WO2019163533A1 - Method for producing honeycomb structure - Google Patents
Method for producing honeycomb structure Download PDFInfo
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- WO2019163533A1 WO2019163533A1 PCT/JP2019/004439 JP2019004439W WO2019163533A1 WO 2019163533 A1 WO2019163533 A1 WO 2019163533A1 JP 2019004439 W JP2019004439 W JP 2019004439W WO 2019163533 A1 WO2019163533 A1 WO 2019163533A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/478—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on aluminium titanates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
Definitions
- the present invention relates to a method for manufacturing a honeycomb structure.
- exhaust gas discharged from an internal combustion engine such as a diesel engine contains particulate matter (hereinafter also referred to as PM).
- PM particulate matter
- various honeycomb filters made of a honeycomb structure using cordierite, silicon carbide, aluminum titanate, or the like have been proposed as filters for collecting PM in the exhaust gas and purifying the exhaust gas.
- the honeycomb structure using aluminum titanate has a higher melting temperature than the honeycomb structure using cordierite, so that it is difficult for melting damage to occur when burning PM as a honeycomb filter, Since the thermal expansion coefficient is lower than that of a honeycomb structure using silicon carbide, it is known that even a large filter is not easily broken by thermal stress applied during PM combustion.
- Patent Document 1 in a method for producing a ceramic honeycomb structure made of aluminum titanate by firing a clay made by mixing a TiO 2 source powder and an Al 2 O 3 source powder, 0.2 to 4 ⁇ m The use of a TiO 2 source powder having relatively small particle size in the range and relatively large particle size in the range of 10-100 ⁇ m is described. According to the method described in Patent Document 1, it is said that an aluminum titanate ceramic honeycomb structure having few cracks and a large average pore diameter can be obtained while maintaining the excellent performance of a low thermal expansion coefficient.
- the present invention has been made to solve the above problems, and an object of the present invention is to provide a method for manufacturing a honeycomb structure having a low thermal expansion coefficient and a low firing shrinkage rate.
- a method for manufacturing a honeycomb structured body of the present invention includes a step of obtaining a honeycomb formed body by forming a raw material composition containing an inorganic powder containing titania powder and alumina powder and a pore former, and the honeycomb formed body described above.
- the volume ratio of particles having a particle diameter of 5 ⁇ m or less and particles having a particle diameter exceeding 5 ⁇ m in the inorganic powder is adjusted to obtain particles having a particle diameter exceeding 5 ⁇ m. Is larger than particles of 5 ⁇ m or less. Thereby, the shrinkage
- the distance between the particles at the time of molding can be taken sufficiently, and the distance between the particles can be kept constant even after firing. This is because it can.
- the ratio of the pore former is preferably 30% by volume to 60% by volume with respect to the total volume of particles contained in the raw material composition.
- the ratio of the pore former is less than 30% by volume, the porosity becomes too small.
- the ratio of the pore former exceeds 60% by volume, the shrinkage during firing becomes too large and cracks are generated. End up.
- the titania powder preferably includes a titania coarse powder and a titania fine powder having an average particle diameter D50 smaller than that of the titania coarse powder.
- titania coarse particles with a large average particle size and titania fine particles with a small average particle size are used in combination.
- the volume ratio of the particles in the raw material composition can be adjusted, shrinkage during firing can be suppressed.
- the pore distribution of the fired aluminum titanate porous body can be sharpened.
- the titania fine particles are present, the synthesis reaction and sintering of aluminum titanate are facilitated, so that deterioration of the thermal expansion coefficient and strength can be suppressed.
- the average particle diameter D50 of the titania coarse powder is 5 to 25 ⁇ m, and the average particle diameter D50 of the titania fine powder is 0.1 to 1.5 ⁇ m. preferable.
- the thermal expansion coefficient can be lowered, the firing shrinkage rate can be reduced, and the pore distribution of the fired aluminum titanate porous body can be sharpened.
- the average particle size D50 of the titania coarse powder is equal to or smaller than the average particle size D50 of the alumina powder. Is preferred. In this case, shrinkage during firing can be further suppressed.
- the inorganic powder preferably further contains silica powder and magnesia powder.
- the silicon element derived from silica and the magnesium element derived from magnesia are dissolved in the aluminum titanate, thermal decomposition of the aluminum titanate can be suppressed, and use at a high temperature is possible.
- Fig. 1 (a) is a perspective view schematically showing an example of a honeycomb structure manufactured by the manufacturing method of the present invention
- Fig. 1 (b) is an A of the honeycomb structure shown in Fig. 1 (a).
- FIG. 1 (a) is a perspective view schematically showing an example of a honeycomb structure manufactured by the manufacturing method of the present invention
- Fig. 1 (b) is an A of the honeycomb structure shown in Fig. 1 (a).
- the method for manufacturing a honeycomb structured body of the present invention includes a forming step for obtaining a honeycomb formed body by forming a raw material composition, and a firing step for firing the honeycomb formed body.
- a honeycomb formed body is obtained by forming a raw material composition containing an inorganic powder and a pore former.
- the inorganic powder in the raw material composition includes titania powder and alumina powder.
- the inorganic powder preferably further contains silica powder and magnesia powder.
- the raw material composition further includes a pore former.
- the inorganic powder contains particles having a particle size of 5 ⁇ m or less in an amount of more than 25% by volume and less than 50% by volume, while the particle size exceeds 5 ⁇ m.
- the particles are contained in an amount of more than 50% by volume and less than 75% by volume.
- the particle size distribution is measured on a volume basis by a laser diffraction / scattering particle size distribution measurement method, and the volume ratio and particle size of particles having a particle size of 5 ⁇ m or less are determined. Determine the volume fraction of particles over 5 ⁇ m.
- a volume-based blending ratio is obtained from the weight-based blending ratio and density of each inorganic powder contained in the raw material composition. From the above values, the volume ratio of the particles having a particle diameter of 5 ⁇ m or less and the particles having a particle diameter exceeding 5 ⁇ m in the inorganic powder can be obtained.
- the titania powder preferably contains a titania coarse powder and a fine titania powder having an average particle diameter D50 smaller than that of the titania coarse powder.
- the average particle diameter D50 of the titania powder is a particle diameter corresponding to 50% cumulative from the smaller diameter side of the volume-based cumulative particle diameter by the laser diffraction / scattering particle size distribution measurement method.
- the average particle diameter D50 of the titania coarse powder is not particularly limited as long as it is larger than the average particle diameter D50 of the titania fine powder, but is equal to the average particle diameter D50 of the alumina powder or from the average particle diameter D50 of the alumina powder. Is preferably small.
- the average particle diameter D50 of the titania coarse powder is preferably 5 ⁇ m or more, and more preferably 10 ⁇ m or more. Further, the average particle diameter D50 of the titania coarse powder is preferably 25 ⁇ m or less, and more preferably 20 ⁇ m or less.
- the average particle diameter D50 of the titania fine powder is preferably 0.1 ⁇ m or more, and more preferably 0.4 ⁇ m or more.
- the average particle diameter D50 of the titania fine powder is preferably 1.5 ⁇ m or less, and more preferably 1 ⁇ m or less.
- the coarse titania powder preferably contains more iron than the fine titania powder. As described above, the sinterability is lowered by increasing the titania particle size. However, the inclusion of iron that facilitates sintering in the titania coarse powder results in uniform sintering, so the spacing between the alumina particles and the titania coarse particles is uniform, and uniform pores are formed in the gaps. can do.
- the titania fine powder may contain iron or may not contain iron (that is, it may be below the detection limit).
- the iron content of titania powder is measured by ICP emission spectroscopic analysis.
- the iron content of the titania crude powder is preferably 0.1 to 0.3%. Further, the iron content of the titania fine powder is preferably less than 0.1%, more preferably less than 0.01%.
- the mixing ratio of the titania coarse powder and the titania fine powder is preferably 40:60 to 80:20, more preferably 45:55 to 75:25, in terms of weight ratio. .
- the titania powder is preferably contained in the raw material composition in an amount of 15 to 40% by weight in total of the titania coarse powder and the titania fine powder.
- the average particle diameter D50 of the alumina powder is not particularly limited, but it is preferably equal to the average particle diameter D50 of the titania coarse powder or larger than the average particle diameter D50 of the titania coarse powder.
- the average particle diameter D50 of the alumina powder is preferably 10 ⁇ m or more, and more preferably 15 ⁇ m or more. Moreover, the average particle diameter D50 of the alumina powder is preferably 40 ⁇ m or less, and more preferably 30 ⁇ m or less.
- the alumina powder is preferably contained in the raw material composition in an amount of 20 to 45% by weight.
- the raw material composition preferably further includes silica powder and magnesia powder as the inorganic powder.
- the average particle diameter D50 of the silica powder is preferably 0.1 ⁇ m or more.
- the average particle diameter D50 of the silica powder is preferably 10 ⁇ m or less, and more preferably 5 ⁇ m or less.
- the silica powder is preferably contained in the raw material composition in an amount of 0.5 to 5% by weight.
- the average particle diameter D50 of the magnesia powder is preferably 1 ⁇ m or more, and more preferably 2 ⁇ m or more. Moreover, it is preferable that the average particle diameter D50 of a magnesia powder is 10 micrometers or less. The average particle diameter D50 of the magnesia powder is preferably larger than the average particle diameter D50 of the silica powder.
- the magnesia powder is preferably contained in the raw material composition in an amount of 0.5 to 5% by weight.
- Examples of the pore former contained in the raw material composition include acrylic resin, graphite, and starch.
- the average particle diameter D50 of the pore former is preferably 10 ⁇ m or more, and more preferably 20 ⁇ m or more. Further, the average particle diameter D50 of the pore former is preferably 60 ⁇ m or less, and more preferably 40 ⁇ m or less.
- the ratio of the pore former is preferably 30% by volume or more, and more preferably 40% by volume or more with respect to the total volume of the particles contained in the raw material composition. Further, the ratio of the pore former is preferably 60% by volume or less, and more preferably 50% by volume or less with respect to the total volume of particles contained in the raw material composition.
- the ratio of a pore former is 40 volume% or more and 70 volume% or less with respect to the total volume of the particle
- the raw material composition may contain a molding aid, an organic binder, and a dispersion medium.
- the molding aid include ethylene glycol, dextrin, fatty acid, fatty acid soap, and polyalcohol.
- the organic binder include hydrophilic organic polymers such as carboxymethyl cellulose, polyvinyl alcohol, methyl cellulose, and ethyl cellulose.
- the dispersion medium include a dispersion medium composed only of water, or a dispersion medium composed of 50% by volume or more of water and an organic solvent.
- the organic solvent include alcohols such as benzene and methanol.
- the raw material composition may further contain other materials.
- other materials include plasticizers, dispersants, lubricants, and the like.
- plasticizer include polyoxyalkylene compounds such as polyoxyethylene alkyl ether and polyoxypropylene alkyl ether.
- dispersant include sorbitan fatty acid esters.
- lubricant include glycerin.
- the raw material composition is formed to obtain a honeycomb formed body.
- the raw material composition put into an extruder is extruded in the mold direction while being mixed and kneaded in a sealed state using a screw having various shapes, etc., to obtain a kneaded state suitable for extrusion molding, Extrusion molding is performed through a mold to produce a continuous body of honeycomb molded bodies in which a large number of through holes are arranged in parallel in the longitudinal direction with a wall portion therebetween.
- a formed body corresponding to a part of the shape of the honeycomb structure may be formed. That is, a molded body having the same shape as the honeycomb structure may be manufactured by forming a formed body corresponding to a part of the shape of the honeycomb structure and combining the formed bodies.
- microwave dryer, hot air dryer, dielectric dryer, vacuum dryer, vacuum Drying is performed using a dryer, a freeze dryer, or the like, followed by a degreasing process for decomposing and eliminating organic components in the honeycomb formed body.
- the honeycomb formed body obtained in the forming step is fired to obtain a fired body.
- the reaction between the alumina particles and the titania particles proceeds to form an aluminum titanate phase.
- the firing temperature is preferably 1300 to 1600 ° C. Firing can be performed using a known single furnace, a so-called batch furnace, or a continuous furnace.
- the firing time is not particularly limited, but it is preferable to hold at the above firing temperature for 1 to 20 hours.
- the oxygen concentration may be adjusted by mixing an inert gas such as nitrogen gas or argon gas in the air atmosphere.
- honeycomb structure made of aluminum titanate can be manufactured.
- FIG. 1 (a) is a perspective view schematically showing an example of a honeycomb structure manufactured by the manufacturing method of the present invention
- Fig. 1 (b) is an A of the honeycomb structure shown in Fig. 1 (a).
