中の各成分の含有量を表に示す。
At this time, the moldability was evaluated, each dimension of the obtained molded body (2) was measured, and the results are shown in the table. In addition, the content of each component in the molded body (2) is shown in the table.
また、成型体(2)の比表面積、細孔容積、圧縮強度および脱硝触媒性能を測定し、結果を表に示す。
［実施例３］
成型体用改質酸化チタン系微粒子粉末(3)の調製
実施例１において、改質剤としてステアリン酸１１．８ｇを用いた以外は同様にして成型体用改質酸化チタン系微粒子粉末(3)を調製した。 Further, the specific surface area, pore volume, compressive strength, and denitration catalyst performance of the molded body (2) were measured, and the results are shown in the table.
[Example 3]
Preparation of Modified Titanium Oxide Fine Particle Powder (3) for Molded Body Modified titanium oxide fine particle powder (3) for molded body was the same as in Example 1 except that 11.8 g of stearic acid was used as a modifier. Was prepared.
［実施例３］
成型体用改質酸化チタン系微粒子粉末(3)の調製
実施例１において、改質剤としてステアリン酸１１．８ｇを用いた以外は同様にして成型体用改質酸化チタン系微粒子粉末(3)を調製した。 Further, the specific surface area, pore volume, compressive strength, and denitration catalyst performance of the molded body (2) were measured, and the results are shown in the table.
[Example 3]
Preparation of Modified Titanium Oxide Fine Particle Powder (3) for Molded Body Modified titanium oxide fine particle powder (3) for molded body was the same as in Example 1 except that 11.8 g of stearic acid was used as a modifier. Was prepared.
成型体用改質酸化チタン系微粒子粉末(3)の平均粒子径および水分脱離率（ＷST％）を測定し、結果を表に示す。また、改質剤の含有量を表に示す。
The average particle diameter and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (3) for molded bodies were measured, and the results are shown in the table. The content of the modifier is shown in the table.
成型体用組成物(3)の調製
実施例１において、成型体用改質酸化チタン系微粒子粉末(3)を用いた以外は同様にして成型体用組成物(3)を調製した。 Preparation of molding composition (3) A molding composition (3) was prepared in the same manner as in Example 1, except that the modified titanium oxide fine particle powder (3) for molding was used.
実施例１において、成型体用改質酸化チタン系微粒子粉末(3)を用いた以外は同様にして成型体用組成物(3)を調製した。 Preparation of molding composition (3) A molding composition (3) was prepared in the same manner as in Example 1, except that the modified titanium oxide fine particle powder (3) for molding was used.
成型体用組成物(3)中の各成分の含有量を表に示す。
The content of each component in the molding composition (3) is shown in the table.
成型体(3)の調製
実施例１において、成型体用組成物(3)を用いた以外は同様にして成型体(3)を調製した。 Preparation of molded body (3) A molded body (3) was prepared in the same manner as in Example 1 except that the molded body composition (3) was used.
実施例１において、成型体用組成物(3)を用いた以外は同様にして成型体(3)を調製した。 Preparation of molded body (3) A molded body (3) was prepared in the same manner as in Example 1 except that the molded body composition (3) was used.
このとき、成型性を評価するとともに、得られた成型体(3)の各寸法を測定し、結果を表に示す。また、成型体(3)中の各成分の含有量を表に示す。
At this time, the moldability was evaluated, each dimension of the obtained molded body (3) was measured, and the results are shown in the table. Further, the content of each component in the molded body (3) is shown in the table.
また、成型体(3)の比表面積、細孔容積、圧縮強度および脱硝触媒性能を測定し、結果を表に示す。
［実施例４］
成型体用改質酸化チタン系微粒子粉末(4)の調製
実施例１において、改質剤としてステアリン酸４７．０ｇを用いた以外は同様にして成型体用改質酸化チタン系微粒子粉末(4)を調製した。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (3) were measured, and the results are shown in the table.
[Example 4]
Preparation of Modified Titanium Oxide Fine Particle Powder (4) for Molded Body Modified Titanium Oxide Fine Particle Powder (4) for Molded Body in the same manner as in Example 1 except that 47.0 g of stearic acid was used as a modifier. Was prepared.
［実施例４］
成型体用改質酸化チタン系微粒子粉末(4)の調製
実施例１において、改質剤としてステアリン酸４７．０ｇを用いた以外は同様にして成型体用改質酸化チタン系微粒子粉末(4)を調製した。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (3) were measured, and the results are shown in the table.
[Example 4]
Preparation of Modified Titanium Oxide Fine Particle Powder (4) for Molded Body Modified Titanium Oxide Fine Particle Powder (4) for Molded Body in the same manner as in Example 1 except that 47.0 g of stearic acid was used as a modifier. Was prepared.
成型体用改質酸化チタン系微粒子粉末(4)の平均粒子径および水分脱離率（ＷST％）を測定し、結果を表に示す。また、改質剤の含有量を表に示す。
The average particle diameter and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (4) for molded bodies were measured, and the results are shown in the table. The content of the modifier is shown in the table.
成型体用組成物(4)の調製
実施例１において、成型体用改質酸化チタン系微粒子粉末(4)を用いた以外は同様にして成型体用組成物(4)を調製した。 Preparation of molding composition (4) A molding composition (4) was prepared in the same manner as in Example 1, except that the modified titanium oxide fine particle powder (4) for molding was used.
実施例１において、成型体用改質酸化チタン系微粒子粉末(4)を用いた以外は同様にして成型体用組成物(4)を調製した。 Preparation of molding composition (4) A molding composition (4) was prepared in the same manner as in Example 1, except that the modified titanium oxide fine particle powder (4) for molding was used.
成型体用組成物(4)中の各成分の含有量を表に示す。
The content of each component in the molding composition (4) is shown in the table.
成型体(4)の調製
実施例１において、成型体用組成物(4)を用いた以外は同様にして成型体(4)を調製した。 Preparation of molded body (4) A molded body (4) was prepared in the same manner as in Example 1, except that the molded body composition (4) was used.
実施例１において、成型体用組成物(4)を用いた以外は同様にして成型体(4)を調製した。 Preparation of molded body (4) A molded body (4) was prepared in the same manner as in Example 1, except that the molded body composition (4) was used.
このとき、成型性を評価するとともに、得られた成型体(4)の各寸法を測定し、結果を表に示す。また、成型体(4)中の各成分の含有量を表に示す。
At this time, the moldability was evaluated, each dimension of the obtained molded body (4) was measured, and the results are shown in the table. Further, the content of each component in the molded body (4) is shown in the table.
また、成型体(4)の比表面積、細孔容積、圧縮強度および脱硝触媒性能を測定し、結果を表に示す。
［実施例５］
成型体用改質酸化チタン系微粒子粉末(5)の調製
実施例１において、改質剤としてステアリン酸１１７．５ｇを用いた以外は同様にして成型体用改質酸化チタン系微粒子粉末(5)を調製した。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (4) were measured, and the results are shown in the table.
[Example 5]
Preparation of Modified Titanium Oxide Fine Particle Powder (5) for Molded Body Modified titanium oxide-based fine particle powder (5) for molded body was the same as in Example 1 except that 117.5 g of stearic acid was used as a modifier. Was prepared.
［実施例５］
成型体用改質酸化チタン系微粒子粉末(5)の調製
実施例１において、改質剤としてステアリン酸１１７．５ｇを用いた以外は同様にして成型体用改質酸化チタン系微粒子粉末(5)を調製した。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (4) were measured, and the results are shown in the table.
[Example 5]
Preparation of Modified Titanium Oxide Fine Particle Powder (5) for Molded Body Modified titanium oxide-based fine particle powder (5) for molded body was the same as in Example 1 except that 117.5 g of stearic acid was used as a modifier. Was prepared.
成型体用改質酸化チタン系微粒子粉末(5)の平均粒子径および水分脱離率（ＷST％）を測定し、結果を表に示す。また、改質剤の含有量を表に示す。
The average particle diameter and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (5) for molded bodies were measured, and the results are shown in the table. The content of the modifier is shown in the table.
成型体用組成物(5)の調製
実施例１において、成型体用改質酸化チタン系微粒子粉末(5)を用いた以外は同様にして成型体用組成物(5)を調製した。 Preparation of molding composition (5) A molding composition (5) was prepared in the same manner as in Example 1 except that the modified titanium oxide fine particle powder (5) for molding was used.
実施例１において、成型体用改質酸化チタン系微粒子粉末(5)を用いた以外は同様にして成型体用組成物(5)を調製した。 Preparation of molding composition (5) A molding composition (5) was prepared in the same manner as in Example 1 except that the modified titanium oxide fine particle powder (5) for molding was used.
成型体用組成物(5)中の各成分の含有量を表に示す。
The content of each component in the molding composition (5) is shown in the table.
成型体(5)の調製
実施例１において、成型体用組成物(5)を用いた以外は同様にして成型体(5)を調製した。 Preparation of molded body (5) A molded body (5) was prepared in the same manner as in Example 1 except that the molded body composition (5) was used.
実施例１において、成型体用組成物(5)を用いた以外は同様にして成型体(5)を調製した。 Preparation of molded body (5) A molded body (5) was prepared in the same manner as in Example 1 except that the molded body composition (5) was used.
このとき、成型性を評価するとともに、得られた成型体(5)の各寸法を測定し、結果を表に示す。また、成型体(5)中の各成分の含有量を表に示す。
At this time, the moldability was evaluated, each dimension of the obtained molded body (5) was measured, and the results are shown in the table. Further, the content of each component in the molded body (5) is shown in the table.
