WO2003004132A1 - Procede de fabrication d'un filtre ceramique poreux - Google Patents

Procede de fabrication d'un filtre ceramique poreux Download PDF

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Publication number
WO2003004132A1
WO2003004132A1 PCT/JP2002/006658 JP0206658W WO03004132A1 WO 2003004132 A1 WO2003004132 A1 WO 2003004132A1 JP 0206658 W JP0206658 W JP 0206658W WO 03004132 A1 WO03004132 A1 WO 03004132A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer particles
hollow polymer
porous ceramic
pore
meth
Prior art date
Application number
PCT/JP2002/006658
Other languages
English (en)
Japanese (ja)
Inventor
Takahiro Ohmura
Toshiharu Furukawa
Yasuhiro Kawaguchi
Original Assignee
Sekisui Chemical Co., Ltd.
Tokuyama Sekisui Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sekisui Chemical Co., Ltd., Tokuyama Sekisui Co., Ltd. filed Critical Sekisui Chemical Co., Ltd.
Publication of WO2003004132A1 publication Critical patent/WO2003004132A1/fr

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Classifications

    • 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
    • C04B38/063—Preparing or treating the raw materials individually or as batches
    • C04B38/0635—Compounding ingredients
    • C04B38/0645—Burnable, meltable, sublimable materials
    • C04B38/065—Burnable, meltable, sublimable materials characterised by physical aspects, e.g. shape, size or porosity
    • C04B38/0655—Porous materials
    • 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
    • B01D39/2068—Other inorganic materials, e.g. ceramics
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00793—Uses not provided for elsewhere in C04B2111/00 as filters or diaphragms