- FIG. The honeycomb structure 10 shown in FIG. 1 (a) has a columnar shape, and the exhaust gas introduction cell 11a and the exhaust gas whose cross-sectional shape perpendicular to the longitudinal direction (the direction indicated by the double arrow a in FIG. 1 (a)) is substantially rectangular. Many discharge cells 11b are formed.
- the exhaust gas introduction cell 11a and the exhaust gas discharge cell 11b are formed with a cell partition wall 13 therebetween.
- An outer peripheral wall 16 is formed on the outer periphery of the honeycomb structure 10.
- the exhaust gas discharge cell 11b is sealed by the sealing portion 12b on the end surface 14 on the side where the exhaust gas is introduced, and the exhaust gas introduction cell 11a is open.
- the exhaust gas introduction cell 11a is sealed by the sealing portion 12a, and the exhaust gas discharge cell 11b is open.
- the exhaust gas G introduced into the exhaust gas introduction cell 11a from the end surface 14 passes through the cell partition wall 13 which is a porous wall, and then passes through the exhaust gas exhaust cell 11b. It is discharged from the end face 15. During this time, PM in the exhaust gas is collected by the cell partition wall 13 and the exhaust gas is purified.
- the honeycomb structure manufactured by the method for manufacturing a honeycomb structure of the present invention preferably functions as a honeycomb filter that removes PM in exhaust gas. Moreover, the honeycomb structure manufactured by the method for manufacturing a honeycomb structure of the present invention may be used as a catalyst carrier by supporting various catalysts and the like without sealing.
- Example 1 Titanium fine powder with D50 of 0.6 ⁇ m (iron content less than 0.01%): 22.2% by weight, alumina powder with D50 of 21.5 ⁇ m: 30.4% by weight, silica powder with D50 of 1.1 ⁇ m: 2.8% by weight, D50 of 3.8 ⁇ m magnesia powder: 1.4% by weight, D50 of 31.9 ⁇ m acrylic resin (pore forming material): 18.5% by weight, methylcellulose (organic binder): 7.1
- a raw material composition was prepared by mixing with a mixer a composition comprising 5% by weight, a molding aid (ester type nonion): 4.7% by weight, and ion-exchanged water (dispersion medium): 12.9% by weight.
- the volume ratio of the particles having a particle diameter of 5 ⁇ m or less and the particles having a particle diameter exceeding 5 ⁇ m is 46.1: 53.9.
- the ratio of the pore former is 43.4% by volume with respect to the total volume of the particles contained in the raw material composition, and 59% with respect to the total volume of the particles having a particle diameter of more than 5 ⁇ m contained in the raw material composition. 8% by volume.
- the prepared raw material composition was put into an extruder and subjected to extrusion to produce a honeycomb formed body having the shape shown in FIG. 1A and having no cells sealed.
- the cells of the honeycomb formed body were alternately plugged using a sealing material having the same composition as the raw material composition. After drying and degreasing, a cylindrical honeycomb structure was produced by firing at 1450 ° C. for 15 hours in an air atmosphere and firing.
- Example 2 “Titanium fine powder with D50 of 0.6 ⁇ m (iron content less than 0.01%): 22.2% by weight” “Rough titania powder with D50 of 13.6 ⁇ m (iron content of 0.25%): 11. 1% by weight, titania fine powder having D50 of 0.6 ⁇ m (iron content less than 0.01%): 11.1% by weight ”A honeycomb structure was manufactured in the same manner as in Example 1. .
- the volume ratio of particles having a particle size of 5 ⁇ m or less and particles having a particle size exceeding 5 ⁇ m is 33.1-66.9.
- the ratio of the pore former is 43.4% by volume with respect to the total volume of the particles contained in the raw material composition, and 54% with respect to the total volume of the particles having a particle diameter of more than 5 ⁇ m contained in the raw material composition. .4% by volume.
- Example 3 A honeycomb structure was manufactured in the same manner as in Example 2 except that the titania coarse powder was changed to 15.5 wt% and the titania fine powder was changed to 6.7 wt%.
- the volume ratio of particles having a particle size of 5 ⁇ m or less and particles having a particle size exceeding 5 ⁇ m is 27.9: 72.1.
- the ratio of the pore former is 43.4% by volume with respect to the total volume of the particles contained in the raw material composition, and 52% with respect to the total volume of the particles having a particle diameter of more than 5 ⁇ m contained in the raw material composition. .5% by volume.
- Example 4 A honeycomb structure was manufactured in the same manner as in Example 2 except that D50 of the alumina powder was changed to 15.4 ⁇ m.
- the volume ratio of particles having a particle diameter of 5 ⁇ m or less and particles having a particle diameter exceeding 5 ⁇ m is 45.3: 54.7.
- the ratio of the pore former is 43.4% by volume with respect to the total volume of the particles contained in the raw material composition, and 58% with respect to the total volume of the particles having a particle diameter of more than 5 ⁇ m contained in the raw material composition. 8% by volume.
- Example 1 “D50 titania fine powder (iron content less than 0.01%): 22.2 wt%” “D50 13.6 ⁇ m titania coarse powder (iron content 0.25%): 22.
- a honeycomb structure was manufactured in the same manner as in Example 1 except that the content was changed to “2 wt%”.
- the volume ratio of particles having a particle size of 5 ⁇ m or less and particles having a particle size exceeding 5 ⁇ m is 20.1: 79.9.
- the ratio of the pore former is 43.4% by volume with respect to the total volume of the particles contained in the raw material composition, and 49% with respect to the total volume of the particles having a particle diameter of more than 5 ⁇ m contained in the raw material composition. .9% by volume.
- Example 2 A honeycomb structure was manufactured in the same manner as in Example 1 except that D50 of the alumina powder was changed to 15.4 ⁇ m.
- the volume ratio of particles having a particle diameter of 5 ⁇ m or less and particles having a particle diameter exceeding 5 ⁇ m is 58.3: 41.7.
- the ratio of the pore former is 43.4% by volume with respect to the total volume of the particles contained in the raw material composition, and 65% with respect to the total volume of the particles having a particle diameter of more than 5 ⁇ m contained in the raw material composition. .2% by volume.
- Firing shrinkage rate (%) [(full length before firing) ⁇ (full length after firing)] / (full length before firing)] ⁇ 100
- the breaking load was measured for ten three-point bending strength measurement samples, and the average value was taken as the bending strength.
- the three-point bending strength test was performed using an Instron 5582 with reference to JIS R 1601, a span distance of 30 mm, and a speed of 1 mm / min.
- AT conversion rate [AT conversion rate] X-ray diffraction measurement was performed using a powder having a particle size of 0.5 mm or less produced by pulverizing a part of the obtained honeycomb structure, and the integrated intensity I AT (101) of the (101) plane of aluminum titanate from the integrated intensity I TiO2 of TiO 2 (110) plane (111) was determined AT conversion ratio from the following equation.
- AT conversion rate (%) [I AT (101) / (I AT (101) + I TiO2 (111) )] ⁇ 100
- thermomechanical analyzer NETZSCH DIL402C
- the average thermal expansion coefficient between 50 and 1000 ° C. was measured by measuring the increase in length in the full length direction when heated from room temperature to 1000 ° C. at a temperature rising rate of 10 ° C./min while applying a constant load of 20 g. Asked.
- the obtained honeycomb structure was cut out to 10 mm ⁇ 10 mm ⁇ 10 mm to prepare a sample for pore distribution measurement.
- the porosity and the pore distribution were measured by a porosimeter (manufactured by Shimadzu Corporation, Autopore III 9420) by a mercury intrusion method.
- the contact angle was 130 ° and the surface tension was 485 mN / m by mercury porosimetry.
- the pore distribution was measured in the range of 1 to 100 ⁇ m, and the pore distribution curve was drawn with the pore diameter ( ⁇ m) on the X axis and the log differential pore volume (mL / g) on the Y axis.
- d10, d50, and d90 were calculated from each pore distribution curve.
- a value represented by the formula (d90-d10) / d50 was calculated and used as the pore sharpness. It can be said that the smaller the value, the sharper the shape of the pore distribution curve.
- d10, d50, and d90 are pore diameters corresponding to cumulative 10%, cumulative 50%, and cumulative 90% from the small diameter side of the cumulative pore volume in the pore distribution curve.
- Examples 1 to 4 have a low firing shrinkage ratio and a high bending strength. Further, the AT conversion rate is 100% and the thermal expansion coefficient is low. Furthermore, it has a sharp pore distribution.
- Comparative Example 1 in which the proportion of particles having a particle diameter exceeding 5 ⁇ m is too large, the synthesis reaction of aluminum titanate hardly proceeds, so the AT conversion rate is low, the bending strength is low, and the thermal expansion coefficient is high.
- Comparative Example 2 in which the proportion of particles having a particle diameter exceeding 5 ⁇ m is too small, the firing shrinkage ratio is large.
- a honeycomb structure having a low thermal expansion coefficient and a low firing shrinkage rate can be obtained by adjusting the volume ratio of particles having a particle size of 5 ⁇ m or less and particles having a particle size exceeding 5 ⁇ m in the inorganic powder. It is thought that it is obtained.
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Abstract
A method of the present invention for producing a honeycomb structure is a method for producing a honeycomb structure made of aluminum titanate the method comprising: a step for obtaining a honeycomb formed body by forming a raw material composition including a pore-forming material and inorganic powder containing titania powder and alumina powder; and a step for baking the honeycomb formed body, wherein the method is characterized in that the volume percentage of particles having a particle diameter of 5 μm or less in the inorganic powder is greater than 25 vol% and less than 50 vol%.
Description
本発明は、ハニカム構造体の製造方法に関する。
The present invention relates to a method for manufacturing a honeycomb structure.
従来、ディーゼルエンジン等の内燃機関から排出される排ガス中には、パティキュレートマター(以下、PMともいう)が含まれており、近年、このPMが環境や人体に害を及ぼすことが問題となっている。
そこで、排ガス中のPMを捕集して排ガスを浄化するフィルタとして、コージェライト、炭化珪素、チタン酸アルミニウムなどを用いたハニカム構造体からなるハニカムフィルタが種々提案されている。 Conventionally, exhaust gas discharged from an internal combustion engine such as a diesel engine contains particulate matter (hereinafter also referred to as PM). In recent years, it has been a problem that this PM is harmful to the environment and the human body. ing.
Accordingly, various honeycomb filters made of a honeycomb structure using cordierite, silicon carbide, aluminum titanate, or the like have been proposed as filters for collecting PM in the exhaust gas and purifying the exhaust gas.
そこで、排ガス中のPMを捕集して排ガスを浄化するフィルタとして、コージェライト、炭化珪素、チタン酸アルミニウムなどを用いたハニカム構造体からなるハニカムフィルタが種々提案されている。 Conventionally, exhaust gas discharged from an internal combustion engine such as a diesel engine contains particulate matter (hereinafter also referred to as PM). In recent years, it has been a problem that this PM is harmful to the environment and the human body. ing.
Accordingly, various honeycomb filters made of a honeycomb structure using cordierite, silicon carbide, aluminum titanate, or the like have been proposed as filters for collecting PM in the exhaust gas and purifying the exhaust gas.
これらのなかで、チタン酸アルミニウムを用いたハニカム構造体は、コージェライトを用いたハニカム構造体よりも溶融温度が高いので、ハニカムフィルタとしてPMを燃焼させる際に溶損が発生しにくく、また、炭化珪素を用いたハニカム構造体よりも熱膨張率が低いので、大型のフィルタであってもPMの燃焼に際してかかる熱応力によって破壊されにくいことが知られている。
Among these, the honeycomb structure using aluminum titanate has a higher melting temperature than the honeycomb structure using cordierite, so that it is difficult for melting damage to occur when burning PM as a honeycomb filter, Since the thermal expansion coefficient is lower than that of a honeycomb structure using silicon carbide, it is known that even a large filter is not easily broken by thermal stress applied during PM combustion.
特許文献1には、TiO2源粉末及びAl2O3源粉末を混合してなる坏土を焼成することによりチタン酸アルミニウムからなるセラミックハニカム構造体を製造する方法において、0.2~4μmの範囲にある比較的小さな粒径の粒子と10~100μmの範囲にある比較的大きな粒径の粒子とを有するTiO2源粉末を使用することが記載されている。特許文献1に記載の方法によれば、低熱膨張係数という優れた性能を維持しつつ、割れが少なく、かつ大きな平均細孔径を有するチタン酸アルミニウム質セラミックハニカム構造体が得られるとされている。
In Patent Document 1, in a method for producing a ceramic honeycomb structure made of aluminum titanate by firing a clay made by mixing a TiO 2 source powder and an Al 2 O 3 source powder, 0.2 to 4 μm The use of a TiO 2 source powder having relatively small particle size in the range and relatively large particle size in the range of 10-100 μm is described. According to the method described in Patent Document 1, it is said that an aluminum titanate ceramic honeycomb structure having few cracks and a large average pore diameter can be obtained while maintaining the excellent performance of a low thermal expansion coefficient.