また、成型体(5)の比表面積、細孔容積、圧縮強度および脱硝触媒性能を測定し、結果を表に示す。
［実施例６］
成型体用改質酸化チタン系微粒子粉末(6)の調製
実施例１において、改質剤としてステアリン酸１８８ｇを用いた以外は同様にして成型体用改質酸化チタン系微粒子粉末(6)を調製した。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (5) were measured, and the results are shown in the table.
[Example 6]
Preparation of Modified Titanium Oxide Fine Particle Powder (6) for Molded Body In Example 1, modified titanium oxide fine particle powder (6) for molded body was prepared in the same manner except that 188 g of stearic acid was used as a modifier. did.
［実施例６］
成型体用改質酸化チタン系微粒子粉末(6)の調製
実施例１において、改質剤としてステアリン酸１８８ｇを用いた以外は同様にして成型体用改質酸化チタン系微粒子粉末(6)を調製した。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (5) were measured, and the results are shown in the table.
[Example 6]
Preparation of Modified Titanium Oxide Fine Particle Powder (6) for Molded Body In Example 1, modified titanium oxide fine particle powder (6) for molded body was prepared in the same manner except that 188 g of stearic acid was used as a modifier. did.
成型体用改質酸化チタン系微粒子粉末(6)の平均粒子径および水分脱離率（ＷST％）を測定し、結果を表に示すとともに図１に重量減少曲線を示し、図２に吸熱曲線を示す。
また、組成（使用量基準）を表に示す。 The average particle diameter and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (6) for molded bodies were measured. The results are shown in the table, the weight loss curve is shown in FIG. 1, and the endotherm is shown in FIG. A curve is shown.
Moreover, a composition (usage amount reference | standard) is shown in a table | surface.
また、組成（使用量基準）を表に示す。 The average particle diameter and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (6) for molded bodies were measured. The results are shown in the table, the weight loss curve is shown in FIG. 1, and the endotherm is shown in FIG. A curve is shown.
Moreover, a composition (usage amount reference | standard) is shown in a table | surface.
成型体用組成物(6)の調製
実施例１において、成型体用改質酸化チタン系微粒子粉末(6)を用いた以外は同様にして成型体用組成物(6)を調製した。 Preparation of molding composition (6) A molding composition (6) was prepared in the same manner as in Example 1 except that the modified titanium oxide fine particle powder (6) for molding was used.
実施例１において、成型体用改質酸化チタン系微粒子粉末(6)を用いた以外は同様にして成型体用組成物(6)を調製した。 Preparation of molding composition (6) A molding composition (6) was prepared in the same manner as in Example 1 except that the modified titanium oxide fine particle powder (6) for molding was used.
成型体用組成物(6)中の各成分の含有量（使用量基準）を表に示す。
The content (usage standard) of each component in the molding composition (6) is shown in the table.
成型体(6)の調製
実施例１において、成型体用組成物(6)を用いた以外は同様にして成型体(6)を調製した。 Preparation of molded body (6) A molded body (6) was prepared in the same manner as in Example 1 except that the molded body composition (6) was used.
実施例１において、成型体用組成物(6)を用いた以外は同様にして成型体(6)を調製した。 Preparation of molded body (6) A molded body (6) was prepared in the same manner as in Example 1 except that the molded body composition (6) was used.
このとき、成型性を評価するとともに、得られた成型体(6)の各寸法を測定し、結果を表に示す。また、成型体(6)中の各成分の含有量（使用量基準）を表に示す。
At this time, the moldability was evaluated, each dimension of the obtained molded body (6) was measured, and the results are shown in the table. In addition, the content (usage standard) of each component in the molded body (6) is shown in the table.
また、成型体(6)の比表面積、細孔容積、圧縮強度および脱硝触媒性能を測定し、結果を表に示す。
［実施例７］
成型体用改質酸化チタン系微粒子粉末(7)の調製
実施例１と同様にして、酸化チタン系微粒子粉末(7)を得た。得られた酸化チタン系微粒子粉末(7)２３．５ｋｇと、改質剤としてステアリン酸２３．５ｇをエタノール中に溶解した溶液１００ｍｌとを２０分間混合後、４０±５℃に調整した恒温槽中で乾燥して、成型体用改質酸化チタン系微粒子粉末(7)を調製した。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (6) were measured, and the results are shown in the table.
[Example 7]
Preparation of Modified Titanium Oxide Fine Particle Powder (7) for Molded Body Titanium oxide fine particle powder (7) was obtained in the same manner as in Example 1. In a thermostatic bath adjusted to 40 ± 5 ° C. after mixing for 20 minutes with 23.5 kg of the resulting titanium oxide fine particle powder (7) and 100 ml of a solution of 23.5 g of stearic acid dissolved in ethanol as a modifier. Was dried to prepare a modified titanium oxide fine particle powder (7) for a molded body.
［実施例７］
成型体用改質酸化チタン系微粒子粉末(7)の調製
実施例１と同様にして、酸化チタン系微粒子粉末(7)を得た。得られた酸化チタン系微粒子粉末(7)２３．５ｋｇと、改質剤としてステアリン酸２３．５ｇをエタノール中に溶解した溶液１００ｍｌとを２０分間混合後、４０±５℃に調整した恒温槽中で乾燥して、成型体用改質酸化チタン系微粒子粉末(7)を調製した。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (6) were measured, and the results are shown in the table.
[Example 7]
Preparation of Modified Titanium Oxide Fine Particle Powder (7) for Molded Body Titanium oxide fine particle powder (7) was obtained in the same manner as in Example 1. In a thermostatic bath adjusted to 40 ± 5 ° C. after mixing for 20 minutes with 23.5 kg of the resulting titanium oxide fine particle powder (7) and 100 ml of a solution of 23.5 g of stearic acid dissolved in ethanol as a modifier. Was dried to prepare a modified titanium oxide fine particle powder (7) for a molded body.
成型体用改質酸化チタン系微粒子粉末(7)の平均粒子径および水分脱離率（ＷST％）を測定し、結果を表に示す。また、改質剤の含有量を表に示す。
The average particle diameter and water desorption rate (W ST %) of the modified titanium oxide fine particle powder (7) for molded bodies were measured, and the results are shown in the table. The content of the modifier is shown in the table.
成型体用組成物(7)の調製
実施例１において、成型体用改質酸化チタン系微粒子粉末(7)を用いた以外は同様にして成型体用組成物(7)を調製した。 Preparation of molding composition (7) A molding composition (7) was prepared in the same manner as in Example 1, except that the modified titanium oxide fine particle powder (7) for molding was used.
実施例１において、成型体用改質酸化チタン系微粒子粉末(7)を用いた以外は同様にして成型体用組成物(7)を調製した。 Preparation of molding composition (7) A molding composition (7) was prepared in the same manner as in Example 1, except that the modified titanium oxide fine particle powder (7) for molding was used.
成型体用組成物(7)中の各成分の含有量を表に示す。
The content of each component in the molding composition (7) is shown in the table.
成型体(7)の調製
実施例１において、成型体用組成物(7)を用いた以外は同様にして成型体(7)を調製した。 Preparation of molded body (7) A molded body (7) was prepared in the same manner as in Example 1 except that the molded body composition (7) was used.
実施例１において、成型体用組成物(7)を用いた以外は同様にして成型体(7)を調製した。 Preparation of molded body (7) A molded body (7) was prepared in the same manner as in Example 1 except that the molded body composition (7) was used.
このとき、成型性を評価するとともに、得られた成型体(7)の各寸法を測定し、結果を表に示す。また、成型体(7)中の各成分の含有量を表に示す。
At this time, the moldability was evaluated, each dimension of the obtained molded body (7) was measured, and the results are shown in the table. Further, the content of each component in the molded body (7) is shown in the table.
また、成型体(7)の比表面積、細孔容積、圧縮強度および脱硝触媒性能を測定し、結果を表に示す。
［実施例８］
成型体用改質酸化チタン系微粒子粉末(8)の調製
実施例１において、改質剤としてラウリル酸23.5gを用いた以外は同様にして成型体用改質酸化チタン系微粒子粉末(8)を調製した。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (7) were measured, and the results are shown in the table.
[Example 8]
Preparation of Modified Titanium Oxide Fine Particle Powder (8) for Molded Body In Example 1, modified titanium oxide fine particle powder (8) for molded body was prepared in the same manner except that 23.5 g of lauric acid was used as a modifier. Prepared.
［実施例８］
成型体用改質酸化チタン系微粒子粉末(8)の調製
実施例１において、改質剤としてラウリル酸23.5gを用いた以外は同様にして成型体用改質酸化チタン系微粒子粉末(8)を調製した。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (7) were measured, and the results are shown in the table.
[Example 8]
Preparation of Modified Titanium Oxide Fine Particle Powder (8) for Molded Body In Example 1, modified titanium oxide fine particle powder (8) for molded body was prepared in the same manner except that 23.5 g of lauric acid was used as a modifier. Prepared.
成型体用改質酸化チタン系微粒子粉末(8)の平均粒子径および水分脱離率（ＷST％）を測定し、結果を表に示す。また、改質剤の含有量を表に示す。
The average particle diameter and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (8) for molded bodies were measured, and the results are shown in the table. The content of the modifier is shown in the table.
成型体用組成物(8)の調製
実施例１において、成型体用改質酸化チタン系微粒子粉末(8)を用いた以外は同様にして成型体用組成物(8)を調製した。 Preparation of molding composition (8) A molding composition (8) was prepared in the same manner as in Example 1, except that the modified titanium oxide fine particle powder (8) for molding was used.
実施例１において、成型体用改質酸化チタン系微粒子粉末(8)を用いた以外は同様にして成型体用組成物(8)を調製した。 Preparation of molding composition (8) A molding composition (8) was prepared in the same manner as in Example 1, except that the modified titanium oxide fine particle powder (8) for molding was used.
