JP2018167217A - ハニカム構造体 - Google Patents
ハニカム構造体 Download PDFInfo
- Publication number
- JP2018167217A JP2018167217A JP2017068342A JP2017068342A JP2018167217A JP 2018167217 A JP2018167217 A JP 2018167217A JP 2017068342 A JP2017068342 A JP 2017068342A JP 2017068342 A JP2017068342 A JP 2017068342A JP 2018167217 A JP2018167217 A JP 2018167217A
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- JP
- Japan
- Prior art keywords
- cell
- honeycomb structure
- cells
- specific
- specific cell
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
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- 238000005192 partition Methods 0.000 claims abstract description 56
- 230000002093 peripheral effect Effects 0.000 claims abstract description 16
- 239000012530 fluid Substances 0.000 claims abstract description 6
- 230000001788 irregular Effects 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 abstract description 28
- 238000000746 purification Methods 0.000 abstract description 20
- 238000005299 abrasion Methods 0.000 abstract description 3
- 210000004027 cell Anatomy 0.000 description 262
- 239000007789 gas Substances 0.000 description 43
- 238000012360 testing method Methods 0.000 description 28
- 230000003628 erosive effect Effects 0.000 description 27
- 239000002994 raw material Substances 0.000 description 24
- 239000000919 ceramic Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- 238000000576 coating method Methods 0.000 description 10
- 238000010304 firing Methods 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 8
- 229910052878 cordierite Inorganic materials 0.000 description 8
- 230000006866 deterioration Effects 0.000 description 8
- 239000004927 clay Substances 0.000 description 7
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000001133 acceleration Effects 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 229910010271 silicon carbide Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000007602 hot air drying Methods 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000002276 dielectric drying Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 2
- SBEQWOXEGHQIMW-UHFFFAOYSA-N silicon Chemical compound [Si].[Si] SBEQWOXEGHQIMW-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 210000001316 polygonal cell Anatomy 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
Classifications
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9431—Processes characterised by a specific device
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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- B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
- B01D46/2418—Honeycomb filters
- B01D46/2451—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure
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- B01D46/2451—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure
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- B01D46/2476—Monolithic structures
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- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