しかしながら、特許文献1に記載の方法では、チタニア等の粒子径を大きくすることで焼結性が悪化することがあり、その結果、得られるハニカム構造体の強度の低下や気孔分布の不均一化を引き起こすおそれがある。
However, in the method described in Patent Document 1, the sinterability may be deteriorated by increasing the particle size of titania or the like. As a result, the strength of the resulting honeycomb structure is reduced and the pore distribution is not uniform. May cause.
本発明は、上記の問題を解決するためになされたものであり、熱膨張係数が低く、焼成収縮率が小さいハニカム構造体を製造する方法を提供することを目的とする。
The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for manufacturing a honeycomb structure having a low thermal expansion coefficient and a low firing shrinkage rate.
本発明のハニカム構造体の製造方法は、チタニア粉末及びアルミナ粉末を含む無機粉末と、造孔材とを含む原料組成物を成形することにより、ハニカム成形体を得る工程と、上記ハニカム成形体を焼成する工程とを含む、チタン酸アルミニウムからなるハニカム構造体の製造方法であって、上記無機粉末中、粒子径が5μm以下の粒子の占める体積割合が25体積%より大きく、50体積%より小さいことを特徴とする。
A method for manufacturing a honeycomb structured body of the present invention includes a step of obtaining a honeycomb formed body by forming a raw material composition containing an inorganic powder containing titania powder and alumina powder and a pore former, and the honeycomb formed body described above. A method of manufacturing a honeycomb structure made of aluminum titanate, including a step of firing, wherein a volume ratio of particles having a particle diameter of 5 μm or less in the inorganic powder is larger than 25 volume% and smaller than 50 volume% It is characterized by that.
本発明のハニカム構造体の製造方法では、無機粉末中の、粒子径が5μm以下の粒子と粒子径が5μmを超える粒子との体積比を調整して、粒子径が5μmを超える粒子を粒子径が5μm以下の粒子よりも多くしている。これにより、焼成時の収縮を抑えることができる。無機粉末中に粒子径が5μmを超える粒子が50体積%よりも多く含まれることにより、成形時の粒子間の距離が充分にとられ、焼成しても粒子間の距離を一定に保つことができるためである。かつ、その成形体の粒子間に粒子径が5μm以下の粒子が入り込むことで、焼成時のチタニア粉末とアルミナ粉末との合成反応が進行しやすくなる。一方、無機粉末中に粒子径が5μmを超える粒子が75体積%よりも少なく含まれることにより、粒子同士の接触点が増え、チタン酸アルミニウムの合成反応が進行しやすくなる。
In the method for manufacturing a honeycomb structured body of the present invention, the volume ratio of particles having a particle diameter of 5 μm or less and particles having a particle diameter exceeding 5 μm in the inorganic powder is adjusted to obtain particles having a particle diameter exceeding 5 μm. Is larger than particles of 5 μm or less. Thereby, the shrinkage | contraction at the time of baking can be suppressed. By including more than 50% by volume of particles having a particle diameter of more than 5 μm in the inorganic powder, the distance between the particles at the time of molding can be taken sufficiently, and the distance between the particles can be kept constant even after firing. This is because it can. In addition, when particles having a particle size of 5 μm or less enter between the particles of the molded body, the synthesis reaction of the titania powder and the alumina powder during the firing easily proceeds. On the other hand, when the inorganic powder contains less than 75% by volume of particles having a particle diameter of more than 5 μm, the contact point between the particles increases, and the synthesis reaction of aluminum titanate easily proceeds.
本発明のハニカム構造体の製造方法では、上記原料組成物に含まれる粒子の合計体積に対して、上記造孔材の割合が、30体積%以上、60体積%以下であることが好ましい。
造孔材の割合が30体積%未満であると、気孔率が小さくなりすぎ、一方、造孔材の割合が60体積%を超えると、焼成時の収縮が大きくなりすぎ、クラックが発生してしまう。 In the method for manufacturing a honeycomb structure of the present invention, the ratio of the pore former is preferably 30% by volume to 60% by volume with respect to the total volume of particles contained in the raw material composition.
When the ratio of the pore former is less than 30% by volume, the porosity becomes too small. On the other hand, when the ratio of the pore former exceeds 60% by volume, the shrinkage during firing becomes too large and cracks are generated. End up.
造孔材の割合が30体積%未満であると、気孔率が小さくなりすぎ、一方、造孔材の割合が60体積%を超えると、焼成時の収縮が大きくなりすぎ、クラックが発生してしまう。 In the method for manufacturing a honeycomb structure of the present invention, the ratio of the pore former is preferably 30% by volume to 60% by volume with respect to the total volume of particles contained in the raw material composition.
When the ratio of the pore former is less than 30% by volume, the porosity becomes too small. On the other hand, when the ratio of the pore former exceeds 60% by volume, the shrinkage during firing becomes too large and cracks are generated. End up.
本発明のハニカム構造体の製造方法において、上記チタニア粉末は、チタニア粗粉末と、上記チタニア粗粉末よりも平均粒子径D50の小さいチタニア微粉末とを含むことが好ましい。
チタニア粉末として、平均粒子径の大きいチタニア粗粉末と平均粒子径の小さいチタニア微粉末を併用する、言い換えると、チタニア粒子として、平均粒子径の大きいチタニア粗粒子と平均粒子径の小さいチタニア微粒子を併用することにより、原料組成物中の粒子の体積比を調整することができるため、焼成時の収縮を抑えることができる。また、チタニア粗粒子とチタニア微粒子を併用することにより、焼成後のチタン酸アルミニウム多孔体の気孔分布をシャープにすることができる。さらに、チタニア微粒子が存在することにより、チタン酸アルミニウムの合成反応や焼結が進行しやすくなるため、熱膨張係数及び強度の悪化を抑制することができる。 In the method for manufacturing a honeycomb structured body of the present invention, the titania powder preferably includes a titania coarse powder and a titania fine powder having an average particle diameter D50 smaller than that of the titania coarse powder.
Use titania coarse powder with a large average particle size and titania fine powder with a small average particle size as titania powder. In other words, titania coarse particles with a large average particle size and titania fine particles with a small average particle size are used in combination. By doing so, since the volume ratio of the particles in the raw material composition can be adjusted, shrinkage during firing can be suppressed. In addition, by using titania coarse particles and titania fine particles in combination, the pore distribution of the fired aluminum titanate porous body can be sharpened. Furthermore, since the titania fine particles are present, the synthesis reaction and sintering of aluminum titanate are facilitated, so that deterioration of the thermal expansion coefficient and strength can be suppressed.
チタニア粉末として、平均粒子径の大きいチタニア粗粉末と平均粒子径の小さいチタニア微粉末を併用する、言い換えると、チタニア粒子として、平均粒子径の大きいチタニア粗粒子と平均粒子径の小さいチタニア微粒子を併用することにより、原料組成物中の粒子の体積比を調整することができるため、焼成時の収縮を抑えることができる。また、チタニア粗粒子とチタニア微粒子を併用することにより、焼成後のチタン酸アルミニウム多孔体の気孔分布をシャープにすることができる。さらに、チタニア微粒子が存在することにより、チタン酸アルミニウムの合成反応や焼結が進行しやすくなるため、熱膨張係数及び強度の悪化を抑制することができる。 In the method for manufacturing a honeycomb structured body of the present invention, the titania powder preferably includes a titania coarse powder and a titania fine powder having an average particle diameter D50 smaller than that of the titania coarse powder.
Use titania coarse powder with a large average particle size and titania fine powder with a small average particle size as titania powder. In other words, titania coarse particles with a large average particle size and titania fine particles with a small average particle size are used in combination. By doing so, since the volume ratio of the particles in the raw material composition can be adjusted, shrinkage during firing can be suppressed. In addition, by using titania coarse particles and titania fine particles in combination, the pore distribution of the fired aluminum titanate porous body can be sharpened. Furthermore, since the titania fine particles are present, the synthesis reaction and sintering of aluminum titanate are facilitated, so that deterioration of the thermal expansion coefficient and strength can be suppressed.
本発明のハニカム構造体の製造方法において、上記チタニア粗粉末の平均粒子径D50は、5~25μmであり、上記チタニア微粉末の平均粒子径D50は、0.1~1.5μmであることが好ましい。
この場合、熱膨張係数を低く、焼成収縮率を小さくし、かつ、焼成後のチタン酸アルミニウム多孔体の気孔分布をシャープにすることができる。 In the method for manufacturing a honeycomb structure of the present invention, the average particle diameter D50 of the titania coarse powder is 5 to 25 μm, and the average particle diameter D50 of the titania fine powder is 0.1 to 1.5 μm. preferable.
In this case, the thermal expansion coefficient can be lowered, the firing shrinkage rate can be reduced, and the pore distribution of the fired aluminum titanate porous body can be sharpened.
この場合、熱膨張係数を低く、焼成収縮率を小さくし、かつ、焼成後のチタン酸アルミニウム多孔体の気孔分布をシャープにすることができる。 In the method for manufacturing a honeycomb structure of the present invention, the average particle diameter D50 of the titania coarse powder is 5 to 25 μm, and the average particle diameter D50 of the titania fine powder is 0.1 to 1.5 μm. preferable.
In this case, the thermal expansion coefficient can be lowered, the firing shrinkage rate can be reduced, and the pore distribution of the fired aluminum titanate porous body can be sharpened.
本発明のハニカム構造体の製造方法において、上記チタニア粗粉末の平均粒子径D50は、上記アルミナ粉末の平均粒子径D50と同等であるか、又は、上記アルミナ粉末の平均粒子径D50よりも小さいことが好ましい。
この場合、焼成時の収縮をさらに抑えることができる。 In the method for manufacturing a honeycomb structure of the present invention, the average particle size D50 of the titania coarse powder is equal to or smaller than the average particle size D50 of the alumina powder. Is preferred.
In this case, shrinkage during firing can be further suppressed.
この場合、焼成時の収縮をさらに抑えることができる。 In the method for manufacturing a honeycomb structure of the present invention, the average particle size D50 of the titania coarse powder is equal to or smaller than the average particle size D50 of the alumina powder. Is preferred.
In this case, shrinkage during firing can be further suppressed.
本発明のハニカム構造体の製造方法において、上記無機粉末は、シリカ粉末及びマグネシア粉末をさらに含むことが好ましい。
シリカ由来のケイ素元素、及び、マグネシア由来のマグネシウム元素が、チタン酸アルミニウムに固溶することにより、チタン酸アルミニウムの熱分解を抑制することができ、高温での使用を可能にする。 In the method for manufacturing a honeycomb structured body of the present invention, the inorganic powder preferably further contains silica powder and magnesia powder.
When the silicon element derived from silica and the magnesium element derived from magnesia are dissolved in the aluminum titanate, thermal decomposition of the aluminum titanate can be suppressed, and use at a high temperature is possible.
シリカ由来のケイ素元素、及び、マグネシア由来のマグネシウム元素が、チタン酸アルミニウムに固溶することにより、チタン酸アルミニウムの熱分解を抑制することができ、高温での使用を可能にする。 In the method for manufacturing a honeycomb structured body of the present invention, the inorganic powder preferably further contains silica powder and magnesia powder.
When the silicon element derived from silica and the magnesium element derived from magnesia are dissolved in the aluminum titanate, thermal decomposition of the aluminum titanate can be suppressed, and use at a high temperature is possible.
(発明の詳細な説明)
以下、本発明のハニカム構造体の製造方法について説明する。
本発明のハニカム構造体の製造方法は、原料組成物を成形することにより、ハニカム成形体を得る成形工程と、上記ハニカム成形体を焼成する焼成工程とを含む。 (Detailed description of the invention)
Hereinafter, the manufacturing method of the honeycomb structure of the present invention will be described.
The method for manufacturing a honeycomb structured body of the present invention includes a forming step for obtaining a honeycomb formed body by forming a raw material composition, and a firing step for firing the honeycomb formed body.
以下、本発明のハニカム構造体の製造方法について説明する。
本発明のハニカム構造体の製造方法は、原料組成物を成形することにより、ハニカム成形体を得る成形工程と、上記ハニカム成形体を焼成する焼成工程とを含む。 (Detailed description of the invention)
Hereinafter, the manufacturing method of the honeycomb structure of the present invention will be described.
The method for manufacturing a honeycomb structured body of the present invention includes a forming step for obtaining a honeycomb formed body by forming a raw material composition, and a firing step for firing the honeycomb formed body.