成型体用組成物(8)中の各成分の含有量を表に示す。
The content of each component in the molding composition (8) is shown in the table.
成型体(8)の調製
実施例１において、成型体用組成物(8)を用いた以外は同様にして成型体(8)を調製した。 Preparation of molded body (8) A molded body (8) was prepared in the same manner as in Example 1, except that the molded body composition (8) was used.
実施例１において、成型体用組成物(8)を用いた以外は同様にして成型体(8)を調製した。 Preparation of molded body (8) A molded body (8) was prepared in the same manner as in Example 1, except that the molded body composition (8) was used.
このとき、成型性を評価するとともに、得られた成型体(8)の各寸法を測定し、結果を表に示す。また、成型体(8)中の各成分の含有量を表に示す。
At this time, the moldability was evaluated, each dimension of the obtained molded body (8) was measured, and the results are shown in the table. In addition, the content of each component in the molded body (8) is shown in the table.
また、成型体(8)の比表面積、細孔容積、圧縮強度および脱硝触媒性能を測定し、結果を表に示す。
［実施例９］
成型体用改質酸化チタン系微粒子粉末(9)の調製
実施例１において、改質剤としてミリスチン酸23.5gを用いた以外は同様にして成型体用改質酸化チタン系微粒子粉末(9)を調製した。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (8) were measured, and the results are shown in the table.
[Example 9]
Preparation of Modified Titanium Oxide Fine Particle Powder (9) for Molded Body In Example 1, modified titanium oxide fine particle powder (9) for molded body was prepared in the same manner except that 23.5 g of myristic acid was used as a modifier. Prepared.
［実施例９］
成型体用改質酸化チタン系微粒子粉末(9)の調製
実施例１において、改質剤としてミリスチン酸23.5gを用いた以外は同様にして成型体用改質酸化チタン系微粒子粉末(9)を調製した。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (8) were measured, and the results are shown in the table.
[Example 9]
Preparation of Modified Titanium Oxide Fine Particle Powder (9) for Molded Body In Example 1, modified titanium oxide fine particle powder (9) for molded body was prepared in the same manner except that 23.5 g of myristic acid was used as a modifier. Prepared.
成型体用改質酸化チタン系微粒子粉末(9)の平均粒子径および水分脱離率（ＷST％）を測定し、結果を表に示す。また、改質剤の含有量を表に示す。
The average particle diameter and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (9) for molded bodies were measured, and the results are shown in the table. The content of the modifier is shown in the table.
成型体用組成物(9)の調製
実施例１において、成型体用改質酸化チタン系微粒子粉末(9)を用いた以外は同様にして成型体用組成物(9)を調製した。 Preparation of molding composition (9) A molding composition (9) was prepared in the same manner as in Example 1 except that the modified titanium oxide fine particle powder (9) for molding was used.
実施例１において、成型体用改質酸化チタン系微粒子粉末(9)を用いた以外は同様にして成型体用組成物(9)を調製した。 Preparation of molding composition (9) A molding composition (9) was prepared in the same manner as in Example 1 except that the modified titanium oxide fine particle powder (9) for molding was used.
成型体用組成物(9)中の各成分の含有量を表に示す。
The content of each component in the molding composition (9) is shown in the table.
成型体(9)の調製
実施例１において、成型体用組成物(9)を用いた以外は同様にして成型体(9)を調製した。 Preparation of molded body (9) A molded body (9) was prepared in the same manner as in Example 1 except that the molded body composition (9) was used.
実施例１において、成型体用組成物(9)を用いた以外は同様にして成型体(9)を調製した。 Preparation of molded body (9) A molded body (9) was prepared in the same manner as in Example 1 except that the molded body composition (9) was used.
このとき、成型性を評価するとともに、得られた成型体(9)の各寸法を測定し、結果を表に示す。また、成型体(9)中の各成分の含有量を表に示す。
At this time, the moldability was evaluated, each dimension of the obtained molded body (9) was measured, and the results are shown in the table. Further, the content of each component in the molded body (9) is shown in the table.
また、成型体(9)の比表面積、細孔容積、圧縮強度および脱硝触媒性能を測定し、結果を表に示す。
［実施例１０］
成型体用改質酸化チタン系微粒子粉末(10)の調製
実施例１において、改質剤としてパルミチン酸23.5gを用いた以外は同様にして成型体用改質酸化チタン系微粒子粉末(10)を調製した。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (9) were measured, and the results are shown in the table.
[Example 10]
Preparation of Modified Titanium Oxide Fine Particle Powder (10) for Molded Body In Example 1, modified titanium oxide fine particle powder (10) for molded body was prepared in the same manner except that 23.5 g of palmitic acid was used as a modifier. Prepared.
［実施例１０］
成型体用改質酸化チタン系微粒子粉末(10)の調製
実施例１において、改質剤としてパルミチン酸23.5gを用いた以外は同様にして成型体用改質酸化チタン系微粒子粉末(10)を調製した。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (9) were measured, and the results are shown in the table.
[Example 10]
Preparation of Modified Titanium Oxide Fine Particle Powder (10) for Molded Body In Example 1, modified titanium oxide fine particle powder (10) for molded body was prepared in the same manner except that 23.5 g of palmitic acid was used as a modifier. Prepared.
成型体用改質酸化チタン系微粒子粉末(10)の平均粒子径および水分脱離率（ＷST％）を測定し、結果を表に示す。また、改質剤の含有量を表に示す。
The average particle diameter and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (10) for molded bodies were measured, and the results are shown in the table. The content of the modifier is shown in the table.
成型体用組成物(10)の調製
実施例１において、成型体用改質酸化チタン系微粒子粉末(10)を用いた以外は同様にして成型体用組成物(10)を調製した。 Preparation of molding composition (10) A molding composition (10) was prepared in the same manner as in Example 1 except that the modified titanium oxide fine particle powder (10) for molding was used.
実施例１において、成型体用改質酸化チタン系微粒子粉末(10)を用いた以外は同様にして成型体用組成物(10)を調製した。 Preparation of molding composition (10) A molding composition (10) was prepared in the same manner as in Example 1 except that the modified titanium oxide fine particle powder (10) for molding was used.
成型体用組成物(10)中の各成分の含有量を表に示す。
The content of each component in the molding composition (10) is shown in the table.
成型体(10)の調製
実施例１において、成型体用組成物(10)を用いた以外は同様にして成型体(10)を調製した。 Preparation of molded body (10) A molded body (10) was prepared in the same manner as in Example 1 except that the molded body composition (10) was used.
実施例１において、成型体用組成物(10)を用いた以外は同様にして成型体(10)を調製した。 Preparation of molded body (10) A molded body (10) was prepared in the same manner as in Example 1 except that the molded body composition (10) was used.
このとき、成型性を評価するとともに、得られた成型体(10)の各寸法を測定し、結果を表に示す。また、成型体(10)中の各成分の含有量を表に示す。
At this time, the moldability was evaluated, each dimension of the obtained molded body (10) was measured, and the results are shown in the table. In addition, the content of each component in the molded body (10) is shown in the table.
また、成型体(10)の比表面積、細孔容積、圧縮強度および脱硝触媒性能を測定し、結果を表に示す。
［実施例１１］
成型体用改質酸化チタン系微粒子粉末(11)の調製
実施例１において、改質剤としてオレイン酸23.5gを用いた以外は同様にして成型体用改質酸化チタン系微粒子粉末(11)を調製した。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (10) were measured, and the results are shown in the table.
[Example 11]
Preparation of Modified Titanium Oxide Fine Particle Powder (11) for Molded Body In Example 1, modified titanium oxide fine particle powder (11) for molded body was prepared in the same manner except that 23.5 g of oleic acid was used as a modifier. Prepared.
［実施例１１］
成型体用改質酸化チタン系微粒子粉末(11)の調製
実施例１において、改質剤としてオレイン酸23.5gを用いた以外は同様にして成型体用改質酸化チタン系微粒子粉末(11)を調製した。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (10) were measured, and the results are shown in the table.
[Example 11]
Preparation of Modified Titanium Oxide Fine Particle Powder (11) for Molded Body In Example 1, modified titanium oxide fine particle powder (11) for molded body was prepared in the same manner except that 23.5 g of oleic acid was used as a modifier. Prepared.
成型体用改質酸化チタン系微粒子粉末(11)の平均粒子径および水分脱離率（ＷST％）を測定し、結果を表に示す。また、改質剤の含有量を表に示す。
The average particle diameter and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (11) for molded bodies were measured, and the results are shown in the table. The content of the modifier is shown in the table.
成型体用組成物(11)の調製
実施例１において、成型体用改質酸化チタン系微粒子粉末(11)を用いた以外は同様にして成型体用組成物(11)を調製した。成型体用組成物(11)中の各成分の含有量を表に示す。 Preparation of molding composition (11) A molding composition (11) was prepared in the same manner as in Example 1 except that the modified titanium oxide fine particle powder (11) for molding was used. The content of each component in the molding composition (11) is shown in the table.
実施例１において、成型体用改質酸化チタン系微粒子粉末(11)を用いた以外は同様にして成型体用組成物(11)を調製した。成型体用組成物(11)中の各成分の含有量を表に示す。 Preparation of molding composition (11) A molding composition (11) was prepared in the same manner as in Example 1 except that the modified titanium oxide fine particle powder (11) for molding was used. The content of each component in the molding composition (11) is shown in the table.
成型体(11)の調製
実施例１において、成型体用組成物(11)を用いた以外は同様にして成型体(11)を調製した。 Preparation of molded body (11) A molded body (11) was prepared in the same manner as in Example 1 except that the molded body composition (11) was used.
実施例１において、成型体用組成物(11)を用いた以外は同様にして成型体(11)を調製した。 Preparation of molded body (11) A molded body (11) was prepared in the same manner as in Example 1 except that the molded body composition (11) was used.
