JP6649777B2 - ハニカム構造体 - Google Patents
ハニカム構造体 Download PDFInfo
- Publication number
- JP6649777B2 JP6649777B2 JP2016007765A JP2016007765A JP6649777B2 JP 6649777 B2 JP6649777 B2 JP 6649777B2 JP 2016007765 A JP2016007765 A JP 2016007765A JP 2016007765 A JP2016007765 A JP 2016007765A JP 6649777 B2 JP6649777 B2 JP 6649777B2
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- JP
- Japan
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- cell
- honeycomb structure
- face
- inscribed circle
- diameter
- 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.)
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- 239000002994 raw material Substances 0.000 claims description 16
- 229910052878 cordierite Inorganic materials 0.000 claims description 15
- 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 claims description 13
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- 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 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 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 claims description 5
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 5
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- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 claims description 4
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Images
Classifications
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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
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/022—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
- F01N3/0222—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous the structure being monolithic, e.g. honeycombs
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- B01D53/34—Chemical or biological purification of waste gases
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- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
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- 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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- 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
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
- F01N3/2825—Ceramics
- F01N3/2828—Ceramic multi-channel monoliths, e.g. honeycombs
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- 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
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2839—Arrangements for mounting catalyst support in housing, e.g. with means for compensating thermal expansion or vibration
- F01N3/2842—Arrangements for mounting catalyst support in housing, e.g. with means for compensating thermal expansion or vibration specially adapted for monolithic supports, e.g. of honeycomb type
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2258/00—Sources of waste gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
- B01D2279/00—Filters adapted for separating dispersed particles from gases or vapours specially modified for specific uses
- B01D2279/30—Filters adapted for separating dispersed particles from gases or vapours specially modified for specific uses for treatment of exhaust gases from IC Engines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
- 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
- B01D46/2498—The honeycomb filter being defined by mathematical relationships
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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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- F01N2330/34—Honeycomb supports characterised by their structural details with flow channels of polygonal cross section
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Description
本発明のハニカム構造体の第一実施形態は、図1〜図4に示すようなハニカム構造体100である。ハニカム構造体100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を区画形成する多孔質の隔壁1を有する柱状のハニカム構造部4、及び、ハニカム構造部4の外周を囲繞するように形成された多孔質の外周壁3、を備えたものである。複数のセル2は、最外周に形成されたセルを除き、その断面形状が四角形であり、図面では、四角形の例を示している。ここで、図1は、本発明のハニカム構造体の第一実施形態を模式的に示す、第一端面側からみた斜視図である。図2は、図1に示すハニカム構造体を、第一端面側からみた平面図である。図3は、図1に示すハニカム構造体を、第二端面側からみた平面図である。図4は、図2のA−A’断面を模式的に示す、断面図である。