(成形工程)
成形工程では、無機粉末と造孔材とを含む原料組成物を成形することにより、ハニカム成形体を得る。 (Molding process)
In the forming step, a honeycomb formed body is obtained by forming a raw material composition containing an inorganic powder and a pore former.
成形工程では、無機粉末と造孔材とを含む原料組成物を成形することにより、ハニカム成形体を得る。 (Molding process)
In the forming step, a honeycomb formed body is obtained by forming a raw material composition containing an inorganic powder and a pore former.
原料組成物中の無機粉末は、チタニア粉末及びアルミナ粉末を含む。無機粉末は、シリカ粉末及びマグネシア粉末をさらに含むことが好ましい。また、原料組成物は、造孔材をさらに含む。
The inorganic powder in the raw material composition includes titania powder and alumina powder. The inorganic powder preferably further contains silica powder and magnesia powder. The raw material composition further includes a pore former.
本発明のハニカム構造体の製造方法においては、無機粉末中、粒子径が5μm以下の粒子が25体積%よりも多く、50体積%よりも少なく含まれており、一方、粒子径が5μmを超える粒子が50体積%よりも多く、75体積%よりも少なく含まれている。
In the method for manufacturing a honeycomb structured body of the present invention, the inorganic powder contains particles having a particle size of 5 μm or less in an amount of more than 25% by volume and less than 50% by volume, while the particle size exceeds 5 μm. The particles are contained in an amount of more than 50% by volume and less than 75% by volume.
具体的には、原料組成物に含まれるそれぞれの無機粉末について、レーザー回折・散乱式粒度分布測定法により体積基準で粒度分布を測定し、粒子径が5μm以下の粒子の体積割合と粒子径が5μmを超える粒子の体積割合を求める。別途、原料組成物に含まれるそれぞれの無機粉末の重量基準の配合比と密度から、体積基準の配合比を求める。以上の値から、無機粉末中の、粒子径が5μm以下の粒子と粒子径が5μmを超える粒子との体積比を求めることができる。
Specifically, for each inorganic powder contained in the raw material composition, the particle size distribution is measured on a volume basis by a laser diffraction / scattering particle size distribution measurement method, and the volume ratio and particle size of particles having a particle size of 5 μm or less are determined. Determine the volume fraction of particles over 5 μm. Separately, a volume-based blending ratio is obtained from the weight-based blending ratio and density of each inorganic powder contained in the raw material composition. From the above values, the volume ratio of the particles having a particle diameter of 5 μm or less and the particles having a particle diameter exceeding 5 μm in the inorganic powder can be obtained.
チタニア粉末は、チタニア粗粉末と、上記チタニア粗粉末よりも平均粒子径D50の小さいチタニア微粉末とを含むことが好ましい。
The titania powder preferably contains a titania coarse powder and a fine titania powder having an average particle diameter D50 smaller than that of the titania coarse powder.
本明細書において、チタニア粉末の平均粒子径D50は、レーザー回折・散乱式粒度分布測定法による体積基準の累積粒径の小径側から累積50%に相当する粒子径である。アルミナ粉末などの平均粒子径D50も同様である。
In this specification, the average particle diameter D50 of the titania powder is a particle diameter corresponding to 50% cumulative from the smaller diameter side of the volume-based cumulative particle diameter by the laser diffraction / scattering particle size distribution measurement method. The same applies to the average particle diameter D50 of alumina powder or the like.
チタニア粗粉末の平均粒子径D50は、チタニア微粉末の平均粒子径D50よりも大きい限り特に限定されないが、アルミナ粉末の平均粒子径D50と同等であるか、又は、アルミナ粉末の平均粒子径D50よりも小さいことが好ましい。
The average particle diameter D50 of the titania coarse powder is not particularly limited as long as it is larger than the average particle diameter D50 of the titania fine powder, but is equal to the average particle diameter D50 of the alumina powder or from the average particle diameter D50 of the alumina powder. Is preferably small.
チタニア粗粉末の平均粒子径D50は、5μm以上であることが好ましく、10μm以上であることがより好ましい。また、チタニア粗粉末の平均粒子径D50は、25μm以下であることが好ましく、20μm以下であることがより好ましい。
The average particle diameter D50 of the titania coarse powder is preferably 5 μm or more, and more preferably 10 μm or more. Further, the average particle diameter D50 of the titania coarse powder is preferably 25 μm or less, and more preferably 20 μm or less.
チタニア微粉末の平均粒子径D50は、0.1μm以上であることが好ましく、0.4μm以上であることがより好ましい。また、チタニア微粉末の平均粒子径D50は、1.5μm以下であることが好ましく、1μm以下であることがより好ましい。
The average particle diameter D50 of the titania fine powder is preferably 0.1 μm or more, and more preferably 0.4 μm or more. The average particle diameter D50 of the titania fine powder is preferably 1.5 μm or less, and more preferably 1 μm or less.
チタニア粗粉末は、チタニア微粉末よりも多くの鉄分を含有していることが好ましい。
上述のとおり、チタニアの粒子径を大きくすることによって焼結性は低下する。しかし、焼結を進行させやすい鉄分をチタニア粗粉末に含有させることにより、全体が均一に焼結するため、アルミナ粒子とチタニア粗粒子との間隔が均一になり、その隙間に均一な気孔を形成することができる。 The coarse titania powder preferably contains more iron than the fine titania powder.
As described above, the sinterability is lowered by increasing the titania particle size. However, the inclusion of iron that facilitates sintering in the titania coarse powder results in uniform sintering, so the spacing between the alumina particles and the titania coarse particles is uniform, and uniform pores are formed in the gaps. can do.
上述のとおり、チタニアの粒子径を大きくすることによって焼結性は低下する。しかし、焼結を進行させやすい鉄分をチタニア粗粉末に含有させることにより、全体が均一に焼結するため、アルミナ粒子とチタニア粗粒子との間隔が均一になり、その隙間に均一な気孔を形成することができる。 The coarse titania powder preferably contains more iron than the fine titania powder.
As described above, the sinterability is lowered by increasing the titania particle size. However, the inclusion of iron that facilitates sintering in the titania coarse powder results in uniform sintering, so the spacing between the alumina particles and the titania coarse particles is uniform, and uniform pores are formed in the gaps. can do.
チタニア微粉末は、鉄分を含有していてもよいし、鉄分を含有していなくてもよい(すなわち、検出限界以下であってもよい)。
The titania fine powder may contain iron or may not contain iron (that is, it may be below the detection limit).
本明細書において、チタニア粉末の鉄分含有量は、ICP発光分光分析により測定される。
In this specification, the iron content of titania powder is measured by ICP emission spectroscopic analysis.
チタニア粗粉末の鉄分含有量は、0.1~0.3%であることが好ましい。また、チタニア微粉末の鉄分含有量は、0.1%未満であることが好ましく、0.01%未満であることがより好ましい。
The iron content of the titania crude powder is preferably 0.1 to 0.3%. Further, the iron content of the titania fine powder is preferably less than 0.1%, more preferably less than 0.01%.
チタニア粗粉末とチタニア微粉末の配合比は、重量比で、チタニア粗粉末:チタニア微粉末=40:60~80:20であることが好ましく、45:55~75:25であることがより好ましい。
The mixing ratio of the titania coarse powder and the titania fine powder is preferably 40:60 to 80:20, more preferably 45:55 to 75:25, in terms of weight ratio. .
チタニア粉末は、チタニア粗粉末とチタニア微粉末の合計で、原料組成物中に15~40重量%含まれていることが好ましい。
The titania powder is preferably contained in the raw material composition in an amount of 15 to 40% by weight in total of the titania coarse powder and the titania fine powder.
アルミナ粉末の平均粒子径D50は特に限定されないが、チタニア粗粉末の平均粒子径D50と同等であるか、又は、チタニア粗粉末の平均粒子径D50よりも大きいことが好ましい。
The average particle diameter D50 of the alumina powder is not particularly limited, but it is preferably equal to the average particle diameter D50 of the titania coarse powder or larger than the average particle diameter D50 of the titania coarse powder.
アルミナ粉末の平均粒子径D50は、10μm以上であることが好ましく、15μm以上であることがより好ましい。また、アルミナ粉末の平均粒子径D50は、40μm以下であることが好ましく、30μm以下であることがより好ましい。
The average particle diameter D50 of the alumina powder is preferably 10 μm or more, and more preferably 15 μm or more. Moreover, the average particle diameter D50 of the alumina powder is preferably 40 μm or less, and more preferably 30 μm or less.
アルミナ粉末は、原料組成物中に20~45重量%含まれていることが好ましい。
The alumina powder is preferably contained in the raw material composition in an amount of 20 to 45% by weight.
上記のとおり、原料組成物は、無機粉末として、シリカ粉末及びマグネシア粉末をさらに含むことが好ましい。
As described above, the raw material composition preferably further includes silica powder and magnesia powder as the inorganic powder.
原料組成物がシリカ粉末を含む場合、シリカ粉末の平均粒子径D50は、0.1μm以上であることが好ましい。また、シリカ粉末の平均粒子径D50は、10μm以下であることが好ましく、5μm以下であることがより好ましい。
When the raw material composition contains silica powder, the average particle diameter D50 of the silica powder is preferably 0.1 μm or more. The average particle diameter D50 of the silica powder is preferably 10 μm or less, and more preferably 5 μm or less.
原料組成物がシリカ粉末を含む場合、シリカ粉末は、原料組成物中に0.5~5重量%含まれていることが好ましい。
When the raw material composition contains silica powder, the silica powder is preferably contained in the raw material composition in an amount of 0.5 to 5% by weight.
原料組成物がマグネシア粉末を含む場合、マグネシア粉末の平均粒子径D50は、1μm以上であることが好ましく、2μm以上であることがより好ましい。また、マグネシア粉末の平均粒子径D50は、10μm以下であることが好ましい。マグネシア粉末の平均粒子径D50は、シリカ粉末の平均粒子径D50よりも大きいことが好ましい。
When the raw material composition contains magnesia powder, the average particle diameter D50 of the magnesia powder is preferably 1 μm or more, and more preferably 2 μm or more. Moreover, it is preferable that the average particle diameter D50 of a magnesia powder is 10 micrometers or less. The average particle diameter D50 of the magnesia powder is preferably larger than the average particle diameter D50 of the silica powder.
原料組成物がマグネシア粉末を含む場合、マグネシア粉末は、原料組成物中に0.5~5重量%含まれていることが好ましい。
When the raw material composition contains magnesia powder, the magnesia powder is preferably contained in the raw material composition in an amount of 0.5 to 5% by weight.
原料組成物に含まれる造孔材としては、アクリル樹脂、グラファイト、デンプンが挙げられる。
Examples of the pore former contained in the raw material composition include acrylic resin, graphite, and starch.
造孔材の平均粒子径D50は、10μm以上であることが好ましく、20μm以上であることがより好ましい。また、造孔材の平均粒子径D50は、60μm以下であることが好ましく、40μm以下であることがより好ましい。
The average particle diameter D50 of the pore former is preferably 10 μm or more, and more preferably 20 μm or more. Further, the average particle diameter D50 of the pore former is preferably 60 μm or less, and more preferably 40 μm or less.
造孔材の割合は、原料組成物に含まれる粒子の合計体積に対して、30体積%以上であることが好ましく、40体積%以上であることがより好ましい。また、造孔材の割合は、原料組成物に含まれる粒子の合計体積に対して、60体積%以下であることが好ましく、50体積%以下であることがより好ましい。
The ratio of the pore former is preferably 30% by volume or more, and more preferably 40% by volume or more with respect to the total volume of the particles contained in the raw material composition. Further, the ratio of the pore former is preferably 60% by volume or less, and more preferably 50% by volume or less with respect to the total volume of particles contained in the raw material composition.
また、造孔材の割合は、原料組成物に含まれる粒子径が5μmを超える粒子の合計体積に対して、40体積%以上、70体積%以下であることが好ましい。
Moreover, it is preferable that the ratio of a pore former is 40 volume% or more and 70 volume% or less with respect to the total volume of the particle | grains in which the particle diameter contained in a raw material composition exceeds 5 micrometers.
原料組成物は、成形助剤、有機バインダー及び分散媒を含んでいてもよい。
成形助剤としては、エチレングリコール、デキストリン、脂肪酸、脂肪酸石鹸、ポリアルコールが挙げられる。有機バインダーとしては、カルボキシメチルセルロース、ポリビニルアルコール、メチルセルロース、エチルセルロース等の親水性有機高分子が挙げられる。分散媒としては、水のみからなる分散媒、又は、50体積%以上の水と有機溶剤とからなる分散媒が挙げられる。有機溶剤としては、ベンゼン、メタノール等のアルコールが挙げられる。 The raw material composition may contain a molding aid, an organic binder, and a dispersion medium.