このとき、成型性を評価するとともに、得られた成型体(11)の各寸法を測定し、結果を表に示す。また、成型体(11)中の各成分の含有量を表に示す。
At this time, the moldability was evaluated, each dimension of the obtained molded body (11) was measured, and the results are shown in the table. Further, the content of each component in the molded body (11) is shown in the table.
また、成型体(11)の比表面積、細孔容積、圧縮強度および脱硝触媒性能を測定し、結果を表に示す。
［実施例１２］
成型体用改質酸化チタン系微粒子粉末(12)の調製
実施例１において、改質剤としてステアリン酸モノグリセライド23.5gを用いた以外は同様にして成型体用改質酸化チタン系微粒子粉末(12)を調製した。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (11) were measured, and the results are shown in the table.
[Example 12]
Preparation of Modified Titanium Oxide Fine Particle Powder (12) for Molded Body The modified titanium oxide fine particle powder (12) for molded body was the same as in Example 1 except that 23.5 g of stearic acid monoglyceride was used as a modifier. Was prepared.
［実施例１２］
成型体用改質酸化チタン系微粒子粉末(12)の調製
実施例１において、改質剤としてステアリン酸モノグリセライド23.5gを用いた以外は同様にして成型体用改質酸化チタン系微粒子粉末(12)を調製した。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (11) were measured, and the results are shown in the table.
[Example 12]
Preparation of Modified Titanium Oxide Fine Particle Powder (12) for Molded Body The modified titanium oxide fine particle powder (12) for molded body was the same as in Example 1 except that 23.5 g of stearic acid monoglyceride was used as a modifier. Was prepared.
成型体用改質酸化チタン系微粒子粉末(12)の平均粒子径および水分脱離率（ＷST％）を測定し、結果を表に示す。また、改質剤の含有量を表に示す。
The average particle diameter and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (12) for molded bodies were measured, and the results are shown in the table. The content of the modifier is shown in the table.
成型体用組成物(12)の調製
実施例１において、成型体用改質酸化チタン系微粒子粉末(12)を用いた以外は同様にして成型体用組成物(12)を調製した。 Preparation of molding composition (12) A molding composition (12) was prepared in the same manner as in Example 1 except that the modified titanium oxide fine particle powder (12) for molding was used.
実施例１において、成型体用改質酸化チタン系微粒子粉末(12)を用いた以外は同様にして成型体用組成物(12)を調製した。 Preparation of molding composition (12) A molding composition (12) was prepared in the same manner as in Example 1 except that the modified titanium oxide fine particle powder (12) for molding was used.
成型体用組成物(12)中の各成分の含有量を表に示す。
The content of each component in the molding composition (12) is shown in the table.
成型体(12)の調製
実施例１において、成型体用組成物(12)を用いた以外は同様にして成型体(12)を調製した。 Preparation of molded body (12) A molded body (12) was prepared in the same manner as in Example 1 except that the molded body composition (12) was used.
実施例１において、成型体用組成物(12)を用いた以外は同様にして成型体(12)を調製した。 Preparation of molded body (12) A molded body (12) was prepared in the same manner as in Example 1 except that the molded body composition (12) was used.
このとき、成型性を評価するとともに、得られた成型体(12)の各寸法を測定し、結果を表に示す。また、成型体(12)中の各成分の含有量を表に示す。
At this time, the moldability was evaluated, each dimension of the obtained molded body (12) was measured, and the results are shown in the table. Further, the content of each component in the molded body (12) is shown in the table.
また、成型体(12)の比表面積、細孔容積、圧縮強度および脱硝触媒性能を測定し、結果を表に示す。
［実施例１３］
成型体用改質酸化チタン系微粒子粉末(13)の調製
メタチタン酸スラリー（石原産業(株)製）７８．３ｋｇを加熱還流器付撹拌槽に仕込み、さらにパラタングステン酸アンモニウム１．９７ｋｇと、水硝子溶液を陽イオン交換樹脂で脱アルカリして調製したＳｉＯ2濃度４．０重量％の酸性ケイ酸液１８．８ｋｇを添加して混合した後、濃度１５重量％のアンモニア水３０．５ｋｇを加えてｐＨを９．５に調整し、さらに９５℃で１時間撹拌しながら熟成した。その後、この混合スラリーを４０℃まで冷却し、ついで、濾過し、掛け水により洗浄して、固形分濃度（ＴｉＯ2・ＷＯ3・ＳｉＯ2）５０重量％の洗浄ケーキを調製した。洗浄ケーキは、乾燥基準でＳＯ4を３．０重量％、Ｎａ2Ｏを０．０３重量％含有していた。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (12) were measured, and the results are shown in the table.
[Example 13]
Preparation of Modified Titanium Oxide Fine Particle Powder (13) for Molded Body 78.3 kg of metatitanic acid slurry (manufactured by Ishihara Sangyo Co., Ltd.) was charged into a stirring tank equipped with a heating reflux, and 1.97 kg of ammonium paratungstate and water After adding 18.8 kg of acid silicate solution having a SiO 2 concentration of 4.0 wt% prepared by dealkalizing the glass solution with a cation exchange resin, 30.5 kg of ammonia water having a concentration of 15 wt% was added. The pH was adjusted to 9.5, and the mixture was further aged with stirring at 95 ° C. for 1 hour. Then, this mixed slurry was cooled to 40 ° C., then filtered, and washed with water to prepare a washing cake having a solid content concentration (TiO 2 · WO 3 · SiO 2 ) of 50% by weight. The washed cake contained 3.0 wt% SO 4 and 0.03 wt% Na 2 O on a dry basis.
［実施例１３］
成型体用改質酸化チタン系微粒子粉末(13)の調製
メタチタン酸スラリー（石原産業(株)製）７８．３ｋｇを加熱還流器付撹拌槽に仕込み、さらにパラタングステン酸アンモニウム１．９７ｋｇと、水硝子溶液を陽イオン交換樹脂で脱アルカリして調製したＳｉＯ2濃度４．０重量％の酸性ケイ酸液１８．８ｋｇを添加して混合した後、濃度１５重量％のアンモニア水３０．５ｋｇを加えてｐＨを９．５に調整し、さらに９５℃で１時間撹拌しながら熟成した。その後、この混合スラリーを４０℃まで冷却し、ついで、濾過し、掛け水により洗浄して、固形分濃度（ＴｉＯ2・ＷＯ3・ＳｉＯ2）５０重量％の洗浄ケーキを調製した。洗浄ケーキは、乾燥基準でＳＯ4を３．０重量％、Ｎａ2Ｏを０．０３重量％含有していた。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (12) were measured, and the results are shown in the table.
[Example 13]
Preparation of Modified Titanium Oxide Fine Particle Powder (13) for Molded Body 78.3 kg of metatitanic acid slurry (manufactured by Ishihara Sangyo Co., Ltd.) was charged into a stirring tank equipped with a heating reflux, and 1.97 kg of ammonium paratungstate and water After adding 18.8 kg of acid silicate solution having a SiO 2 concentration of 4.0 wt% prepared by dealkalizing the glass solution with a cation exchange resin, 30.5 kg of ammonia water having a concentration of 15 wt% was added. The pH was adjusted to 9.5, and the mixture was further aged with stirring at 95 ° C. for 1 hour. Then, this mixed slurry was cooled to 40 ° C., then filtered, and washed with water to prepare a washing cake having a solid content concentration (TiO 2 · WO 3 · SiO 2 ) of 50% by weight. The washed cake contained 3.0 wt% SO 4 and 0.03 wt% Na 2 O on a dry basis.
ついで、洗浄ケーキを１１０℃で２０時間乾燥した後、さらに５５０℃で５時間焼成して酸化チタンと酸化タングステンとシリカの複合酸化物（ＴｉＯ2－ＷＯ3－ＳｉＯ2、重量比：ＴｉＯ2／ＷＯ3／ＳｉＯ2＝９０／７／３）からなる酸化チタン系微粒子粉末(13)を得た。
Next, the washed cake was dried at 110 ° C. for 20 hours, and further calcined at 550 ° C. for 5 hours to be a composite oxide of titanium oxide, tungsten oxide and silica (TiO 2 —WO 3 —SiO 2 , weight ratio: TiO 2 / A titanium oxide fine particle powder (13) composed of WO 3 / SiO 2 = 90/7/3) was obtained.
酸化チタン系微粒子粉末(13)の平均粒子径を測定し、結果を表に示す。また組成（調合基準）を表に示す。また、水分脱離率（Ｗ％）を測定し、結果を表に示す。
The average particle diameter of the titanium oxide fine particle powder (13) was measured, and the results are shown in the table. The composition (preparation standard) is shown in the table. Further, the moisture desorption rate (W%) was measured, and the results are shown in the table.
以下、実施例１において酸化チタン系微粒子粉末(13)を用いた以外は同様にして成型体用改質酸化チタン系微粒子粉末(13)を調製した。
Hereinafter, a modified titanium oxide fine particle powder (13) for a molded body was prepared in the same manner except that the titanium oxide fine particle powder (13) was used in Example 1.
成型体用改質酸化チタン系微粒子粉末(13)の平均粒子径および水分脱離率（ＷST％）を測定し、結果を表に示す。また、改質剤の含有量を表に示す。
The average particle diameter and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (13) for molded bodies were measured, and the results are shown in the table. The content of the modifier is shown in the table.
成型体用組成物(13)の調製
実施例１において、成型体用改質酸化チタン系微粒子粉末(13)を用いた以外は同様にして成型体用組成物(13)を調製した。 Preparation of molding composition (13) A molding composition (13) was prepared in the same manner as in Example 1, except that the modified titanium oxide fine particle powder (13) for molding was used.
