WO2014104071A1 - Poudre de particules fines modifiées d'oxyde de titane pour des corps moulés, composition pour des corps moulés et corps moulé - Google Patents

Poudre de particules fines modifiées d'oxyde de titane pour des corps moulés, composition pour des corps moulés et corps moulé Download PDF

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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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titanium oxide
molded body
fine particle
particle powder
content
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PCT/JP2013/084607
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English (en)
Japanese (ja)
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健太郎 山口
足立　健太郎
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日揮触媒化成株式会社
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Priority to JP2014554480A priority Critical patent/JP6068512B2/ja
Priority to CN201380068347.3A priority patent/CN104936927B/zh
Publication of WO2014104071A1 publication Critical patent/WO2014104071A1/fr

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    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
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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

La présente invention concerne une poudre modifiée d'oxyde de titane qui est susceptible de produire un corps moulé en nid d'abeilles dont l'épaisseur et le poids peuvent être réduits, même si le nombre de pas est augmenté, tout en présentant d'excellentes propriétés d'aptitude au moulage, de solidité, de résistance à l'usure, de résistance à la fissuration et similaires. La présente invention concerne une poudre de particules fines modifiées d'oxyde de titane qui se compose de particules fines d'oxyde de titane et est caractérisée en ce que : les particules fines d'oxyde de titane sont modifiées par un agent modifiant qui se compose d'un acide gras et/ou d'un ester d'acide gras ; et la teneur de l'agent modifiant est dans l'intervalle de 0,01 à 1,0 % en poids. Une poudre de particules fines modifiées d'oxyde de titane est caractérisée en ce que l'acide gras est un acide gras saturé représenté par la formule (1) et/ou un acide gras insaturé représenté par la formule (2). CnH2n-CO2H (1) Cn'H2n'-2m+1-CO2H (2) (Dans les formules, n représente un nombre entier de 4 à 23 ; n' représente un nombre entier de 13 à 23 ; et m représente un nombre entier de 1 à 6 qui est le nombre de doubles liaisons).
PCT/JP2013/084607 2012-12-28 2013-12-25 Poudre de particules fines modifiées d'oxyde de titane pour des corps moulés, composition pour des corps moulés et corps moulé WO2014104071A1 (fr)

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JP2014554480A JP6068512B2 (ja) 2012-12-28 2013-12-25 成型体用改質酸化チタン系微粒子粉末および成型体用組成物ならびに成型体
CN201380068347.3A CN104936927B (zh) 2012-12-28 2013-12-25 成形体用改性氧化钛类微粒粉末及成形体用组合物以及成形体

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