Examples of the molding aid include ethylene glycol, dextrin, fatty acid, fatty acid soap, and polyalcohol. Examples of the organic binder include hydrophilic organic polymers such as carboxymethyl cellulose, polyvinyl alcohol, methyl cellulose, and ethyl cellulose. Examples of the dispersion medium include a dispersion medium composed only of water, or a dispersion medium composed of 50% by volume or more of water and an organic solvent. Examples of the organic solvent include alcohols such as benzene and methanol.
成形助剤としては、エチレングリコール、デキストリン、脂肪酸、脂肪酸石鹸、ポリアルコールが挙げられる。有機バインダーとしては、カルボキシメチルセルロース、ポリビニルアルコール、メチルセルロース、エチルセルロース等の親水性有機高分子が挙げられる。分散媒としては、水のみからなる分散媒、又は、50体積%以上の水と有機溶剤とからなる分散媒が挙げられる。有機溶剤としては、ベンゼン、メタノール等のアルコールが挙げられる。 The raw material composition may contain a molding aid, an organic binder, and a dispersion medium.
Examples of the molding aid include ethylene glycol, dextrin, fatty acid, fatty acid soap, and polyalcohol. Examples of the organic binder include hydrophilic organic polymers such as carboxymethyl cellulose, polyvinyl alcohol, methyl cellulose, and ethyl cellulose. Examples of the dispersion medium include a dispersion medium composed only of water, or a dispersion medium composed of 50% by volume or more of water and an organic solvent. Examples of the organic solvent include alcohols such as benzene and methanol.
また、原料組成物は、その他の材料をさらに含んでいてもよい。その他の材料としては、例えば、可塑剤、分散剤、潤滑剤等が挙げられる。
可塑剤としては、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシプロピレンアルキルエーテル等のポリオキシアルキレン系化合物が挙げられる。分散剤としては、例えば、ソルビタン脂肪酸エステルが挙げられる。潤滑剤としては、例えば、グリセリンが挙げられる。 The raw material composition may further contain other materials. Examples of other materials include plasticizers, dispersants, lubricants, and the like.
Examples of the plasticizer include polyoxyalkylene compounds such as polyoxyethylene alkyl ether and polyoxypropylene alkyl ether. Examples of the dispersant include sorbitan fatty acid esters. Examples of the lubricant include glycerin.
可塑剤としては、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシプロピレンアルキルエーテル等のポリオキシアルキレン系化合物が挙げられる。分散剤としては、例えば、ソルビタン脂肪酸エステルが挙げられる。潤滑剤としては、例えば、グリセリンが挙げられる。 The raw material composition may further contain other materials. Examples of other materials include plasticizers, dispersants, lubricants, and the like.
Examples of the plasticizer include polyoxyalkylene compounds such as polyoxyethylene alkyl ether and polyoxypropylene alkyl ether. Examples of the dispersant include sorbitan fatty acid esters. Examples of the lubricant include glycerin.
成形工程では、原料組成物を成形してハニカム成形体を得る。
例えば、押出成形機に投入された原料組成物を種々の形状を有するスクリュー等を用いて密閉状態で混合及び混練を行いながら金型方向に押し出し、押出成形に適した混練状態とした後、金型を介して押出成形を行い、多数の貫通孔が壁部を隔てて長手方向に並設されたハニカム成形体の連続体を作製する。 In the forming step, the raw material composition is formed to obtain a honeycomb formed body.
For example, the raw material composition put into an extruder is extruded in the mold direction while being mixed and kneaded in a sealed state using a screw having various shapes, etc., to obtain a kneaded state suitable for extrusion molding, Extrusion molding is performed through a mold to produce a continuous body of honeycomb molded bodies in which a large number of through holes are arranged in parallel in the longitudinal direction with a wall portion therebetween.
例えば、押出成形機に投入された原料組成物を種々の形状を有するスクリュー等を用いて密閉状態で混合及び混練を行いながら金型方向に押し出し、押出成形に適した混練状態とした後、金型を介して押出成形を行い、多数の貫通孔が壁部を隔てて長手方向に並設されたハニカム成形体の連続体を作製する。 In the forming step, the raw material composition is formed to obtain a honeycomb formed body.
For example, the raw material composition put into an extruder is extruded in the mold direction while being mixed and kneaded in a sealed state using a screw having various shapes, etc., to obtain a kneaded state suitable for extrusion molding, Extrusion molding is performed through a mold to produce a continuous body of honeycomb molded bodies in which a large number of through holes are arranged in parallel in the longitudinal direction with a wall portion therebetween.
また、成形工程では、ハニカム構造体の一部の形状に対応する成形体を成形してもよい。すなわち、ハニカム構造体の一部の形状に対応する成形体を成形し、それらの成形体を組み合わせることによってハニカム構造体と同一形状を有するハニカム成形体を作製してもよい。
In the forming step, a formed body corresponding to a part of the shape of the honeycomb structure may be formed. That is, a molded body having the same shape as the honeycomb structure may be manufactured by forming a formed body corresponding to a part of the shape of the honeycomb structure and combining the formed bodies.
その後、必要に応じて、貫通孔が露出した両端面において、多数の貫通孔のうち所定の貫通孔の目封じを行い、マイクロ波乾燥機、熱風乾燥機、誘電乾燥機、減圧乾燥器、真空乾燥機、凍結乾燥機等を用いて乾燥させ、続いてハニカム成形体中の有機分を分解消失させる脱脂処理を行う。
Then, if necessary, plug the predetermined through-holes among the many through-holes on both end faces where the through-holes are exposed, microwave dryer, hot air dryer, dielectric dryer, vacuum dryer, vacuum Drying is performed using a dryer, a freeze dryer, or the like, followed by a degreasing process for decomposing and eliminating organic components in the honeycomb formed body.
(焼成工程)
焼成工程では、成形工程により得られたハニカム成形体を焼成して焼成体とする。
焼成工程では、アルミナ粒子とチタニア粒子との反応が進行して、チタン酸アルミニウムの相が形成される。 (Baking process)
In the firing step, the honeycomb formed body obtained in the forming step is fired to obtain a fired body.
In the firing step, the reaction between the alumina particles and the titania particles proceeds to form an aluminum titanate phase.
焼成工程では、成形工程により得られたハニカム成形体を焼成して焼成体とする。
焼成工程では、アルミナ粒子とチタニア粒子との反応が進行して、チタン酸アルミニウムの相が形成される。 (Baking process)
In the firing step, the honeycomb formed body obtained in the forming step is fired to obtain a fired body.
In the firing step, the reaction between the alumina particles and the titania particles proceeds to form an aluminum titanate phase.
焼成温度は、1300~1600℃とすることが好ましい。
焼成は、公知の単独炉、いわゆるバッチ炉や、連続炉を用いて行うことができる。焼成時間は特に限定されないが、上記の焼成温度において1~20時間保持することが好ましい。また、焼成工程は大気雰囲気下で行うことが好ましい。大気雰囲気に窒素ガスやアルゴンガス等の不活性ガスを混合することにより、酸素濃度を調整してもよい。 The firing temperature is preferably 1300 to 1600 ° C.
Firing can be performed using a known single furnace, a so-called batch furnace, or a continuous furnace. The firing time is not particularly limited, but it is preferable to hold at the above firing temperature for 1 to 20 hours. Moreover, it is preferable to perform a baking process in an atmospheric condition. The oxygen concentration may be adjusted by mixing an inert gas such as nitrogen gas or argon gas in the air atmosphere.
焼成は、公知の単独炉、いわゆるバッチ炉や、連続炉を用いて行うことができる。焼成時間は特に限定されないが、上記の焼成温度において1~20時間保持することが好ましい。また、焼成工程は大気雰囲気下で行うことが好ましい。大気雰囲気に窒素ガスやアルゴンガス等の不活性ガスを混合することにより、酸素濃度を調整してもよい。 The firing temperature is preferably 1300 to 1600 ° C.
Firing can be performed using a known single furnace, a so-called batch furnace, or a continuous furnace. The firing time is not particularly limited, but it is preferable to hold at the above firing temperature for 1 to 20 hours. Moreover, it is preferable to perform a baking process in an atmospheric condition. The oxygen concentration may be adjusted by mixing an inert gas such as nitrogen gas or argon gas in the air atmosphere.
上記工程を経ることにより、チタン酸アルミニウムからなるハニカム構造体を製造することができる。
Through the above steps, a honeycomb structure made of aluminum titanate can be manufactured.
図1(a)は、本発明の製造方法により製造されるハニカム構造体の一例を模式的に示す斜視図であり、図1(b)は、図1(a)に示すハニカム構造体のA-A線断面図である。
図1(a)に示すハニカム構造体10は円柱形状であり、長手方向(図1(a)中、両矢印aで示す方向)に垂直な断面の形状が略四角形の排ガス導入セル11a及び排ガス排出セル11bが多数形成されている。排ガス導入セル11aと排ガス排出セル11bとは、セル隔壁13を隔てて形成されている。また、ハニカム構造体10の外周には外周壁16が形成されている。 Fig. 1 (a) is a perspective view schematically showing an example of a honeycomb structure manufactured by the manufacturing method of the present invention, and Fig. 1 (b) is an A of the honeycomb structure shown in Fig. 1 (a). FIG.
Thehoneycomb structure 10 shown in FIG. 1 (a) has a columnar shape, and the exhaust gas introduction cell 11a and the exhaust gas whose cross-sectional shape perpendicular to the longitudinal direction (the direction indicated by the double arrow a in FIG. 1 (a)) is substantially rectangular. Many discharge cells 11b are formed. The exhaust gas introduction cell 11a and the exhaust gas discharge cell 11b are formed with a cell partition wall 13 therebetween. An outer peripheral wall 16 is formed on the outer periphery of the honeycomb structure 10.
図1(a)に示すハニカム構造体10は円柱形状であり、長手方向(図1(a)中、両矢印aで示す方向)に垂直な断面の形状が略四角形の排ガス導入セル11a及び排ガス排出セル11bが多数形成されている。排ガス導入セル11aと排ガス排出セル11bとは、セル隔壁13を隔てて形成されている。また、ハニカム構造体10の外周には外周壁16が形成されている。 Fig. 1 (a) is a perspective view schematically showing an example of a honeycomb structure manufactured by the manufacturing method of the present invention, and Fig. 1 (b) is an A of the honeycomb structure shown in Fig. 1 (a). FIG.
The
図1(b)に示すように、排ガスが導入される側の端面14では、排ガス排出セル11bが封止部12bにより目封じされており、排ガス導入セル11aは開口している。一方、排ガスが排出される側の端面15では、排ガス導入セル11aが封止部12aにより目封じされており、排ガス排出セル11bは開口している。
As shown in FIG. 1B, the exhaust gas discharge cell 11b is sealed by the sealing portion 12b on the end surface 14 on the side where the exhaust gas is introduced, and the exhaust gas introduction cell 11a is open. On the other hand, on the end face 15 on the exhaust gas discharge side, the exhaust gas introduction cell 11a is sealed by the sealing portion 12a, and the exhaust gas discharge cell 11b is open.
排ガス導入セル11aの端面15は目封じされているため、端面14から排ガス導入セル11aに導入された排ガスGは、多孔質壁であるセル隔壁13を通過した後、排ガス排出セル11bを通って端面15から排出される。この間に排ガス中のPMがセル隔壁13で捕集され、排ガスが浄化される。
Since the end surface 15 of the exhaust gas introduction cell 11a is sealed, the exhaust gas G introduced into the exhaust gas introduction cell 11a from the end surface 14 passes through the cell partition wall 13 which is a porous wall, and then passes through the exhaust gas exhaust cell 11b. It is discharged from the end face 15. During this time, PM in the exhaust gas is collected by the cell partition wall 13 and the exhaust gas is purified.
本発明のハニカム構造体の製造方法により製造されるハニカム構造体は、排ガス中のPMを除去するハニカムフィルタとして機能することが好ましい。また、本発明のハニカム構造体の製造方法により製造されるハニカム構造体は、目封じすることなく、種々の触媒等を担持することにより触媒担体として使用してもよい。
The honeycomb structure manufactured by the method for manufacturing a honeycomb structure of the present invention preferably functions as a honeycomb filter that removes PM in exhaust gas. Moreover, the honeycomb structure manufactured by the method for manufacturing a honeycomb structure of the present invention may be used as a catalyst carrier by supporting various catalysts and the like without sealing.
以下、本発明のハニカム構造体の製造方法をさらに具体化した実施例について説明する。
Hereinafter, examples that further embody the method for manufacturing a honeycomb structure of the present invention will be described.