実施例１において、成型体用改質酸化チタン系微粒子粉末(13)を用いた以外は同様にして成型体用組成物(13)を調製した。 Preparation of molding composition (13) A molding composition (13) was prepared in the same manner as in Example 1, except that the modified titanium oxide fine particle powder (13) for molding was used.
成型体用組成物(13)中の各成分の含有量を表に示す。
The content of each component in the molding composition (13) is shown in the table.
成型体(13)の調製
実施例１において、成型体用組成物(13)を用いた以外は同様にして成型体(13)を調製した。 Preparation of molded body (13) A molded body (13) was prepared in the same manner as in Example 1, except that the molded body composition (13) was used.
実施例１において、成型体用組成物(13)を用いた以外は同様にして成型体(13)を調製した。 Preparation of molded body (13) A molded body (13) was prepared in the same manner as in Example 1, except that the molded body composition (13) was used.
このとき、成型性を評価するとともに、得られた成型体(13)の各寸法を測定し、結果を表に示す。また、成型体(13)中の各成分の含有量を表に示す。
At this time, the moldability was evaluated, each dimension of the obtained molded body (13) was measured, and the results are shown in the table. In addition, the content of each component in the molded body (13) is shown in the table.
また、成型体(13)の比表面積、細孔容積、圧縮強度および脱硝触媒性能を測定し、結果を表に示す。
［比較例１］
成型体用酸化チタン系微粒子粉末(R1)の調製
実施例１において、改質剤を使用しなかった以外は同様にして成型体用酸化チタン系微粒子粉末(R1)を調製した。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (13) were measured, and the results are shown in the table.
[Comparative Example 1]
Preparation of Titanium Oxide Fine Particle Powder (R1) for Molded Body Titanium oxide fine particle powder (R1) for molded body was prepared in the same manner as in Example 1 except that no modifier was used.
［比較例１］
成型体用酸化チタン系微粒子粉末(R1)の調製
実施例１において、改質剤を使用しなかった以外は同様にして成型体用酸化チタン系微粒子粉末(R1)を調製した。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (13) were measured, and the results are shown in the table.
[Comparative Example 1]
Preparation of Titanium Oxide Fine Particle Powder (R1) for Molded Body Titanium oxide fine particle powder (R1) for molded body was prepared in the same manner as in Example 1 except that no modifier was used.
成型体用成型体用酸化チタン系微粒子粉末(R1)の平均粒子径を測定し、結果を表に示す。
The average particle diameter of the titanium oxide fine particle powder (R1) for molded bodies for molded bodies was measured, and the results are shown in the table.
成型体用組成物(R1)の調製
実施例１において、成型体用酸化チタン系微粒子粉末(R1)を用いた以外は同様にして成型体用組成物(R1)を調製した。 Preparation of molding composition (R1) A molding composition (R1) was prepared in the same manner as in Example 1 except that the titanium oxide fine particle powder (R1) for molding was used.
実施例１において、成型体用酸化チタン系微粒子粉末(R1)を用いた以外は同様にして成型体用組成物(R1)を調製した。 Preparation of molding composition (R1) A molding composition (R1) was prepared in the same manner as in Example 1 except that the titanium oxide fine particle powder (R1) for molding was used.
成型体用組成物(R1)中の各成分の含有量を表に示す。
The content of each component in the molding composition (R1) is shown in the table.
成型体(R1)の調製
実施例１において、成型体用組成物(R1)を用いた以外は同様にして押出成型を開始したが、間もなく目詰まりして成型ができなかった。
［比較例２］
成型体用酸化チタン系微粒子粉末(R2)の調製
実施例１３において、改質剤を使用しなかった以外は同様にして成型体用酸化チタン系微粒子粉末(R2)を調製した。 Preparation of molded body (R1) In Example 1, extrusion molding was started in the same manner except that the molded body composition (R1) was used, but it was soon clogged and could not be molded.
[Comparative Example 2]
Preparation of Titanium Oxide Fine Particle Powder (R2) for Molded Body Titanium oxide fine particle powder (R2) for molded body was prepared in the same manner as in Example 13 except that no modifier was used.
実施例１において、成型体用組成物(R1)を用いた以外は同様にして押出成型を開始したが、間もなく目詰まりして成型ができなかった。
［比較例２］
成型体用酸化チタン系微粒子粉末(R2)の調製
実施例１３において、改質剤を使用しなかった以外は同様にして成型体用酸化チタン系微粒子粉末(R2)を調製した。 Preparation of molded body (R1) In Example 1, extrusion molding was started in the same manner except that the molded body composition (R1) was used, but it was soon clogged and could not be molded.
[Comparative Example 2]
Preparation of Titanium Oxide Fine Particle Powder (R2) for Molded Body Titanium oxide fine particle powder (R2) for molded body was prepared in the same manner as in Example 13 except that no modifier was used.
成型体用酸化チタン系微粒子粉末(R2)の平均粒子径を測定し、結果を表に示す。
The average particle diameter of the titanium oxide fine particle powder (R2) for molding was measured, and the results are shown in the table.
成型体用組成物(R2)の調製
実施例１において、成型体用酸化チタン系微粒子粉末(R2)を用いた以外は同様にして成型体用組成物(R2)を調製した。 Preparation of molded body composition (R2) A molded body composition (R2) was prepared in the same manner as in Example 1, except that the molded body titanium oxide fine particle powder (R2) was used.
実施例１において、成型体用酸化チタン系微粒子粉末(R2)を用いた以外は同様にして成型体用組成物(R2)を調製した。 Preparation of molded body composition (R2) A molded body composition (R2) was prepared in the same manner as in Example 1, except that the molded body titanium oxide fine particle powder (R2) was used.
成型体用組成物(R2)中の各成分の含有量を表に示す。
The content of each component in the molding composition (R2) is shown in the table.
成型体(R2)の調製
実施例１において、成型体用組成物(R2)を用いた以外は同様にして押出成型を開始したが、間もなく目詰まりして成型ができなかった。
［比較例３］
成型体用組成物（R3）の調製
実施例１と同様にして調製した酸化チタン系微粒子粉末(1)２３．５ｋｇに、モノエタノールアミン０．３７５ｋｇにメタバナジン酸アンモニウムをＶ2Ｏ5として１．２８ｋｇを溶解した溶液を加え、ついで、ステアリン酸２３．５ｇを加え、次いでアンモニア水と水を加えてこの混合スラリーのｐＨを９とし、ニーダーにて１１０℃に加熱しながら捏和した。 Preparation of molded body (R2) Extrusion molding was started in the same manner as in Example 1 except that the molded body composition (R2) was used, but it was soon clogged and could not be molded.
[Comparative Example 3]
Preparation of composition for molding (R3) 1. 23.5 kg of titanium oxide fine particle powder (1) prepared in the same manner as in Example 1, 0.375 kg of monoethanolamine, and ammonium metavanadate as V 2 O 5 . A solution in which 28 kg was dissolved was added, then 23.5 g of stearic acid was added, then ammonia water and water were added to adjust the pH of the mixed slurry to 9, and kneaded while heating to 110 ° C. with a kneader.
実施例１において、成型体用組成物(R2)を用いた以外は同様にして押出成型を開始したが、間もなく目詰まりして成型ができなかった。
［比較例３］
成型体用組成物（R3）の調製
実施例１と同様にして調製した酸化チタン系微粒子粉末(1)２３．５ｋｇに、モノエタノールアミン０．３７５ｋｇにメタバナジン酸アンモニウムをＶ2Ｏ5として１．２８ｋｇを溶解した溶液を加え、ついで、ステアリン酸２３．５ｇを加え、次いでアンモニア水と水を加えてこの混合スラリーのｐＨを９とし、ニーダーにて１１０℃に加熱しながら捏和した。 Preparation of molded body (R2) Extrusion molding was started in the same manner as in Example 1 except that the molded body composition (R2) was used, but it was soon clogged and could not be molded.
[Comparative Example 3]
Preparation of composition for molding (R3) 1. 23.5 kg of titanium oxide fine particle powder (1) prepared in the same manner as in Example 1, 0.375 kg of monoethanolamine, and ammonium metavanadate as V 2 O 5 . A solution in which 28 kg was dissolved was added, then 23.5 g of stearic acid was added, then ammonia water and water were added to adjust the pH of the mixed slurry to 9, and kneaded while heating to 110 ° C. with a kneader.
その後、補強材としてグラスファイバー（オーウェンスコーニング(株)製：チョップドストランド０３ ＤＥ、長さ３ｍｍ、繊維径５μｍ）１．２５ｋｇ、（フィラー）として酸性白土１．２５ｋｇ、及び有機添加剤としてポリエチレンオキサイド０．５ｋｇを加えて、さらに捏和して、成型体用組成物(1)を調製した。
Thereafter, 1.25 kg of glass fiber (made by Owens Corning Co., Ltd .: chopped strand 03 DE, length 3 mm, fiber diameter 5 μm) as a reinforcing material, 1.25 kg of acid clay as (filler), and polyethylene oxide as an organic additive 0.5 kg was added and further kneaded to prepare a molding composition (1).
成型体用組成物(R3)中の各成分の含有量を表に示す。
The content of each component in the molding composition (R3) is shown in the table.
成型体(R3)の調製
実施例１において、成型体用組成物(R3)を用いた以外は同様にして成型体(R3)を調製した。 Preparation of molded body (R3) A molded body (R3) was prepared in the same manner as in Example 1 except that the molded body composition (R3) was used.
実施例１において、成型体用組成物(R3)を用いた以外は同様にして成型体(R3)を調製した。 Preparation of molded body (R3) A molded body (R3) was prepared in the same manner as in Example 1 except that the molded body composition (R3) was used.