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- C04B2235/661—Multi-step sintering
- C04B2235/662—Annealing after sintering
- C04B2235/663—Oxidative annealing
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- F01N2260/00—Exhaust treating devices having provisions not otherwise provided for
- F01N2260/06—Exhaust treating devices having provisions not otherwise provided for for improving exhaust evacuation or circulation, or reducing back-pressure
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- F01N2260/00—Exhaust treating devices having provisions not otherwise provided for
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- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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- F01N2330/00—Structure of catalyst support or particle filter
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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- F01N2330/00—Structure of catalyst support or particle filter
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F01N2510/00—Surface coverings
- F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Physics & Mathematics (AREA)
- Geometry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
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Abstract
【解決手段】第一端面から第二端面まで延びる流体の流路となる複数のセル2を区画するように配設された多孔質の隔壁、及び隔壁を囲繞するように配設された外周壁を有する、柱状のハニカム構造部を備え、隔壁は、セル2内に延びるように突出し、且つ、セル2の延びる方向に連続して設けられた、突起部21を有し、セル2の延びる方向に直交する断面において、セル2の形状が多角形であり、複数のセル2は、一辺あたりに設けられている突起部21の個数が異なる二辺が交わるように構成された部位を少なくとも1箇所有する、特定セル2aを複数個含み、セル2の延びる方向に直交する断面において、特定セル2aにおける突起部21を含むセル形状の配置方向が、一の特定セル2aと、一の特定セル2a以外の他の特定セル2aとで異なる、ハニカム構造体。
【選択図】図3
Description
前記隔壁は、前記セル内に延びるように突出し、且つ、前記セルの延びる方向に連続して設けられた、突起部を有し、
前記セルの延びる方向に直交する断面において、前記セルの形状が多角形であり、
複数の前記セルは、一辺あたりに設けられている前記突起部の個数が異なる二辺が交わるように構成された部位を少なくとも1箇所有する、特定セルを複数個含み、
前記セルの延びる方向に直交する断面において、前記特定セルにおける前記突起部を含むセル形状の配置方向が、一の前記特定セルと、一の前記特定セル以外の他の前記特定セルとで異なる、ハニカム構造体。
本発明のハニカム構造体の一実施形態は、図1〜図3に示すハニカム構造体100である。ハニカム構造体100は、柱状のハニカム構造部10を備えている。ハニカム構造部10は、第一端面11から第二端面12まで延びる流体の流路となる複数のセル2を区画するように配設された多孔質の隔壁1、及びこの隔壁1を囲繞するように配設された外周壁20を有している。隔壁1は、セル2内に延びるように突出し、且つ、セル2の延びる方向に連続して設けられた、突起部21を有している。セル2の延びる方向に直交する断面において、セル2の形状は多角形である。そして、複数のセル2は、一辺あたりに設けられている突起部21の個数が異なる二辺が交わるように構成された部位を少なくとも1箇所有する、特定セル2aを複数個含んでいる。更に、セル2の延びる方向に直交する断面において、特定セル2aにおける突起部21を含むセル形状の配置方向は、一の特定セル2aと、一の特定セル2a以外の他の特定セル2aとで異なっている。
ハニカム構造体100は、上記の通り隔壁1が突起部21を有している。そのため、ハニカム構造体100に触媒を担持させると、ハニカム構造体100は、突起部21が設けられている分だけ、突起部21が設けられていないハニカム構造体に比べて触媒の担持面積が増える。その結果、触媒と排ガスとの接触性が高まり、排ガスの浄化性能が向上することになる。
本発明のハニカム構造体は、セルの延びる方向に直交する断面において、セルの形状が多角形である。当該セルの形状としては、具体的には、三角形、四角形、五角形、六角形、八角形等の多角形、円形、又は楕円形、あるいは四角形と、六角形又は八角形等との組合せとすることができる。なお、本明細書において「セルの形状が多角形」とは、セルの形状が多角形に準ずる形状を含む概念である。
外周壁20は、隔壁1を囲繞するように配設された壁である。外周壁20は、隔壁1と一体に形成したものであってもよい。
本発明のハニカム構造体は、ハニカム成形工程と、焼成工程と、を有する方法により製造できる。以下に各工程について説明する。
本工程においては、セラミック原料を含有するセラミック成形原料を成形して、流体の流路となる複数のセルを区画するように配設された隔壁を有するハニカム成形体を形成する。