[ハニカム構造体の作製]
(実施例1)
D50が0.6μmのチタニア微粉末(鉄分含有量0.01%未満):22.2重量%、D50が21.5μmのアルミナ粉末:30.4重量%、D50が1.1μmのシリカ粉末:2.8重量%、D50が3.8μmのマグネシア粉末:1.4重量%、D50が31.9μmのアクリル樹脂(造孔材):18.5重量%、メチルセルロース(有機バインダー):7.1重量%、成形助剤(エステル型ノニオン):4.7重量%、イオン交換水(分散媒):12.9重量%からなる組成のものを混合機で混合し、原料組成物を作製した。
原料組成物の作製に使用したチタニア粗粉末とチタニア微粉末の配合比は、重量比で、チタニア粗粉末:チタニア微粉末=0:100である。
無機粉末中、粒子径が5μm以下の粒子と粒子径が5μmを超える粒子との体積比は、46.1:53.9である。
また、造孔材の割合は、原料組成物に含まれる粒子の合計体積に対して43.4体積%であり、原料組成物に含まれる粒子径が5μmを超える粒子の合計体積に対して59.8体積%である。 [Preparation of honeycomb structure]
Example 1
Titanium fine powder with D50 of 0.6 μm (iron content less than 0.01%): 22.2% by weight, alumina powder with D50 of 21.5 μm: 30.4% by weight, silica powder with D50 of 1.1 μm: 2.8% by weight, D50 of 3.8 μm magnesia powder: 1.4% by weight, D50 of 31.9 μm acrylic resin (pore forming material): 18.5% by weight, methylcellulose (organic binder): 7.1 A raw material composition was prepared by mixing with a mixer a composition comprising 5% by weight, a molding aid (ester type nonion): 4.7% by weight, and ion-exchanged water (dispersion medium): 12.9% by weight.
The compounding ratio of the titania coarse powder and the titania fine powder used in the preparation of the raw material composition is a titania coarse powder: titania fine powder = 0: 100 in weight ratio.
In the inorganic powder, the volume ratio of the particles having a particle diameter of 5 μm or less and the particles having a particle diameter exceeding 5 μm is 46.1: 53.9.
The ratio of the pore former is 43.4% by volume with respect to the total volume of the particles contained in the raw material composition, and 59% with respect to the total volume of the particles having a particle diameter of more than 5 μm contained in the raw material composition. 8% by volume.
(実施例1)
D50が0.6μmのチタニア微粉末(鉄分含有量0.01%未満):22.2重量%、D50が21.5μmのアルミナ粉末:30.4重量%、D50が1.1μmのシリカ粉末:2.8重量%、D50が3.8μmのマグネシア粉末:1.4重量%、D50が31.9μmのアクリル樹脂(造孔材):18.5重量%、メチルセルロース(有機バインダー):7.1重量%、成形助剤(エステル型ノニオン):4.7重量%、イオン交換水(分散媒):12.9重量%からなる組成のものを混合機で混合し、原料組成物を作製した。
原料組成物の作製に使用したチタニア粗粉末とチタニア微粉末の配合比は、重量比で、チタニア粗粉末:チタニア微粉末=0:100である。
無機粉末中、粒子径が5μm以下の粒子と粒子径が5μmを超える粒子との体積比は、46.1:53.9である。
また、造孔材の割合は、原料組成物に含まれる粒子の合計体積に対して43.4体積%であり、原料組成物に含まれる粒子径が5μmを超える粒子の合計体積に対して59.8体積%である。 [Preparation of honeycomb structure]
Example 1
Titanium fine powder with D50 of 0.6 μm (iron content less than 0.01%): 22.2% by weight, alumina powder with D50 of 21.5 μm: 30.4% by weight, silica powder with D50 of 1.1 μm: 2.8% by weight, D50 of 3.8 μm magnesia powder: 1.4% by weight, D50 of 31.9 μm acrylic resin (pore forming material): 18.5% by weight, methylcellulose (organic binder): 7.1 A raw material composition was prepared by mixing with a mixer a composition comprising 5% by weight, a molding aid (ester type nonion): 4.7% by weight, and ion-exchanged water (dispersion medium): 12.9% by weight.
The compounding ratio of the titania coarse powder and the titania fine powder used in the preparation of the raw material composition is a titania coarse powder: titania fine powder = 0: 100 in weight ratio.
In the inorganic powder, the volume ratio of the particles having a particle diameter of 5 μm or less and the particles having a particle diameter exceeding 5 μm is 46.1: 53.9.
The ratio of the pore former is 43.4% by volume with respect to the total volume of the particles contained in the raw material composition, and 59% with respect to the total volume of the particles having a particle diameter of more than 5 μm contained in the raw material composition. 8% by volume.
作製した原料組成物を押出成形機に投入して押出成形を行うことにより、図1(a)に示す形状を有し、セルが封止されていないハニカム成形体を作製した。
The prepared raw material composition was put into an extruder and subjected to extrusion to produce a honeycomb formed body having the shape shown in FIG. 1A and having no cells sealed.
上記原料組成物と同じ組成の封止材を用いて、ハニカム成形体のセルを互い違いに目封止した。乾燥、脱脂の後、大気雰囲気下、1450℃で15時間保持して焼成することにより、円柱状のハニカム構造体を作製した。
The cells of the honeycomb formed body were alternately plugged using a sealing material having the same composition as the raw material composition. After drying and degreasing, a cylindrical honeycomb structure was produced by firing at 1450 ° C. for 15 hours in an air atmosphere and firing.
(実施例2)
「D50が0.6μmのチタニア微粉末(鉄分含有量0.01%未満):22.2重量%」を「D50が13.6μmのチタニア粗粉末(鉄分含有量0.25%):11.1重量%、D50が0.6μmのチタニア微粉末(鉄分含有量0.01%未満):11.1重量%」に変更したことを除いて、実施例1と同様にハニカム構造体を作製した。
原料組成物の作製に使用したチタニア粗粉末とチタニア微粉末の配合比は、重量比で、チタニア粗粉末:チタニア微粉末=50:50である。
無機粉末中、粒子径が5μm以下の粒子と粒子径が5μmを超える粒子との体積比は、33.1:66.9である。
また、造孔材の割合は、原料組成物に含まれる粒子の合計体積に対して43.4体積%であり、原料組成物に含まれる粒子径が5μmを超える粒子の合計体積に対して54.4体積%である。 (Example 2)
“Titanium fine powder with D50 of 0.6 μm (iron content less than 0.01%): 22.2% by weight” “Rough titania powder with D50 of 13.6 μm (iron content of 0.25%): 11. 1% by weight, titania fine powder having D50 of 0.6 μm (iron content less than 0.01%): 11.1% by weight ”A honeycomb structure was manufactured in the same manner as in Example 1. .
The compounding ratio of the titania coarse powder and the titania fine powder used in the preparation of the raw material composition is a titania coarse powder: titania fine powder = 50: 50 in weight ratio.
In the inorganic powder, the volume ratio of particles having a particle size of 5 μm or less and particles having a particle size exceeding 5 μm is 33.1-66.9.
The ratio of the pore former is 43.4% by volume with respect to the total volume of the particles contained in the raw material composition, and 54% with respect to the total volume of the particles having a particle diameter of more than 5 μm contained in the raw material composition. .4% by volume.
「D50が0.6μmのチタニア微粉末(鉄分含有量0.01%未満):22.2重量%」を「D50が13.6μmのチタニア粗粉末(鉄分含有量0.25%):11.1重量%、D50が0.6μmのチタニア微粉末(鉄分含有量0.01%未満):11.1重量%」に変更したことを除いて、実施例1と同様にハニカム構造体を作製した。
原料組成物の作製に使用したチタニア粗粉末とチタニア微粉末の配合比は、重量比で、チタニア粗粉末:チタニア微粉末=50:50である。
無機粉末中、粒子径が5μm以下の粒子と粒子径が5μmを超える粒子との体積比は、33.1:66.9である。
また、造孔材の割合は、原料組成物に含まれる粒子の合計体積に対して43.4体積%であり、原料組成物に含まれる粒子径が5μmを超える粒子の合計体積に対して54.4体積%である。 (Example 2)
“Titanium fine powder with D50 of 0.6 μm (iron content less than 0.01%): 22.2% by weight” “Rough titania powder with D50 of 13.6 μm (iron content of 0.25%): 11. 1% by weight, titania fine powder having D50 of 0.6 μm (iron content less than 0.01%): 11.1% by weight ”A honeycomb structure was manufactured in the same manner as in Example 1. .
The compounding ratio of the titania coarse powder and the titania fine powder used in the preparation of the raw material composition is a titania coarse powder: titania fine powder = 50: 50 in weight ratio.
In the inorganic powder, the volume ratio of particles having a particle size of 5 μm or less and particles having a particle size exceeding 5 μm is 33.1-66.9.
The ratio of the pore former is 43.4% by volume with respect to the total volume of the particles contained in the raw material composition, and 54% with respect to the total volume of the particles having a particle diameter of more than 5 μm contained in the raw material composition. .4% by volume.
(実施例3)
チタニア粗粉末を15.5重量%、チタニア微粉末を6.7重量%に変更したことを除いて、実施例2と同様にハニカム構造体を作製した。
原料組成物の作製に使用したチタニア粗粉末とチタニア微粉末の配合比は、重量比で、チタニア粗粉末:チタニア微粉末=70:30である。
無機粉末中、粒子径が5μm以下の粒子と粒子径が5μmを超える粒子との体積比は、27.9:72.1である。
また、造孔材の割合は、原料組成物に含まれる粒子の合計体積に対して43.4体積%であり、原料組成物に含まれる粒子径が5μmを超える粒子の合計体積に対して52.5体積%である。 (Example 3)
A honeycomb structure was manufactured in the same manner as in Example 2 except that the titania coarse powder was changed to 15.5 wt% and the titania fine powder was changed to 6.7 wt%.
The compounding ratio of the titania coarse powder and the titania fine powder used for the preparation of the raw material composition is a titania coarse powder: titania fine powder = 70: 30 in weight ratio.
In the inorganic powder, the volume ratio of particles having a particle size of 5 μm or less and particles having a particle size exceeding 5 μm is 27.9: 72.1.
Further, the ratio of the pore former is 43.4% by volume with respect to the total volume of the particles contained in the raw material composition, and 52% with respect to the total volume of the particles having a particle diameter of more than 5 μm contained in the raw material composition. .5% by volume.
チタニア粗粉末を15.5重量%、チタニア微粉末を6.7重量%に変更したことを除いて、実施例2と同様にハニカム構造体を作製した。
原料組成物の作製に使用したチタニア粗粉末とチタニア微粉末の配合比は、重量比で、チタニア粗粉末:チタニア微粉末=70:30である。
無機粉末中、粒子径が5μm以下の粒子と粒子径が5μmを超える粒子との体積比は、27.9:72.1である。
また、造孔材の割合は、原料組成物に含まれる粒子の合計体積に対して43.4体積%であり、原料組成物に含まれる粒子径が5μmを超える粒子の合計体積に対して52.5体積%である。 (Example 3)
A honeycomb structure was manufactured in the same manner as in Example 2 except that the titania coarse powder was changed to 15.5 wt% and the titania fine powder was changed to 6.7 wt%.
The compounding ratio of the titania coarse powder and the titania fine powder used for the preparation of the raw material composition is a titania coarse powder: titania fine powder = 70: 30 in weight ratio.
In the inorganic powder, the volume ratio of particles having a particle size of 5 μm or less and particles having a particle size exceeding 5 μm is 27.9: 72.1.
Further, the ratio of the pore former is 43.4% by volume with respect to the total volume of the particles contained in the raw material composition, and 52% with respect to the total volume of the particles having a particle diameter of more than 5 μm contained in the raw material composition. .5% by volume.
(実施例4)
アルミナ粉末のD50を15.4μmに変更したことを除いて、実施例2と同様にハニカム構造体を作製した。
原料組成物の作製に使用したチタニア粗粉末とチタニア微粉末の配合比は、重量比で、チタニア粗粉末:チタニア微粉末=50:50である。
無機粉末中、粒子径が5μm以下の粒子と粒子径が5μmを超える粒子との体積比は、45.3:54.7である。
また、造孔材の割合は、原料組成物に含まれる粒子の合計体積に対して43.4体積%であり、原料組成物に含まれる粒子径が5μmを超える粒子の合計体積に対して58.8体積%である。 Example 4
A honeycomb structure was manufactured in the same manner as in Example 2 except that D50 of the alumina powder was changed to 15.4 μm.
The compounding ratio of the titania coarse powder and the titania fine powder used in the preparation of the raw material composition is a titania coarse powder: titania fine powder = 50: 50 in weight ratio.