このとき、成型性を評価するとともに、得られた成型体(R3)の各寸法を測定し、結果を表に示す。また、成型体(R3)中の各成分の含有量を表に示す。
At this time, the moldability was evaluated, each dimension of the obtained molded body (R3) was measured, and the results are shown in the table. Further, the content of each component in the molded body (R3) is shown in the table.
また、成型体(R3)の比表面積、細孔容積、圧縮強度および脱硝触媒性能を測定し、結果を表に示す。
［比較例４］
成型体用酸化チタン系微粒子粉末(R4)の調製
実施例１において、改質剤としてステアリン酸１１７５ｇを用いた以外は同様にして成型体用酸化チタン系微粒子粉末(R4)を調製した。成型体用酸化チタン系微粒子粉末(R4)の平均粒子径および水分脱離率（ＷST％）を測定し、結果を表に示すとともに図１に重量減少曲線を示し、図２に吸熱曲線を示す。また、改質剤の含有量を表に示す。
成型体用組成物(R4)の調製
実施例１において、成型体用酸化チタン系微粒子粉末(R4)を用いた以外は同様にして成型体用組成物(R4)を調製した。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (R3) were measured, and the results are shown in the table.
[Comparative Example 4]
Preparation of Titanium Oxide Fine Particle Powder (R4) for Molded Body Titanium oxide fine particle powder (R4) for molded body was prepared in the same manner as in Example 1 except that 1175 g of stearic acid was used as a modifier. The average particle diameter and moisture desorption rate (W ST %) of the titanium oxide fine particle powder (R4) for molded bodies were measured. The results are shown in the table, the weight loss curve is shown in FIG. 1, and the endothermic curve is shown in FIG. Show. The content of the modifier is shown in the table.
Preparation of molded body composition (R4) A molded body composition (R4) was prepared in the same manner as in Example 1, except that the molded body titanium oxide fine particle powder (R4) was used.
［比較例４］
成型体用酸化チタン系微粒子粉末(R4)の調製
実施例１において、改質剤としてステアリン酸１１７５ｇを用いた以外は同様にして成型体用酸化チタン系微粒子粉末(R4)を調製した。成型体用酸化チタン系微粒子粉末(R4)の平均粒子径および水分脱離率（ＷST％）を測定し、結果を表に示すとともに図１に重量減少曲線を示し、図２に吸熱曲線を示す。また、改質剤の含有量を表に示す。
成型体用組成物(R4)の調製
実施例１において、成型体用酸化チタン系微粒子粉末(R4)を用いた以外は同様にして成型体用組成物(R4)を調製した。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (R3) were measured, and the results are shown in the table.
[Comparative Example 4]
Preparation of Titanium Oxide Fine Particle Powder (R4) for Molded Body Titanium oxide fine particle powder (R4) for molded body was prepared in the same manner as in Example 1 except that 1175 g of stearic acid was used as a modifier. The average particle diameter and moisture desorption rate (W ST %) of the titanium oxide fine particle powder (R4) for molded bodies were measured. The results are shown in the table, the weight loss curve is shown in FIG. 1, and the endothermic curve is shown in FIG. Show. The content of the modifier is shown in the table.
Preparation of molded body composition (R4) A molded body composition (R4) was prepared in the same manner as in Example 1, except that the molded body titanium oxide fine particle powder (R4) was used.
成型体用組成物(R4)中の各成分の含有量を表に示す。
成型体(R4)の調製
実施例１において、成型体用組成物(R4)を用いた以外は同様にして成型体(R4)を調製した。 The content of each component in the molding composition (R4) is shown in the table.
Preparation of molded body (R4) A molded body (R4) was prepared in the same manner as in Example 1 except that the molded body composition (R4) was used.
成型体(R4)の調製
実施例１において、成型体用組成物(R4)を用いた以外は同様にして成型体(R4)を調製した。 The content of each component in the molding composition (R4) is shown in the table.
Preparation of molded body (R4) A molded body (R4) was prepared in the same manner as in Example 1 except that the molded body composition (R4) was used.
このとき、成型性を評価するとともに、得られた成型体(R4)の各寸法を測定し、結果を表に示す。また、成型体(R4)中の各成分の含有量を表に示す。
At this time, the moldability was evaluated, each dimension of the obtained molded body (R4) was measured, and the results are shown in the table. In addition, the content of each component in the molded body (R4) is shown in the table.
また、成型体(R4)の比表面積、細孔容積、圧縮強度および脱硝触媒性能を測定し、結果を表に示す。
［比較例５］
成型体用酸化チタン系微粒子粉末(R5)の調製
実施例１において、改質剤としてステアリン酸１．２ｇを用いた以外は同様にして成型体用酸化チタン系微粒子粉末(R5)を調製した。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (R4) were measured, and the results are shown in the table.
[Comparative Example 5]
Preparation of Titanium Oxide Fine Particle Powder (R5) for Molded Body Titanium oxide fine particle powder (R5) for molded body was prepared in the same manner as in Example 1 except that 1.2 g of stearic acid was used as a modifier.
［比較例５］
成型体用酸化チタン系微粒子粉末(R5)の調製
実施例１において、改質剤としてステアリン酸１．２ｇを用いた以外は同様にして成型体用酸化チタン系微粒子粉末(R5)を調製した。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (R4) were measured, and the results are shown in the table.
[Comparative Example 5]
Preparation of Titanium Oxide Fine Particle Powder (R5) for Molded Body Titanium oxide fine particle powder (R5) for molded body was prepared in the same manner as in Example 1 except that 1.2 g of stearic acid was used as a modifier.
成型体用酸化チタン系微粒子粉末(R5)の平均粒子径および水分脱離率（ＷST％）を測定し、結果を表に示す。また、改質剤の含有量を表に示す。
成型体用組成物(R5)の調製
実施例１において、成型体用酸化チタン系微粒子粉末(R5)を用いた以外は同様にして成型体用組成物(R5)を調製した。 The average particle diameter and moisture desorption rate (W ST %) of the titanium oxide fine particle powder (R5) for molded bodies were measured, and the results are shown in the table. The content of the modifier is shown in the table.
Preparation of molding composition (R5) A molding composition (R5) was prepared in the same manner as in Example 1 except that the titanium oxide fine particle powder (R5) for molding was used.
成型体用組成物(R5)の調製
実施例１において、成型体用酸化チタン系微粒子粉末(R5)を用いた以外は同様にして成型体用組成物(R5)を調製した。 The average particle diameter and moisture desorption rate (W ST %) of the titanium oxide fine particle powder (R5) for molded bodies were measured, and the results are shown in the table. The content of the modifier is shown in the table.
Preparation of molding composition (R5) A molding composition (R5) was prepared in the same manner as in Example 1 except that the titanium oxide fine particle powder (R5) for molding was used.
成型体用組成物(R5)中の各成分の含有量を表に示す。
成型体(R5)の調製
実施例１において、成型体用組成物(R5)を用いた以外は同様にして成型体(R5)を調製した。 The content of each component in the molding composition (R5) is shown in the table.
Preparation of molded body (R5) A molded body (R5) was prepared in the same manner as in Example 1 except that the molded body composition (R5) was used.
成型体(R5)の調製
実施例１において、成型体用組成物(R5)を用いた以外は同様にして成型体(R5)を調製した。 The content of each component in the molding composition (R5) is shown in the table.
Preparation of molded body (R5) A molded body (R5) was prepared in the same manner as in Example 1 except that the molded body composition (R5) was used.
このとき、成型性を評価するとともに、得られた成型体(R5)の各寸法を測定し、結果を表に示す。また、成型体(R5)中の各成分の含有量を表に示す。
At this time, the moldability was evaluated, each dimension of the obtained molded body (R5) was measured, and the results are shown in the table. The contents of each component in the molded body (R5) are shown in the table.
また、成型体(R5)の比表面積、細孔容積、圧縮強度および脱硝触媒性能を測定し、結果を表に示す。
［実施例14］
成型体用改質酸化チタン系微粒子粉末(14)の調製
メタチタン酸スラリー（石原産業(株)製）８７．０ｋｇを加熱還流器付撹拌槽に仕込み、濃度１５重量％のアンモニア水２０．５ｋｇを加えてｐＨを９．５に調整し、さらに９５℃で１時間撹拌しながら熟成した。その後、この混合スラリーを４０℃まで冷却し、ついで、濾過し、掛け水により洗浄して、固形分濃度（ＴｉＯ2）４９重量％の洗浄ケーキを調製した。洗浄ケーキは、乾燥基準でＳＯ4を３．０重量％、Ｎａ2Ｏを０．０３重量％含有していた。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (R5) were measured, and the results are shown in the table.
Example 14
Preparation of Modified Titanium Oxide Fine Particle Powder (14) for Molded Body 87.0 kg of metatitanic acid slurry (manufactured by Ishihara Sangyo Co., Ltd.) was charged into a stirring tank equipped with a heating reflux, and 20.5 kg of 15% by weight ammonia water In addition, the pH was adjusted to 9.5, and the mixture was further aged with stirring at 95 ° C. for 1 hour. Thereafter, the mixed slurry was cooled to 40 ° C., then filtered and washed with water to prepare a washing cake having a solid content concentration (TiO 2 ) of 49% by weight. The washed cake contained 3.0 wt% SO 4 and 0.03 wt% Na 2 O on a dry basis.