Definitions

  • the present invention relates to a method for producing a porous ceramic filter having high porosity and high heat resistance.
  • porous ceramic filter As a porous ceramic filter, the partition walls of a honeycomb structure formed by sintering silicon carbide (SiC) powder have been made to have a porous structure.
  • SiC silicon carbide
  • Various porous honeycomb filters having a filter function for a fluid have been proposed, and have been put to practical use, for example, as a filter (diesel particulate filter) for collecting particulates of exhaust gas discharged from diesel vehicles.
  • the average pore diameter (hereinafter referred to as the pore diameter) and the porosity of the porous material are very important factors for determining the performance of the filter, and such as a diesel particulate filter.
  • a filter having a large pore diameter and a large porosity is desired in view of the collection efficiency, pressure loss and collection time of the fine particles.
  • the pore size of a ceramic filter has been controlled by appropriately selecting the aggregate particle size of a ceramic composition as a raw material.
  • a method of controlling the pore size in order to improve the filter performance for example, a method of adding an organic polymer to a ceramic composition has been proposed (Japanese Patent Application Laid-Open No. 2000-288832). No. 5).
  • Japanese Patent Application Laid-Open No. 3-215374 discloses an average particle diameter of 100 to 150 ⁇ and an average particle diameter of 20 ⁇ m.
  • the S i C powder having a particle size distribution 9 0 weight 0/0 or within% is present, interconnected by crushing a surface portion thereof, so as to remain in the molded body during not collapse inside the force its
  • an object of the present invention is to provide a method for manufacturing a porous ceramic filter which has low thermal expansion and thermal shock resistance and has improved porosity.
  • a porous ceramic filter with improved porosity without thermal deformation can be obtained by shaping a predetermined molded body from a ceramic composition using hollow polymer particles as a pore-forming agent and then firing it.
  • the present invention has been completed.
  • the present invention is characterized in that a predetermined molded body is molded from a ceramic composition containing silicon carbide powder as a main component and containing hollow polymer particles as a pore-forming agent, and then the molded body is fired.
  • a ceramic composition containing silicon carbide (SiC) powder as a main component and hollow polymer particles as a pore-forming agent is used.
  • the amount of the hollow polymer particles added is not particularly limited, but if the amount is too small, sufficient porosity cannot be obtained, and if the amount is too large, the strength of the fired ceramic molded body decreases.
  • the content is 10 to 50% by weight in the composition.
  • the above hollow polymer particles those having an average particle size of 5 to 100 ⁇ and a compressive strength of 10% or more of 1.5 MPa are preferable.
  • the average particle size is smaller than 5 im, the pore size of the obtained porous ceramic filter becomes smaller, the pressure loss of the filter increases, and the collection time becomes shorter.
  • the average particle size is larger than 10 ⁇ , the pore size of the ceramic filter increases, The pressure loss of the filter decreases, but the collection efficiency decreases.
  • the 10% compressive strength is 1.5 MPa or more.
  • hollow particles having a honeycomb-like morphology comprising a plurality of pores have superior compressive strength. That is, by using hollow polymer particles having a plurality of pores as the pore-forming agent, the number of particles broken in the process of forming the filter is reduced, and the porosity can be improved.
  • the method for producing the hollow polymer particles is not particularly limited, but a production method comprising the following two steps of suspension polymerization and solvent removal is preferred.
  • a monomer solution is prepared by mixing a non-polymerizable organic solvent with a mixed monomer composed of a hydrophilic monomer, a polyfunctional monomer and other monomers, and the monomer solution is suspended in a polar solvent. It comprises a first step of polymerizing the components to obtain polymer particles containing the non-polymerizable organic solvent, and a second step of removing the organic solvent in the polymer particles to obtain hollow polymer particles.
  • the polymerization method is not particularly limited, but it is preferable to use a suspension polymerization method because it is easy to control the particle diameter and easily form particles containing effective voids.
  • the hydrophilic monomer constituting the above monomer component has a higher affinity for a polar solvent than an organic solvent, it is considered that the hydrophilic monomer is localized at the oil droplet interface in the suspended oil droplets of the monomer solution, resulting in polymerization. Thereby, the outer wall surface of the hollow polymer particles is formed.
  • the hydrophilic monomer preferably has a solubility in water of 1% by weight or more.
  • the weight is more preferably 30 to 99.9. / 0 .
  • the polyfunctional monomer constituting the above monomer component is added for the purpose of improving the compression resistance of the particles, and di (meth) acrylate and tri (meth) acrylate are suitably used.
  • di (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and 1,6-hexanediol di (meth).
  • Examples of the tri (meth) acrylate include trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate.
  • Examples of the polyfunctional monomer other than the above include, for example, pentaerythritol tetra (meth) acrylate, dipentaerythritolhexa (meth) acrylate, diarylphthalate, diarylmalate, diarylfumarate, diarylsuccinate, triallylisolate. Examples thereof include di- or triallyl compounds such as cyanurate and the like, and dibutyl compounds such as dibutylbenzene and butadiene.
  • These polyfunctional monomers can be used alone or in combination of two or more.