In the inorganic powder, the volume ratio of particles having a particle diameter of 5 μm or less and particles having a particle diameter exceeding 5 μm is 45.3: 54.7.
Further, the ratio of the pore former is 43.4% by volume with respect to the total volume of the particles contained in the raw material composition, and 58% with respect to the total volume of the particles having a particle diameter of more than 5 μm contained in the raw material composition. 8% by volume.
アルミナ粉末のD50を15.4μmに変更したことを除いて、実施例2と同様にハニカム構造体を作製した。
原料組成物の作製に使用したチタニア粗粉末とチタニア微粉末の配合比は、重量比で、チタニア粗粉末:チタニア微粉末=50:50である。
無機粉末中、粒子径が5μm以下の粒子と粒子径が5μmを超える粒子との体積比は、45.3:54.7である。
また、造孔材の割合は、原料組成物に含まれる粒子の合計体積に対して43.4体積%であり、原料組成物に含まれる粒子径が5μmを超える粒子の合計体積に対して58.8体積%である。 Example 4
A honeycomb structure was manufactured in the same manner as in Example 2 except that D50 of the alumina powder was changed to 15.4 μm.
The compounding ratio of the titania coarse powder and the titania fine powder used in the preparation of the raw material composition is a titania coarse powder: titania fine powder = 50: 50 in weight ratio.
In the inorganic powder, the volume ratio of particles having a particle diameter of 5 μm or less and particles having a particle diameter exceeding 5 μm is 45.3: 54.7.
Further, the ratio of the pore former is 43.4% by volume with respect to the total volume of the particles contained in the raw material composition, and 58% with respect to the total volume of the particles having a particle diameter of more than 5 μm contained in the raw material composition. 8% by volume.
(比較例1)
「D50が0.6μmのチタニア微粉末(鉄分含有量0.01%未満):22.2重量%」を「D50が13.6μmのチタニア粗粉末(鉄分含有量0.25%):22.2重量%」に変更したことを除いて、実施例1と同様にハニカム構造体を作製した。
原料組成物の作製に使用したチタニア粗粉末とチタニア微粉末の配合比は、重量比で、チタニア粗粉末:チタニア微粉末=100:0である。
無機粉末中、粒子径が5μm以下の粒子と粒子径が5μmを超える粒子との体積比は、20.1:79.9である。
また、造孔材の割合は、原料組成物に含まれる粒子の合計体積に対して43.4体積%であり、原料組成物に含まれる粒子径が5μmを超える粒子の合計体積に対して49.9体積%である。 (Comparative Example 1)
“D50 titania fine powder (iron content less than 0.01%): 22.2 wt%” “D50 13.6 μm titania coarse powder (iron content 0.25%): 22. A honeycomb structure was manufactured in the same manner as in Example 1 except that the content was changed to “2 wt%”.
The compounding ratio of the titania coarse powder and the titania fine powder used for the preparation of the raw material composition is a titania coarse powder: titania fine powder = 100: 0.
In the inorganic powder, the volume ratio of particles having a particle size of 5 μm or less and particles having a particle size exceeding 5 μm is 20.1: 79.9.
Further, the ratio of the pore former is 43.4% by volume with respect to the total volume of the particles contained in the raw material composition, and 49% with respect to the total volume of the particles having a particle diameter of more than 5 μm contained in the raw material composition. .9% by volume.
「D50が0.6μmのチタニア微粉末(鉄分含有量0.01%未満):22.2重量%」を「D50が13.6μmのチタニア粗粉末(鉄分含有量0.25%):22.2重量%」に変更したことを除いて、実施例1と同様にハニカム構造体を作製した。
原料組成物の作製に使用したチタニア粗粉末とチタニア微粉末の配合比は、重量比で、チタニア粗粉末:チタニア微粉末=100:0である。
無機粉末中、粒子径が5μm以下の粒子と粒子径が5μmを超える粒子との体積比は、20.1:79.9である。
また、造孔材の割合は、原料組成物に含まれる粒子の合計体積に対して43.4体積%であり、原料組成物に含まれる粒子径が5μmを超える粒子の合計体積に対して49.9体積%である。 (Comparative Example 1)
“D50 titania fine powder (iron content less than 0.01%): 22.2 wt%” “D50 13.6 μm titania coarse powder (iron content 0.25%): 22. A honeycomb structure was manufactured in the same manner as in Example 1 except that the content was changed to “2 wt%”.
The compounding ratio of the titania coarse powder and the titania fine powder used for the preparation of the raw material composition is a titania coarse powder: titania fine powder = 100: 0.
In the inorganic powder, the volume ratio of particles having a particle size of 5 μm or less and particles having a particle size exceeding 5 μm is 20.1: 79.9.
Further, the ratio of the pore former is 43.4% by volume with respect to the total volume of the particles contained in the raw material composition, and 49% with respect to the total volume of the particles having a particle diameter of more than 5 μm contained in the raw material composition. .9% by volume.
(比較例2)
アルミナ粉末のD50を15.4μmに変更したことを除いて、実施例1と同様にハニカム構造体を作製した。
原料組成物の作製に使用したチタニア粗粉末とチタニア微粉末の配合比は、重量比で、チタニア粗粉末:チタニア微粉末=0:100である。
無機粉末中、粒子径が5μm以下の粒子と粒子径が5μmを超える粒子との体積比は、58.3:41.7である。
また、造孔材の割合は、原料組成物に含まれる粒子の合計体積に対して43.4体積%であり、原料組成物に含まれる粒子径が5μmを超える粒子の合計体積に対して65.2体積%である。 (Comparative Example 2)
A honeycomb structure was manufactured in the same manner as in Example 1 except that D50 of the alumina powder was changed to 15.4 μm.
The compounding ratio of the titania coarse powder and the titania fine powder used in the preparation of the raw material composition is a titania coarse powder: titania fine powder = 0: 100 in weight ratio.
In the inorganic powder, the volume ratio of particles having a particle diameter of 5 μm or less and particles having a particle diameter exceeding 5 μm is 58.3: 41.7.
The ratio of the pore former is 43.4% by volume with respect to the total volume of the particles contained in the raw material composition, and 65% with respect to the total volume of the particles having a particle diameter of more than 5 μm contained in the raw material composition. .2% by volume.
アルミナ粉末のD50を15.4μmに変更したことを除いて、実施例1と同様にハニカム構造体を作製した。
原料組成物の作製に使用したチタニア粗粉末とチタニア微粉末の配合比は、重量比で、チタニア粗粉末:チタニア微粉末=0:100である。
無機粉末中、粒子径が5μm以下の粒子と粒子径が5μmを超える粒子との体積比は、58.3:41.7である。
また、造孔材の割合は、原料組成物に含まれる粒子の合計体積に対して43.4体積%であり、原料組成物に含まれる粒子径が5μmを超える粒子の合計体積に対して65.2体積%である。 (Comparative Example 2)
A honeycomb structure was manufactured in the same manner as in Example 1 except that D50 of the alumina powder was changed to 15.4 μm.
The compounding ratio of the titania coarse powder and the titania fine powder used in the preparation of the raw material composition is a titania coarse powder: titania fine powder = 0: 100 in weight ratio.
In the inorganic powder, the volume ratio of particles having a particle diameter of 5 μm or less and particles having a particle diameter exceeding 5 μm is 58.3: 41.7.
The ratio of the pore former is 43.4% by volume with respect to the total volume of the particles contained in the raw material composition, and 65% with respect to the total volume of the particles having a particle diameter of more than 5 μm contained in the raw material composition. .2% by volume.
[焼成収縮率]
得られたハニカム構造体の焼成前後の全長を測定して、以下の式から焼成収縮率を算出した。
焼成収縮率(%)=[(焼成前の全長)-(焼成後の全長)]/(焼成前の全長)]×100 [Baking shrinkage]
The total length of the obtained honeycomb structure before and after firing was measured, and the firing shrinkage rate was calculated from the following formula.
Firing shrinkage rate (%) = [(full length before firing) − (full length after firing)] / (full length before firing)] × 100
得られたハニカム構造体の焼成前後の全長を測定して、以下の式から焼成収縮率を算出した。
焼成収縮率(%)=[(焼成前の全長)-(焼成後の全長)]/(焼成前の全長)]×100 [Baking shrinkage]
The total length of the obtained honeycomb structure before and after firing was measured, and the firing shrinkage rate was calculated from the following formula.
Firing shrinkage rate (%) = [(full length before firing) − (full length after firing)] / (full length before firing)] × 100
[機械的強度]
ハニカム構造体の機械的強度として、以下の方法により、曲げ強度を測定した。
まず、3点曲げ強度測定用サンプルとして、各実施例及び比較例と同じ配合で混合、混練した原料組成物を直方体に成形して、同条件で脱脂、焼成後に6mm×6mm×40mmに加工した部材を10本準備した。3点曲げ強度測定用サンプルの主面(サンプルの外周面のうち広い方の面)に対して垂直な方向に荷重を印加し、破壊荷重(サンプルが破壊した荷重)を測定した。10本の3点曲げ強度測定用サンプルについて破壊荷重を測定し、その平均値を曲げ強度とした。3点曲げ強度試験は、JIS R 1601を参考に、インストロン5582を用い、スパン間距離:30mm、スピード1mm/minで行った。 [Mechanical strength]
As the mechanical strength of the honeycomb structure, the bending strength was measured by the following method.
First, as a sample for measuring three-point bending strength, a raw material composition mixed and kneaded with the same composition as each example and comparative example was formed into a rectangular parallelepiped, degreased under the same conditions, and processed into 6 mm × 6 mm × 40 mm after firing. Ten members were prepared. A load was applied in a direction perpendicular to the main surface of the three-point bending strength measurement sample (the wider one of the outer peripheral surfaces of the sample), and the breaking load (the load at which the sample broke) was measured. The breaking load was measured for ten three-point bending strength measurement samples, and the average value was taken as the bending strength. The three-point bending strength test was performed using an Instron 5582 with reference to JIS R 1601, a span distance of 30 mm, and a speed of 1 mm / min.
ハニカム構造体の機械的強度として、以下の方法により、曲げ強度を測定した。
まず、3点曲げ強度測定用サンプルとして、各実施例及び比較例と同じ配合で混合、混練した原料組成物を直方体に成形して、同条件で脱脂、焼成後に6mm×6mm×40mmに加工した部材を10本準備した。3点曲げ強度測定用サンプルの主面(サンプルの外周面のうち広い方の面)に対して垂直な方向に荷重を印加し、破壊荷重(サンプルが破壊した荷重)を測定した。10本の3点曲げ強度測定用サンプルについて破壊荷重を測定し、その平均値を曲げ強度とした。3点曲げ強度試験は、JIS R 1601を参考に、インストロン5582を用い、スパン間距離:30mm、スピード1mm/minで行った。 [Mechanical strength]
As the mechanical strength of the honeycomb structure, the bending strength was measured by the following method.
First, as a sample for measuring three-point bending strength, a raw material composition mixed and kneaded with the same composition as each example and comparative example was formed into a rectangular parallelepiped, degreased under the same conditions, and processed into 6 mm × 6 mm × 40 mm after firing. Ten members were prepared. A load was applied in a direction perpendicular to the main surface of the three-point bending strength measurement sample (the wider one of the outer peripheral surfaces of the sample), and the breaking load (the load at which the sample broke) was measured. The breaking load was measured for ten three-point bending strength measurement samples, and the average value was taken as the bending strength. The three-point bending strength test was performed using an Instron 5582 with reference to JIS R 1601, a span distance of 30 mm, and a speed of 1 mm / min.
[AT化率]
得られたハニカム構造体の一部を粉砕して作製した粒径0.5mm以下の粉末を用いてX線回折測定を行い、チタン酸アルミニウムの(101)面の積分強度IAT(101)とTiO2の(110)面の積分強度ITiO2(111)より、以下の式からAT化率を求めた。
AT化率(%)=[IAT(101)/(IAT(101)+ITiO2(111))]×100 [AT conversion rate]
X-ray diffraction measurement was performed using a powder having a particle size of 0.5 mm or less produced by pulverizing a part of the obtained honeycomb structure, and the integrated intensity I AT (101) of the (101) plane of aluminum titanate from the integrated intensity I TiO2 of TiO 2 (110) plane (111) was determined AT conversion ratio from the following equation.