［実施例14］
成型体用改質酸化チタン系微粒子粉末(14)の調製
メタチタン酸スラリー（石原産業(株)製）８７．０ｋｇを加熱還流器付撹拌槽に仕込み、濃度１５重量％のアンモニア水２０．５ｋｇを加えてｐＨを９．５に調整し、さらに９５℃で１時間撹拌しながら熟成した。その後、この混合スラリーを４０℃まで冷却し、ついで、濾過し、掛け水により洗浄して、固形分濃度（ＴｉＯ2）４９重量％の洗浄ケーキを調製した。洗浄ケーキは、乾燥基準でＳＯ4を３．０重量％、Ｎａ2Ｏを０．０３重量％含有していた。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (R5) were measured, and the results are shown in the table.
Example 14
Preparation of Modified Titanium Oxide Fine Particle Powder (14) for Molded Body 87.0 kg of metatitanic acid slurry (manufactured by Ishihara Sangyo Co., Ltd.) was charged into a stirring tank equipped with a heating reflux, and 20.5 kg of 15% by weight ammonia water In addition, the pH was adjusted to 9.5, and the mixture was further aged with stirring at 95 ° C. for 1 hour. Thereafter, the mixed slurry was cooled to 40 ° C., then filtered and washed with water to prepare a washing cake having a solid content concentration (TiO 2 ) of 49% by weight. The washed cake contained 3.0 wt% SO 4 and 0.03 wt% Na 2 O on a dry basis.
ついで、洗浄ケーキを１１０℃で２０時間乾燥した後、さらに５４０℃で５時間焼成して酸化チタン酸化物（ＴｉＯ2）からなる酸化チタン系微粒子粉末(14)を得た。酸化チタン系微粒子粉末(14)の平均粒子径を測定し、結果を表に示す。また組成（調合基準）を表に示す。また、水分脱離率（Ｗ％）を測定し、結果を表に示す。
Next, the washed cake was dried at 110 ° C. for 20 hours, and further calcined at 540 ° C. for 5 hours to obtain titanium oxide fine particle powder (14) made of titanium oxide oxide (TiO 2 ). The average particle diameter of the titanium oxide fine particle powder (14) was measured, and the results are shown in the table. The composition (formulation standard) is shown in the table. Further, the moisture desorption rate (W%) was measured, and the results are shown in the table.
以下、実施例１において酸化チタン系微粒子粉末(14)を用いた以外は同様にして成型体用改質酸化チタン系微粒子粉末(14)を調製した。成型体用改質酸化チタン系微粒子粉末(14)の平均粒子径および水分脱離率（ＷST％）を測定し、結果を表に示す。また、改質剤の含有量を表に示す。
成型体用組成物(14)の調製
実施例１において、成型体用改質酸化チタン系微粒子粉末(14)を用いた以外は同様にして成型体用組成物(14)を調製した。成型体用組成物(14)中の各成分の含有量を表に示す。
成型体(14)の調製
実施例１において、成型体用組成物(14)を用いた以外は同様にして成型体(14)を調製した。 Thereafter, a modified titanium oxide fine particle powder (14) for a molded body was prepared in the same manner except that the titanium oxide fine particle powder (14) was used in Example 1. The average particle diameter and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (14) for molded bodies were measured, and the results are shown in the table. The content of the modifier is shown in the table.
Preparation of molding composition (14) A molding composition (14) was prepared in the same manner as in Example 1, except that the modified titanium oxide fine particle powder (14) for molding was used. The content of each component in the molding composition (14) is shown in the table.
Preparation of molded body (14) A molded body (14) was prepared in the same manner as in Example 1 except that the molded body composition (14) was used.
成型体用組成物(14)の調製
実施例１において、成型体用改質酸化チタン系微粒子粉末(14)を用いた以外は同様にして成型体用組成物(14)を調製した。成型体用組成物(14)中の各成分の含有量を表に示す。
成型体(14)の調製
実施例１において、成型体用組成物(14)を用いた以外は同様にして成型体(14)を調製した。 Thereafter, a modified titanium oxide fine particle powder (14) for a molded body was prepared in the same manner except that the titanium oxide fine particle powder (14) was used in Example 1. The average particle diameter and moisture desorption rate (W ST %) of the modified titanium oxide fine particle powder (14) for molded bodies were measured, and the results are shown in the table. The content of the modifier is shown in the table.
Preparation of molding composition (14) A molding composition (14) was prepared in the same manner as in Example 1, except that the modified titanium oxide fine particle powder (14) for molding was used. The content of each component in the molding composition (14) is shown in the table.
Preparation of molded body (14) A molded body (14) was prepared in the same manner as in Example 1 except that the molded body composition (14) was used.
このとき、成型性を評価するとともに、得られた成型体(14)の各寸法を測定し、結果を表に示す。また、成型体(14)中の各成分の含有量を表に示す。
At this time, the moldability was evaluated, each dimension of the obtained molded body (14) was measured, and the results are shown in the table. In addition, the content of each component in the molded body (14) is shown in the table.
また、成型体(14)の比表面積、細孔容積、圧縮強度および脱硝触媒性能を測定し、結果を表に示す。
［比較例6］
成型体用酸化チタン系微粒子粉末(R6)の調製
実施例１４において、改質剤を使用しなかった以外は同様にして成型体用酸化チタン系微粒子粉末(R6)を調製した。
成型体用酸化チタン系微粒子粉末(R6)の平均粒子径を測定し、結果を表に示す。
成型体用組成物(R6)の調製
実施例１において、成型体用酸化チタン系微粒子粉末(R6)を用いた以外は同様にして成型体用組成物(R6)を調製した。成型体用組成物(R6)中の各成分の含有量を表に示す。
成型体(R6)の調製
実施例１において、成型体用組成物(R6)を用いた以外は同様にして成型体(R6)を調製した。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (14) were measured, and the results are shown in the table.
[Comparative Example 6]
Preparation of Titanium Oxide Fine Particle Powder (R6) for Molded Body Titanium oxide fine particle powder (R6) for molded body was prepared in the same manner as in Example 14 except that no modifier was used.
The average particle diameter of the titanium oxide fine particle powder (R6) for molded bodies was measured, and the results are shown in the table.
Preparation of molded body composition (R6) A molded body composition (R6) was prepared in the same manner as in Example 1 except that the molded body titanium oxide fine particle powder (R6) was used. The content of each component in the molding composition (R6) is shown in the table.
Preparation of molded body (R6) A molded body (R6) was prepared in the same manner as in Example 1 except that the molded body composition (R6) was used.
［比較例6］
成型体用酸化チタン系微粒子粉末(R6)の調製
実施例１４において、改質剤を使用しなかった以外は同様にして成型体用酸化チタン系微粒子粉末(R6)を調製した。
成型体用酸化チタン系微粒子粉末(R6)の平均粒子径を測定し、結果を表に示す。
成型体用組成物(R6)の調製
実施例１において、成型体用酸化チタン系微粒子粉末(R6)を用いた以外は同様にして成型体用組成物(R6)を調製した。成型体用組成物(R6)中の各成分の含有量を表に示す。
成型体(R6)の調製
実施例１において、成型体用組成物(R6)を用いた以外は同様にして成型体(R6)を調製した。 Further, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (14) were measured, and the results are shown in the table.
[Comparative Example 6]
Preparation of Titanium Oxide Fine Particle Powder (R6) for Molded Body Titanium oxide fine particle powder (R6) for molded body was prepared in the same manner as in Example 14 except that no modifier was used.
The average particle diameter of the titanium oxide fine particle powder (R6) for molded bodies was measured, and the results are shown in the table.
Preparation of molded body composition (R6) A molded body composition (R6) was prepared in the same manner as in Example 1 except that the molded body titanium oxide fine particle powder (R6) was used. The content of each component in the molding composition (R6) is shown in the table.
Preparation of molded body (R6) A molded body (R6) was prepared in the same manner as in Example 1 except that the molded body composition (R6) was used.
このとき、成型性を評価するとともに、得られた成型体(R6)の各寸法を測定し、結果を表に示す。また、成型体(R6)中の各成分の含有量を表に示す。
At this time, the moldability was evaluated, each dimension of the obtained molded body (R6) was measured, and the results are shown in the table. The contents of each component in the molded body (R6) are shown in the table.
また、成型体(R6)の比表面積、細孔容積、圧縮強度および脱硝触媒性能を測定し、結果を表に示す。
Also, the specific surface area, pore volume, compressive strength and denitration catalyst performance of the molded body (R6) were measured, and the results are shown in the table.
Claims (15)
- 酸化チタン系微粒子からなり、かつ該酸化チタン系微粒子が、脂肪酸および／または脂肪酸エステルからなる改質剤で改質されてなり、かつ該改質剤の含有量が０．０１～１．５重量％の範囲にあることを特徴とする成型体用改質酸化チタン系微粒子粉末。 It consists of titanium oxide-based fine particles, and the titanium oxide-based fine particles are modified with a modifier comprising a fatty acid and / or a fatty acid ester, and the content of the modifier is 0.01 to 1.5 wt. % Modified titanium oxide fine particle powder for molded bodies, characterized in that it is in the range of%.
- 前記脂肪酸が下記式(1)で表される飽和脂肪酸および／または下記式(2)で表される不飽和脂肪酸であることを特徴とする請求項１に記載の成型体用改質酸化チタン系微粒子粉末。
ＣnＨ2n－ＣＯ2Ｈ・・・・・・・・・・・・・・・・（１）
（但し、ｎは４～２３の整数）
Ｃn'Ｈ2n'-2m+1－ＣＯ2Ｈ・・・・・・（２）
（但し、ｎ'は１３～２３の整数、ｍは２重結合の数を表す１～６の整数） The modified titanium oxide system for molded articles according to claim 1, wherein the fatty acid is a saturated fatty acid represented by the following formula (1) and / or an unsaturated fatty acid represented by the following formula (2): Fine powder.