次に、ハニカム成形体を焼成してハニカム焼成体を作製する。ハニカム成形体の焼成(本焼成)は、仮焼したハニカム成形体を構成する成形原料を焼結させて緻密化し、所定の強度を確保するために行われる。焼成条件(温度、時間、雰囲気等)は、成形原料の種類により異なるため、その種類に応じて適当な条件を選択すればよい。例えば、コージェライト化原料を使用している場合には、焼成温度は、1410〜1440℃が好ましい。また、焼成時間は、最高温度でのキープ時間として、4〜8時間が好ましい。仮焼、本焼成を行う装置としては、電気炉、ガス炉等を用いることができる。以上のようして得られたハニカム焼成体を、本発明のハニカム構造体とすることができる。なお、ハニカム構造体の製造方法においては、以下に示すような外周コート工程を更に有していてもよい。
本工程では、得られたハニカム焼成体の外周に、外周コート材を塗布して外周壁を形成する。なお、外周壁は、ハニカム成形体の作製時に、隔壁とともに一体形成により作製してもよい。外周コート工程によって更に外周壁を形成することにより、ハニカム構造体に外力が加わった際にハニカム構造体が欠けてしまうことを防止できる。
実施例1においては、まず、ハニカム構造体を作製するための成形原料を調製した。セラミック原料に、バインダ、界面活性剤、造孔材、水を添加して成形原料とした。なお、使用したセラミック原料としては、コージェライト化原料である、カオリン、タルク、アルミナを用いた。
作製したハニカム構造体について、以下のようにして、米国Fedral Test ProcedureのLA−4モードに基づく試験を行った。まず、ハニカム構造体の隔壁には、触媒(三元触媒)を200g/L担持させた。触媒を担持したハニカム構造体は電気炉を用い、950℃で12時間エージング処理を行った。次に、触媒を担持させたハニカム構造体を、排気量が2400ccの車両の床下位置に搭載し、LA−4試験を行った。LA−4試験においては、排ガス測定装置(HORIBA社製、型番「MEXA−7400」)を用いてガス成分ごとのダイレクトモーダルマスを測定した。また、代表的な排ガス成分としてHCの排出量を測定した。なお、この試験による排ガスの空間速度は、約10000/時間(高流量)であった。
隔壁が突起部を有さないハニカム構造体に対して、隔壁が突起部を有しているハニカム構造体が、Bagエミッションにおいて有利となるためには、加速から2山目の前後のHC排出増加量(%)が35%以下である必要がある。このため、LA−4試験の判定を以下の基準により行った。
判定「良」:HC排出増加量が35%以下である場合を「良」とする。
判定「不可」:HC排出増加量が35%超である場合を「不可」とする。
まず、ハニカム構造体の乾燥質量と体積から「試験前かさ密度」を求めた。なお、乾燥質量とは、熱風の温度120℃において、2時間の熱風乾燥した後のハニカム構造体の質量をいう。次に、このハニカム構造体をアルミナマットで巻いた上で金属製の収納容器に挿入し、LPガスを燃焼とするバーナー試験装置の先端に取り付けた。次に、バーナー試験装置のガス温度を700℃とし、ハニカム構造体のバーナー側の端面近傍のガス流速が270m/秒となるように流量を調節した。また、ハニカム構造体のバーナー側の端面に対するガスの流入角度を、45°とした。次に、ハニカム構造体のバーナー側の端面から平均粒子径50μmのSiC砥粒を1分毎に1g、合計15g投入し、エロージョン試験を行った。そして、エロージョン試験後のハニカム構造体の乾燥質量を測った。また、試験前かさ密度、及び、エロージョン試験前後のハニカム構造体の乾燥質量の差から、エロージョン試験により削られた体積を算出し、エロージョン削れ量(cc)とした。結果を表2及び表4に示す。
まず、セルの延びる方向に直交する断面において、セルの全ての辺に同じ数の突起部を等間隔で有するハニカム構造体をそれぞれ基準構造1〜3とした。即ち、セル形状が四角形であり、全ての辺に2つずつ突起部を有する比較例1、セル形状が四角形であり、全ての辺に3つずつ突起部を有する比較例3、及び、セル形状が六角形であり、全ての辺に2つずつ突起部を有する比較例5をそれぞれ基準構造1〜3とした。
判定「OK」:エロージョン悪化率が1.20未満である場合を「OK」とする。
判定「NG」:エロージョン悪化率が1.20以上である場合を「NG」とする。
作製したハニカム構造体について、大型風洞試験機を用いて圧力損失を測定した。このとき、ガス温度は25℃とし、ガス流量は10Nm3/分とした。評価基準は、各基準構造に対する圧力損失の割合(式:実施例または比較例のハニカム構造体の圧力損失/基準構造の圧力損失により算出される値)を求め、この値が1.20以下の場合を「OK」とし、1.20超の場合を「NG」とした。
LA−4試験の判定と、エロージョン試験の判定と、圧力損失の評価とに基づいて以下の基準により総合判定を行った。
判定「良」:LA−4試験の判定が「良」であり、エロージョン試験の判定が「OK」であり、圧力損失の評価が「OK」である場合を「良」とする。
判定「不可」:LA−4試験の判定、エロージョン試験の判定、または圧力損失の評価に「不可」または「NG」がある場合を「不可」とする。
表1、表3に示すように、所定の数の突起部及び突起部を含むセル形状の配置方向のバリエーションとなるように作製したこと以外は、実施例1と同様にして作製した。
表2及び表4に示すように、実施例1〜18のハニカム構造体は、特定セルを含むことで、特定セルを有さない比較例1,3,5,6のハニカム構造体に比べて、排ガスの浄化性能が高いことが分かる。
Claims (4)
- 第一端面から第二端面まで延びる流体の流路となる複数のセルを区画するように配設された多孔質の隔壁、及び前記隔壁を囲繞するように配設された外周壁を有する、柱状のハニカム構造部を備え、
前記隔壁は、前記セル内に延びるように突出し、且つ、前記セルの延びる方向に連続して設けられた、突起部を有し、
前記セルの延びる方向に直交する断面において、前記セルの形状が多角形であり、
複数の前記セルは、一辺あたりに設けられている前記突起部の個数が異なる二辺が交わるように構成された部位を少なくとも1箇所有する、特定セルを複数個含み、
前記セルの延びる方向に直交する断面において、前記特定セルにおける前記突起部を含むセル形状の配置方向が、一の前記特定セルと、一の前記特定セル以外の他の前記特定セルとで異なる、ハニカム構造体。 - 前記特定セルにおいて、一辺あたりに設けられている前記突起部の個数が3個以下である、請求項1に記載のハニカム構造体。
- 前記セルの延びる方向に直交する断面において、複数個の前記特定セルが一の方向に配列し、当該一の方向において、前記突起部を含むセル形状の配置方向のバリエーションが、規則性を有する、請求項1又は2に記載のハニカム構造体。
- 前記セルの延びる方向に直交する断面において、複数個の前記特定セルが一の方向に配列し、当該一の方向において、前記突起部を含むセル形状の配置方向のバリエーションが、不規則である、請求項1又は2に記載のハニカム構造体。
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