AT conversion rate (%) = [I AT (101) / (I AT (101) + I TiO2 (111) )] × 100
得られたハニカム構造体の一部を粉砕して作製した粒径0.5mm以下の粉末を用いてX線回折測定を行い、チタン酸アルミニウムの(101)面の積分強度IAT(101)とTiO2の(110)面の積分強度ITiO2(111)より、以下の式からAT化率を求めた。
AT化率(%)=[IAT(101)/(IAT(101)+ITiO2(111))]×100 [AT conversion rate]
X-ray diffraction measurement was performed using a powder having a particle size of 0.5 mm or less produced by pulverizing a part of the obtained honeycomb structure, and the integrated intensity I AT (101) of the (101) plane of aluminum titanate from the integrated intensity I TiO2 of TiO 2 (110) plane (111) was determined AT conversion ratio from the following equation.
AT conversion rate (%) = [I AT (101) / (I AT (101) + I TiO2 (111) )] × 100
[熱膨張係数]
得られたハニカム構造体から、断面形状4.8mm×4.8mm×全長20mmの寸法のサンプルを、全長の方向が流路方向にほぼ一致するように切り出し、熱機械分析装置(NETZSCH DIL402C)を用いて、一定荷重20gをかけながら、昇温速度10℃/minで室温から1000℃まで加熱したときの全長方向の長さの増加量を測定して、50~1000℃間の平均熱膨張係数を求めた。 [Thermal expansion coefficient]
A sample having a cross-sectional shape of 4.8 mm × 4.8 mm × total length 20 mm was cut out from the obtained honeycomb structure so that the direction of the total length substantially coincided with the flow path direction, and a thermomechanical analyzer (NETZSCH DIL402C) was used. The average thermal expansion coefficient between 50 and 1000 ° C. was measured by measuring the increase in length in the full length direction when heated from room temperature to 1000 ° C. at a temperature rising rate of 10 ° C./min while applying a constant load of 20 g. Asked.
得られたハニカム構造体から、断面形状4.8mm×4.8mm×全長20mmの寸法のサンプルを、全長の方向が流路方向にほぼ一致するように切り出し、熱機械分析装置(NETZSCH DIL402C)を用いて、一定荷重20gをかけながら、昇温速度10℃/minで室温から1000℃まで加熱したときの全長方向の長さの増加量を測定して、50~1000℃間の平均熱膨張係数を求めた。 [Thermal expansion coefficient]
A sample having a cross-sectional shape of 4.8 mm × 4.8 mm × total length 20 mm was cut out from the obtained honeycomb structure so that the direction of the total length substantially coincided with the flow path direction, and a thermomechanical analyzer (NETZSCH DIL402C) was used. The average thermal expansion coefficient between 50 and 1000 ° C. was measured by measuring the increase in length in the full length direction when heated from room temperature to 1000 ° C. at a temperature rising rate of 10 ° C./min while applying a constant load of 20 g. Asked.
[気孔率及び気孔分布]
得られたハニカム構造体を10mm×10mm×10mmに切り出して、気孔分布測定用サンプルを準備した。気孔分布測定用サンプルを用いて、水銀圧入法によるポロシメーター(島津製作所社製、オートポアIII 9420)により気孔率及び気孔分布を測定した。水銀圧入法にて接触角を130°、表面張力を485mN/mの条件とした。細孔直径1~100μmの範囲で細孔分布を測定してX軸に細孔直径(μm)を、Y軸にlog微分細孔容積(mL/g)をとって気孔分布曲線を描いた。 [Porosity and pore distribution]
The obtained honeycomb structure was cut out to 10 mm × 10 mm × 10 mm to prepare a sample for pore distribution measurement. Using the sample for pore distribution measurement, the porosity and the pore distribution were measured by a porosimeter (manufactured by Shimadzu Corporation, Autopore III 9420) by a mercury intrusion method. The contact angle was 130 ° and the surface tension was 485 mN / m by mercury porosimetry. The pore distribution was measured in the range of 1 to 100 μm, and the pore distribution curve was drawn with the pore diameter (μm) on the X axis and the log differential pore volume (mL / g) on the Y axis.
得られたハニカム構造体を10mm×10mm×10mmに切り出して、気孔分布測定用サンプルを準備した。気孔分布測定用サンプルを用いて、水銀圧入法によるポロシメーター(島津製作所社製、オートポアIII 9420)により気孔率及び気孔分布を測定した。水銀圧入法にて接触角を130°、表面張力を485mN/mの条件とした。細孔直径1~100μmの範囲で細孔分布を測定してX軸に細孔直径(μm)を、Y軸にlog微分細孔容積(mL/g)をとって気孔分布曲線を描いた。 [Porosity and pore distribution]
The obtained honeycomb structure was cut out to 10 mm × 10 mm × 10 mm to prepare a sample for pore distribution measurement. Using the sample for pore distribution measurement, the porosity and the pore distribution were measured by a porosimeter (manufactured by Shimadzu Corporation, Autopore III 9420) by a mercury intrusion method. The contact angle was 130 ° and the surface tension was 485 mN / m by mercury porosimetry. The pore distribution was measured in the range of 1 to 100 μm, and the pore distribution curve was drawn with the pore diameter (μm) on the X axis and the log differential pore volume (mL / g) on the Y axis.
各気孔分布曲線から、d10、d50、d90の値を算出した。
また、気孔分布曲線の形状がシャープであるかの指標として、(d90-d10)/d50の式で示される値を算出し、気孔シャープ度とした。この値が小さいほど気孔分布曲線の形状はシャープであるといえる。
d10、d50、d90は、気孔分布曲線における累積細孔容積の小径側から累積10%、累積50%、累積90%に相当する細孔径である。 The values of d10, d50, and d90 were calculated from each pore distribution curve.
In addition, as an index of whether the shape of the pore distribution curve is sharp, a value represented by the formula (d90-d10) / d50 was calculated and used as the pore sharpness. It can be said that the smaller the value, the sharper the shape of the pore distribution curve.
d10, d50, and d90 are pore diameters corresponding to cumulative 10%, cumulative 50%, and cumulative 90% from the small diameter side of the cumulative pore volume in the pore distribution curve.
また、気孔分布曲線の形状がシャープであるかの指標として、(d90-d10)/d50の式で示される値を算出し、気孔シャープ度とした。この値が小さいほど気孔分布曲線の形状はシャープであるといえる。
d10、d50、d90は、気孔分布曲線における累積細孔容積の小径側から累積10%、累積50%、累積90%に相当する細孔径である。 The values of d10, d50, and d90 were calculated from each pore distribution curve.
In addition, as an index of whether the shape of the pore distribution curve is sharp, a value represented by the formula (d90-d10) / d50 was calculated and used as the pore sharpness. It can be said that the smaller the value, the sharper the shape of the pore distribution curve.
d10, d50, and d90 are pore diameters corresponding to cumulative 10%, cumulative 50%, and cumulative 90% from the small diameter side of the cumulative pore volume in the pore distribution curve.
各測定結果をまとめて表1に示す。
The measurement results are summarized in Table 1.
表1より、実施例1~実施例4では、焼成収縮率が小さく、曲げ強度が高い。また、AT化率が100%であり、熱膨張係数が低い。さらに、シャープな気孔分布を有している。
From Table 1, Examples 1 to 4 have a low firing shrinkage ratio and a high bending strength. Further, the AT conversion rate is 100% and the thermal expansion coefficient is low. Furthermore, it has a sharp pore distribution.
これに対し、粒子径が5μmを超える粒子の割合が多すぎる比較例1では、チタン酸アルミニウムの合成反応が進行しにくいため、AT化率が低く、曲げ強度が低く、熱膨張係数が高い。また、粒子径が5μmを超える粒子の割合が少なすぎる比較例2では、焼成収縮率が大きい。
On the other hand, in Comparative Example 1 in which the proportion of particles having a particle diameter exceeding 5 μm is too large, the synthesis reaction of aluminum titanate hardly proceeds, so the AT conversion rate is low, the bending strength is low, and the thermal expansion coefficient is high. In Comparative Example 2 in which the proportion of particles having a particle diameter exceeding 5 μm is too small, the firing shrinkage ratio is large.
以上の結果から、無機粉末中の、粒子径が5μm以下の粒子と粒子径が5μmを超える粒子との体積比を調整することにより、熱膨張係数が低く、焼成収縮率が小さいハニカム構造体が得られると考えられる。
From the above results, a honeycomb structure having a low thermal expansion coefficient and a low firing shrinkage rate can be obtained by adjusting the volume ratio of particles having a particle size of 5 μm or less and particles having a particle size exceeding 5 μm in the inorganic powder. It is thought that it is obtained.
10 ハニカム構造体
11a 排ガス導入セル
11b 排ガス排出セル
12a,12b 封止部
13 セル隔壁
14 排ガスが導入される側の端面
15 排ガスが排出される側の端面
16 外周壁
G 排ガス DESCRIPTION OFSYMBOLS 10 Honeycomb structure 11a Exhaust gas introduction cell 11b Exhaust gas discharge cell 12a, 12b Sealing part 13 Cell partition wall 14 End surface 15 in which exhaust gas is introduced End surface 16 in which exhaust gas is exhausted Outer wall G
11a 排ガス導入セル
11b 排ガス排出セル
12a,12b 封止部
13 セル隔壁
14 排ガスが導入される側の端面
15 排ガスが排出される側の端面
16 外周壁
G 排ガス DESCRIPTION OF
Claims (6)
- チタニア粉末及びアルミナ粉末を含む無機粉末と、造孔材とを含む原料組成物を成形することにより、ハニカム成形体を得る工程と、
前記ハニカム成形体を焼成する工程とを含む、チタン酸アルミニウムからなるハニカム構造体の製造方法であって、
前記無機粉末中、粒子径が5μm以下の粒子の占める体積割合が25体積%より大きく、50体積%より小さいことを特徴とするハニカム構造体の製造方法。 A step of obtaining a honeycomb formed body by molding a raw material composition containing an inorganic powder containing titania powder and alumina powder, and a pore former;
A method of manufacturing a honeycomb structure made of aluminum titanate, including a step of firing the honeycomb formed body,
A method for manufacturing a honeycomb structure, wherein a volume ratio of particles having a particle diameter of 5 μm or less in the inorganic powder is larger than 25% by volume and smaller than 50% by volume. - 前記原料組成物に含まれる粒子の合計体積に対して、前記造孔材の割合が、30体積%以上、60体積%以下である請求項1に記載のハニカム構造体の製造方法。 The method for manufacturing a honeycomb structured body according to claim 1, wherein a ratio of the pore former is 30% by volume or more and 60% by volume or less with respect to a total volume of particles contained in the raw material composition.
- 前記チタニア粉末は、チタニア粗粉末と、前記チタニア粗粉末よりも平均粒子径D50の小さいチタニア微粉末とを含む請求項1又は2に記載のハニカム構造体の製造方法。 The method for manufacturing a honeycomb structure according to claim 1 or 2, wherein the titania powder includes a titania coarse powder and a fine titania powder having an average particle diameter D50 smaller than the titania coarse powder.
- 前記チタニア粗粉末の平均粒子径D50は、5~25μmであり、
前記チタニア微粉末の平均粒子径D50は、0.1~1.5μmである請求項3に記載のハニカム構造体の製造方法。 The average particle diameter D50 of the titania coarse powder is 5 to 25 μm,
The method for manufacturing a honeycomb structured body according to claim 3, wherein the titania fine powder has an average particle diameter D50 of 0.1 to 1.5 µm. - 前記チタニア粗粉末の平均粒子径D50は、前記アルミナ粉末の平均粒子径D50と同等であるか、又は、前記アルミナ粉末の平均粒子径D50よりも小さい請求項3又は4に記載のハニカム構造体の製造方法。 5. The honeycomb structure according to claim 3, wherein an average particle diameter D50 of the titania coarse powder is equal to or smaller than an average particle diameter D50 of the alumina powder. Production method.
- 前記無機粉末は、シリカ粉末及びマグネシア粉末をさらに含む請求項1~5のいずれか1項に記載のハニカム構造体の製造方法。 The method for manufacturing a honeycomb structured body according to any one of claims 1 to 5, wherein the inorganic powder further includes silica powder and magnesia powder.
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WO2010067859A1 (en) * | 2008-12-11 | 2010-06-17 | 住友化学株式会社 | Process for producing aluminum titanate-based fired product |
JP2011526573A (en) * | 2008-07-04 | 2011-10-13 | サン−ゴバン サントル ドゥ ルシェルシェ エ デトゥードゥ ユーロペン | Particle mixture for producing an aluminum titanate type porous structure |
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WO2008078747A1 (en) * | 2006-12-27 | 2008-07-03 | Hitachi Metals, Ltd. | Process for producing aluminum-titanate-based ceramic honeycomb structure |
JP2011526573A (en) * | 2008-07-04 | 2011-10-13 | サン−ゴバン サントル ドゥ ルシェルシェ エ デトゥードゥ ユーロペン | Particle mixture for producing an aluminum titanate type porous structure |
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