  • the amount of the polyfunctional monomer used is too small, the compression resistance of the hollow polymer particles is not sufficient, and if the amount is too large, the aggregation of the particles occurs during polymerization.
  • % Preferably 0.3 to 5% by weight.
  • the content of the other monomer is preferably 89.9% by weight or less, More preferably, it is 69.9% by weight or less.
  • the non-polymerizable organic solvent added to the monomer component is desirably localized at the center of the oil droplets in the oil droplets suspended in the monomer solution, and has a water solubility of 0.2% by weight or less.
  • the type is not particularly limited, but for example, butane, pentane, hexane, cyclohexane, toluene, xylene and the like are preferably used. Above all, highly volatile butane, pentane, hexane and cyclohexane are more preferred.
  • the amount of the non-polymerizable organic solvent is too small, the porosity of the particles will be low, and if too large, the porosity will be too high and the strength of the particles will be reduced. It is preferably 1 to 400 parts by weight, more preferably 10 to 200 parts by weight.
  • a talc powder component such as talc and calcined talc as an inorganic binder, a silica powder represented by amorphous silica, a pore-forming agent, Kaolin, calcined kaolin, boron oxide, alumina, aluminum hydroxide and the like are appropriately blended to prepare a ceramic composition mainly composed of SiC powder.
  • the amount of the inorganic binder to be added to the SiC powder is not particularly limited, and is appropriately determined depending on the quality of the hollow polymer particles and the like.
  • a plasticizer, a binder and the like are added to the ceramic composition thus prepared in the same manner as in the conventional method, and the plastic composition is plasticized to obtain a shapeable extrusion molding raw material.
  • the raw material is extruded into a honeycomb formed body having a predetermined shape, dried, and then fired at a temperature of 160 to 220 ° C.
  • Manufacture a porous ceramic filter In the production method of the present invention, low thermal expansion is imparted to the porous ceramic filter, and porosity and thermal shock resistance are improved by incorporating hollow polymer particles as a pore-forming agent into the ceramic composition. (1) It is possible to provide a filter capable of suppressing the rise in pressure loss while maintaining the collection efficiency and effectively extending the collection time.
  • the volume occupied by the pore-forming agent increases, and the porosity can be improved.
  • the heat of combustion of the particles during firing decreases, and the strain applied to the ceramic molded product is reduced, so that low thermal expansion properties are imparted and thermal shock resistance is improved.
  • the pressure in the polymerization vessel was reduced to deoxygenate the inside of the vessel, and then nitrogen was injected to return the pressure to atmospheric pressure. After the inside was set to a nitrogen atmosphere, the above suspended monomer solution was added all at once. Then, the temperature of the polymerization vessel was raised to 80 ° C. to start polymerization. After 5 hours, the polymerization was completed. After an aging period of 1 hour, the polymerization reactor was cooled to room temperature.
  • the slurry was dehydrated with a centrifuge and the organic solvent was removed by vacuum drying to obtain hollow polymer particles (a) to (e).
  • Expandable particles (“F-85D” manufactured by Matsumoto Yushi Co., Ltd.) were heated at 170 ° C. for 1 minute, and solid polymer particles were used.
  • Particles are sampled from three arbitrary locations, and the volume average particle size of the hollow polymer particles is measured for each sample using a laser diffraction single particle size distribution analyzer “LA-910” manufactured by Horiba, Ltd. The average was determined.
  • the equatorial section of the hollow polymer particles was applied to a thin film, and the internal morphology was observed with a transmission electron microscope.
  • the porosity of the hollow polymer particles was measured using an Amcone earth porosimeter “2000”. Mercury filling pressure 2, OOO k gZcm 2 and then, using a hollow polymer particle sample 0. 5 g sample from any location in the evaluation.
  • the 10% compressive strength of the hollow polymer particles was measured using a micro compression tester “MCTM-500” manufactured by Shimadzu Corporation.
  • MMA methyl methacrylate
  • MAC methacrylic acid
  • TMP Trimethylolpropane triatarylate
  • Colloidal silica, calcium phosphate 20% by weight aqueous solution
  • each clay obtained by shaping by a known extrusion molding method rib thickness: 4 3 0 m
  • the number of cells 1 6 diameter having a Z cm 2: 1 1 8 mm, ⁇ of: 1
  • a 52-mm cylindrical honeycomb structure was fabricated.
  • the temperature was raised to 500 at a heating rate of 40 ° C./hour, a degreasing step was performed for 1 hour, and further performed under an inert gas atmosphere at 2100 ° C. And fired for 2 hours to obtain a porous ceramic filter.
  • a porous ceramic finoleta was obtained in the same manner as in Example 2, except that solid polymer particles (f) were used as the pore former.
  • the thermal expansion coefficient in the height direction (A-axis) and in the cylinder diameter direction (B-axis) was measured using “TMA100” manufactured by Seiko Istrungmen.
  • the measurement temperature was 40 to 800 ° C, and the heating rate was 40.
  • the porosity was measured by the same method.
  • the sample used was the filter obtained.
  • the method for producing a porous ceramic filter of the present invention has the above-described configuration, and by using hollow polymer particles as a pore-forming agent, a porous ceramic filter having a high porosity and a high thermal shock resistance can be obtained. it can.
  • the obtained porous ceramic filter is suitably used especially as a diesel particulate filter.
  • Types of hollow polymer particles (a) (b) (C) (d) (e) (f)
  • Agent Ratio in ceramic composition 30 30 30 30 30 30 30 F A-axis 0.46 0.60 0.61 0.60 0.82 0.79 Thermal expansion coefficient