C n H 2n -CO 2 H (1)
(Where n is an integer from 4 to 23)
C n ′ H 2n′-2m + 1 —CO 2 H (2)
(Where n ′ is an integer from 13 to 23, m is an integer from 1 to 6 representing the number of double bonds) - 前記改質酸化チタン系微粒子の平均粒子径が０．０３～２．５μｍの範囲にあることを特徴とする請求項１に記載の成型体用改質酸化チタン系微粒子粉末。 The modified titanium oxide fine particle powder for molded bodies according to claim 1, wherein the average particle diameter of the modified titanium oxide fine particles is in the range of 0.03 to 2.5 µm.
- 前記酸化チタン系微粒子の平均粒子径が０．０３～２．０μｍの範囲にあることを特徴とする請求項１に記載の成型体用改質酸化チタン系微粒子粉末。 2. The modified titanium oxide-based fine particle powder for molded bodies according to claim 1, wherein the average particle diameter of the titanium oxide-based fine particles is in the range of 0.03 to 2.0 μm.
- 酸化チタン系微粒子が、酸化チタンとともに、酸化タングステン（ＷＯ3）、酸化モリブデン（ＭoＯ3）、酸化珪素（ＳiＯ2）、酸化ジルコニウム（ＺrＯ2）から選ばれる酸化物の少なくとも１種を含み、酸化チタン系微粒子中の含有量が酸化物として０．５～４０重量％の範囲にあることを特徴とする請求項１に記載の成型体用改質酸化チタン系微粒子粉末。 The titanium oxide fine particles contain at least one oxide selected from tungsten oxide (WO 3 ), molybdenum oxide (MoO 3 ), silicon oxide (SiO 2 ), and zirconium oxide (ZrO 2 ) together with titanium oxide. 2. The modified titanium oxide fine particle powder for molded bodies according to claim 1, wherein the content of the titanium fine particles is in the range of 0.5 to 40% by weight as an oxide.
- 水分を１５重量％に調整した前記酸化チタン系微粒子の示唆熱分析における３０℃から１００℃に昇温した際の重量減少率（Ｗ（％））と、水分を１５重量％に調整した前記成型体用改質酸化チタン系微粒子粉末の示唆熱分析における３０℃から１００℃に昇温した際の重量減少率（ＷST（％））との重量減少率比（ＷST（％））／（Ｗ（％））が１．０２～１．２０の範囲にあることを特徴とする請求項１～５のいずれかに記載の成型体用改質酸化チタン系微粒子粉末。 The weight reduction rate (W (%)) when the temperature was raised from 30 ° C. to 100 ° C. in the suggested thermal analysis of the titanium oxide fine particles adjusted to 15% by weight, and the molding adjusted to 15% by weight. -body modified titanium oxide-based fine particles of the differential thermal analysis weight loss rate when the temperature was raised to 100 ° C. from 30 ° C. in (W ST (%)) and weight loss ratio (W ST (%)) / ( 6. The modified titanium oxide-based fine particle powder for molded bodies according to any one of claims 1 to 5, wherein W (%) is in the range of 1.02 to 1.20.
- (i)請求項１～６のいずれかに記載の成型体用改質酸化チタン系微粒子粉末、
(ii)補強材、
(iii)活性成分前駆体化合物 を含む組成物であり、
該組成物中の(i) 成型体用改質酸化チタン系微粒子粉末の含有量が、３３～８０．８重量％の範囲にあり、(ii)補強材の含有量が１．８～１２．８重量％の範囲にあり、(iii)活性成分前駆体化合物の含有量が酸化物換算して０．０００６～１２．８重量％の範囲にあり、
全固形分濃度が６０～８５重量％の範囲にあることを特徴とする成型体用組成物。 (i) Modified titanium oxide-based fine particle powder for molded body according to any one of claims 1 to 6,
(ii) reinforcement,
(iii) a composition containing an active ingredient precursor compound,
In the composition, the content of (i) the modified titanium oxide fine particle powder for molded bodies is in the range of 33 to 80.8% by weight, and (ii) the content of the reinforcing material is 1.8 to 12. (Iii) the content of the active ingredient precursor compound is in the range of 0.0006 to 12.8% by weight in terms of oxide,
A molding composition, wherein the total solid concentration is in the range of 60 to 85% by weight. - さらに、フィラーを含んでなり、該フィラーの含有量が固形分として０．６～１２．８重量％の範囲にあることを特徴とする請求項７に記載の成型体用組成物。 The composition for molded bodies according to claim 7, further comprising a filler, wherein the content of the filler is in the range of 0.6 to 12.8% by weight as a solid content.
- さらに、前記改質剤以外の有機添加剤を０．０３～４．５重量％の範囲で含んでなることを特徴とする請求項７に記載の成型体用組成物。 The molded article composition according to claim 7, further comprising an organic additive other than the modifier in a range of 0.03 to 4.5% by weight.
- 前記活性成分前駆体化合物が、Ｖ、Ｗ、Ｍｏ、Ｃｒ、Ｍｎ、Ｆｅ、Ｎｉ、Ｃｕ、Ａｇ、Ａｕ、Ｐｄ、Ｙ、Ｃｅ、Ｎｄ、Ｉｎ、Ｉｒからなる群から選ばれる少なくとも１種の元素の化合物であることを特徴とする請求項７に記載の成型体用組成物。 The active component precursor compound is at least one element selected from the group consisting of V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, and Ir. The composition for molded bodies according to claim 7, which is a compound of:
- (i)請求項１～６のいずれかに記載の成型体用改質酸化チタン系微粒子粉末、
(ii)補強材、
(iii)活性成分 を含み
(i) 成型体用改質酸化チタン系微粒子粉末の含有量が５５～９５重量％の範囲にあり、(ii)補強材の含有量が３～１５重量％の範囲にあり、(iii)活性成分の含有量が酸化物として０．００１～１５重量％の範囲にあることを特徴とする成型体。 (i) Modified titanium oxide-based fine particle powder for molded body according to any one of claims 1 to 6,
(ii) reinforcement,
(iii) contains active ingredient (i) content of modified titanium oxide fine particle powder for molded body is in the range of 55 to 95% by weight, and (ii) content of reinforcing material is in the range of 3 to 15% by weight (Iii) A molded product characterized in that the content of the active ingredient is in the range of 0.001 to 15% by weight as an oxide. - さらに、フィラーを含み、該フィラーの含有量が１～１５重量％の範囲にあることを特徴とする請求項１１に記載の成型体。 The molded article according to claim 11, further comprising a filler, wherein the filler content is in the range of 1 to 15% by weight.
- 前記成型体がハニカム成型体であり、該ハニカムの外径が３０～４００ｍｍの範囲にあり、長さが３～１５００ｍｍの範囲にあり、ピッチが６～５００ｃｐｓｉの範囲にあり、肉厚が０．１～１．５ｍｍの範囲にあることを特徴とする請求項１１または１２に記載の成型体。 The molded body is a honeycomb molded body, the outer diameter of the honeycomb is in the range of 30 to 400 mm, the length is in the range of 3 to 1500 mm, the pitch is in the range of 6 to 500 cpsi, and the wall thickness is 0. The molded article according to claim 11 or 12, wherein the molded article is in the range of 1 to 1.5 mm.
- 前記活性成分が、Ｖ、Ｗ、Ｍｏ、Ｃｒ、Ｍｎ、Ｆｅ、Ｎｉ、Ｃｕ、Ａｇ、Ａｕ、Ｐｄ、Ｙ、Ｃｅ、Ｎｄ、Ｉｎ、Ｉｒから選ばれる少なくとも1種の元素の金属または金属酸化物であることを特徴とする請求項１１～１３のいずれかに記載の成型体。 The active component is a metal or metal oxide of at least one element selected from V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, and Ir The molded body according to any one of claims 11 to 13, wherein
- 前記肉厚が０．１～０．３ｍｍの範囲にあることを特徴とする請求項１３に記載の成型体。 The molded body according to claim 13, wherein the thickness is in the range of 0.1 to 0.3 mm.
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| JP2014554480A JP6068512B2 (en) | 2012-12-28 | 2013-12-25 | Modified titanium oxide fine particle powder for molded body, composition for molded body, and molded body |
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| JPH09249459A (en) * | 1996-03-14 | 1997-09-22 | Murata Mfg Co Ltd | Production of composite material of ceramic with resin and production of ceramic sintered compact |
| JPH09328369A (en) * | 1996-02-16 | 1997-12-22 | Murata Mfg Co Ltd | Production of ceramic sintered compact |
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| CN101233090B (en) * | 2005-08-01 | 2012-07-04 | 日立金属株式会社 | Process for producing ceramic honeycomb structure |
| JP5142569B2 (en) * | 2007-03-27 | 2013-02-13 | 京セラ株式会社 | Heat-resistant ceramic material |
| CN101260006B (en) * | 2007-11-01 | 2011-06-29 | 北京奥福(临邑)精细陶瓷有限公司 | Method for preparing honeycomb ceramic containing titanium dioxide |
| WO2009141881A1 (en) * | 2008-05-20 | 2009-11-26 | イビデン株式会社 | Honeycomb structure |
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| JPH09328369A (en) * | 1996-02-16 | 1997-12-22 | Murata Mfg Co Ltd | Production of ceramic sintered compact |
| JPH09249459A (en) * | 1996-03-14 | 1997-09-22 | Murata Mfg Co Ltd | Production of composite material of ceramic with resin and production of ceramic sintered compact |
| JP2009226583A (en) * | 2008-02-27 | 2009-10-08 | Jgc Catalysts & Chemicals Ltd | Ceramic molding clay and its manufacturing method, method of manufacturing ceramic molding using ceramic molding clay, and ceramic molding manufactured thereby |
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| CN117259758A (en) * | 2023-10-05 | 2023-12-22 | 广东三浩铸锻科技有限公司 | Method for preparing part from waste steel |
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