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Filtering Materials (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un filtre céramique poreux caractérisé en ce qu'une composition céramique contenant un carbure de silicium en tant que constituant primaire et des particules polymères creuses en tant qu'agent porogène est formée dans un article de forme prédéterminée, et en ce que l'article formé résultant est soumis à cuisson.
PCT/JP2002/006658 2001-07-05 2002-07-01 Procede de fabrication d'un filtre ceramique poreux WO2003004132A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001-204725 2001-07-05
JP2001204725A JP4991057B2 (ja) 2001-07-05 2001-07-05 多孔質セラミックフィルタの製造方法

Publications (1)

Publication Number Publication Date
WO2003004132A1 true WO2003004132A1 (fr) 2003-01-16

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WO (1) WO2003004132A1 (fr)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4224368B2 (ja) * 2003-08-12 2009-02-12 積水化学工業株式会社 中空樹脂粒子の製造方法及び中空樹脂粒子
JP4183603B2 (ja) * 2003-11-19 2008-11-19 積水化学工業株式会社 中空樹脂粒子の製造方法及び中空樹脂粒子
JP2005145937A (ja) * 2003-11-19 2005-06-09 Sekisui Chem Co Ltd 多孔質セラミックフィルタ成形用造孔剤及び吸油性もしくは吸水性化粧用粒子
US20090014925A1 (en) * 2004-01-13 2009-01-15 Ngk Insulators, Ltd. Method for manufacturing ceramic structure
US7387829B2 (en) 2004-01-13 2008-06-17 Ibiden Co., Ltd. Honeycomb structure, porous body, pore forming material for the porous body, and methods for manufacturing the pore forming material, the porous body and the honeycomb structure
JP4745964B2 (ja) * 2004-04-22 2011-08-10 日本碍子株式会社 多孔質ハニカム構造体の製造方法及び多孔質ハニカム構造体
JP4630696B2 (ja) * 2005-03-08 2011-02-09 積水化学工業株式会社 鈴構造樹脂粒子の製造方法
JP4668654B2 (ja) * 2005-03-23 2011-04-13 積水化学工業株式会社 加熱消滅性中空樹脂粒子及び加熱消滅性中空樹脂粒子の製造方法
US8138252B2 (en) 2005-03-23 2012-03-20 Sekisui Chemical Co., Ltd. Thermally disappearing resin particle
JP2007073946A (ja) * 2005-08-10 2007-03-22 Sekisui Chem Co Ltd 固体電解コンデンサ用陽極体の製造方法
JP5596611B2 (ja) * 2011-03-31 2014-09-24 日本碍子株式会社 ハニカム構造体の製造方法
JP6943714B2 (ja) * 2017-01-27 2021-10-06 積水化学工業株式会社 固体酸化物型燃料電池電極造孔剤用樹脂微粒子
US11230503B2 (en) * 2017-06-27 2022-01-25 General Electric Company Resin for production of porous ceramic stereolithography and methods of its use
JP6513273B1 (ja) * 2018-08-31 2019-05-15 三井化学株式会社 樹脂粒子

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59174561A (ja) * 1983-03-18 1984-10-03 三井造船株式会社 多孔質セラミツクスの製造方法
JPS6239639A (ja) * 1985-08-14 1987-02-20 マン　テクノロジ−　ゲ−エムベ−ハ− 多孔性物体の製造方法
JPH02290211A (ja) * 1989-04-28 1990-11-30 Kanebo Ltd セラミックフィルター及びその製造方法
WO1993005864A1 (fr) * 1991-09-13 1993-04-01 Calgon Carbon Corporation Appareil et procede destines a eliminer les composes organiques d'un flux de gaz
JPH06227874A (ja) * 1993-02-04 1994-08-16 Kanebo Ltd 多孔質焼結体の製造方法
JPH08323123A (ja) * 1995-05-31 1996-12-10 Matsushita Electric Ind Co Ltd 排ガスフィルタおよびその製造方法
JPH11128639A (ja) * 1997-10-31 1999-05-18 Asahi Glass Co Ltd セラミックスフィルタ及びその製造方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4394329B2 (ja) * 2001-03-01 2010-01-06 日本碍子株式会社 セラミックス構造体の製造方法
US7319114B2 (en) * 2001-03-14 2008-01-15 Sekisui Chemical Co., Ltd. Hollow polymer particles, method for preparing hollow polymer particles, porous ceramic filter, and method for preparing porous ceramic filter

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59174561A (ja) * 1983-03-18 1984-10-03 三井造船株式会社 多孔質セラミツクスの製造方法
JPS6239639A (ja) * 1985-08-14 1987-02-20 マン　テクノロジ−　ゲ−エムベ−ハ− 多孔性物体の製造方法
JPH02290211A (ja) * 1989-04-28 1990-11-30 Kanebo Ltd セラミックフィルター及びその製造方法
WO1993005864A1 (fr) * 1991-09-13 1993-04-01 Calgon Carbon Corporation Appareil et procede destines a eliminer les composes organiques d'un flux de gaz
JPH06227874A (ja) * 1993-02-04 1994-08-16 Kanebo Ltd 多孔質焼結体の製造方法
JPH08323123A (ja) * 1995-05-31 1996-12-10 Matsushita Electric Ind Co Ltd 排ガスフィルタおよびその製造方法
JPH11128639A (ja) * 1997-10-31 1999-05-18 Asahi Glass Co Ltd セラミックスフィルタ及びその製造方法

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JP2003010617A (ja) 2003-01-14
JP4991057B2 (ja) 2012-08-01

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