次に、本発明のハニカム構造体を製造する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としては、ハニカム成形体を作製する工程、ハニカム成形体を乾燥及び焼成する工程、を備えたものを挙げることができる。また、必要に応じて、ハニカム成形体又はハニカム成形体を乾燥したハニカム乾燥体のセル形状を変形させる工程を、更に有していてもよい。以下、ハニカム成形体を作製する工程を、成形工程として説明する。ハニカム成形体を乾燥及び焼成する工程を、焼成工程として説明する。また、セル形状を変形させる工程を、セル変形工程として説明する。
成形工程は、成形原料を混練して得られる坏土をハニカム形状に押出成形してハニカム成形体を得る工程である。ハニカム成形体は、第一端面から第二端面まで延びるセルを区画形成する隔壁、及びこの隔壁の最外周を囲繞するように形成された外周壁を有するものである。隔壁によって構成されたハニカム構造の部分が、ハニカム構造部となる。成形工程においては、まず、成形原料を混練して坏土とする。次に、得られた坏土を押出成形して、隔壁と外周壁とが一体的に成形されたハニカム成形体を得る。
次に、必要に応じて、得られたハニカム成形体の第一端面側に、剣山のような先端の尖った部材(以下、「セル変形部材」ということがある)を押し当てて、所定のセルの形状を部分的に変形させるセル変形工程を行ってもよい。このセル変形工程を行うことにより、ハニカム成形体の第一端面の面積の1〜80%の範囲に開口部を有するセルについて、その「最大内接円変化率」及び第一端面から20mm以下の範囲の「内部最大内接円変化率」を1〜80%とすることができる。すなわち、このセル変形工程を行うことにより、ハニカム成形体の第一端面の面積の1〜80%の範囲に開口部を有するセルを、第一端面から20mm以下の範囲のみに開口変化部を有する特定開口セルに変形させることができる。例えば、セル変形部材の先端の形状やその長さ、また、第一端面側に押し当てる範囲などを調整することにより、所望形状の特定開口セルを形成することができる。なお、後述する焼成工程の乾燥時又は焼成時に、所定のセルを特定開口セルに変形させることもできる。このため、セル変形工程は、必要に応じて行えばよい。また、上記したように、セル変形工程は、ハニカム成形体を乾燥したハニカム乾燥体に対して行ってもよい。
焼成工程は、ハニカム成形体を焼成して、ハニカム構造体を得る工程である。ハニカム成形体を焼成する前に、得られたハニカム成形体を、例えば、マイクロ波及び熱風で乾燥してもよい。また、製造するハニカム構造体として、目封止部を備えたものとする場合には、ハニカム成形体を乾燥した後に、ハニカム成形体の作製に用いた材料と同様の材料で、セルの開口部を目封止することで目封止部を作製してもよい。目封止部を作製した後に、ハニカム成形体を更に乾燥してもよい。
コージェライト化原料100質量部に、造孔材を0.5質量部、分散媒を33質量部、有機バインダを5.6質量部、それぞれ添加し、混合、混練して坏土を調製した。コージェライト化原料としては、アルミナ、水酸化アルミニウム、カオリン、タルク、及びシリカを使用した。分散媒としては水を使用し、造孔材としては平均粒子径10〜50μmの吸水性ポリマーを使用し、有機バインダとしてはメチルセルロースを使用し、分散剤としてはデキストリンを使用した。
まず、ハニカム構造体の隔壁に、三元触媒をディッピング法によって担持し、ハニカム触媒体を得た。三元触媒の担持量は、200g/Lとした。
(1−(各実施例のハニカム構造体のHCエミッション値/基準ハニカム構造体のHCエミッション値))×100 (a)
評価B:基準ハニカム構造体に対して、浄化性能が、2%を超え、5%以下の範囲で向上が見られるもの。
評価C:基準ハニカム構造体に対して、浄化性能が、2%以下の向上に留まるもの。
浄化性能の評価に用いたハニカム触媒体に、圧力損失の測定用ガス(空気)を、25℃、流量10Nm3/minで通気して、第一端面側と第二端面側との圧力をそれぞれ測定し、その圧力差を算出した。算出した圧力差を、ハニカム構造体の圧力損失とした。そして、以下の評価基準に基づき、圧力損失の評価を行った。下記の評価基準においては、上述した「基準ハニカム構造体」に対する、圧力損失上昇率を判断基準とした。圧力損失上昇率は、下記式(b)で表される。圧力損失の上昇を抑えることができれば、出力の低下を抑えることができ、燃費向上が期待できる。
(各実施例のハニカム構造体の圧力損失値/基準ハニカム構造体の圧力損失値)×100 (b)
評価A:基準ハニカム構造体に対して、圧力損失上昇率が、2%以内のもの。
評価B:基準ハニカム構造体に対して、圧力損失上昇率が、2%を超え、5%以下の範囲のもの。
評価C:基準ハニカム構造体に対して、圧力損失上昇率が、5%を超えるもの。
実施例2〜18においては、セル構造、気孔率、断面形状、直径、長径、短径、全長を表1に示すように変更し、更に、各実施例2〜18において、以下のように焼成方法を変更すること以外は、実施例1と同様の方法で、ハニカム構造体を作製した。ここで、「長径」とは、セルの延びる方向に直交する断面におけるハニカム構造体の外周縁上の2点を結んだ直線のうち最も長いものをいう。そして、「短径」とは、セルの延びる方向に直交する断面において、上記「長径」に直交する直線をいう。実施例14においては、ハニカム構造体の断面形状が楕円形であり、長径が228.6mmで、短径が137.2mmである。実施例15においては、ハニカム構造体の断面形状が楕円形であり、長径が95.0mmで、短径が70.0mmである。実施例16においては、ハニカム構造体の断面形状が台形であり、長径が122.0mmで、短径が104.0mmである。実施例17においては、ハニカム構造体の断面形状が台形であり、長径が169.7mmで、短径が80.8mmである。
比較例1〜11においては、セル構造、気孔率、断面形状、直径、長径、短径、全長を表3に示すように変更し、更に、各比較例1〜11において、以下のように焼成方法を変更すること以外は、実施例1と同様の方法で、ハニカム構造体を作製した。比較例9においては、ハニカム構造体の断面形状が楕円形であり、長径が228.6mmで、短径が137.2mmである。
表2に示すように、ハニカム構造体は、最大内接円変化率(%)及び内部最大内接円変化率(%)が大きくなるにしたがって、浄化性能が向上する傾向が確認された。また、特定開口セルの面積率が、1〜80%の範囲内であれば、圧力損失が小さく、排ガス浄化用の触媒担体として良好に用いられるものであった。また、開口変化部の第一端面からの長さが、20mm以下であれば、排ガス浄化用の触媒担体として十分な浄化性能を維持しつつ、圧力損失の上昇を抑制することが可能であった。
Claims (7)
- 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形成する多孔質の隔壁を有する柱状のハニカム構造部、及び、前記ハニカム構造部の外周を囲繞するように形成された多孔質の外周壁、を備え、
前記複数のセルは、最外周に形成されたセルを除き、その断面形状が四角形であり、
前記複数のセルのうちの、前記ハニカム構造部の前記第一端面の面積の1〜80%の範囲に開口部を有するセルが、特定開口セルであり、
前記特定開口セルは、前記セルの前記第二端面における開口部の周縁に接する内接円の直径D2と、前記セルの前記第一端面における開口部の周縁に接する内接円の直径D1とが、1≦|(1−(D1/D2))×100|≦80の関係を満たし、且つ、前記セルの前記第二端面における開口部の周縁に接する内接円の直径D2と、前記第一端面から前記第二端面に向かう方向に直交する断面における前記セルの周縁に接する内接円の直径D3とが、前記第一端面から20mm以下の一部の範囲において、1≦|(1−(D3/D2))×100|≦80の関係を満たす、開口変化部を有し、
前記特定開口セルの前記開口変化部が、当該特定開口セルの前記第一端面から20mm以下の範囲のみに存在し、
前記複数のセルのうちの、前記特定開口セル以外のセルは、前記開口変化部を有しておらず、当該セルの開口部の大きさが変化していない、又は、前記開口変化部よりも当該セルの開口部における変化率が小さい、非特定開口セルである、ハニカム構造体であって、
前記特定開口セルは、前記セルの前記第二端面における開口部の周縁に接する内接円の直径D2と、前記第一端面から前記第二端面に向かう方向の直交する断面における、前記第一端面から20mmを超える範囲の前記セルの周縁に接する内接円の直径D3Xとが、|(1−(D3X/D2))×100|<1の関係を満たし、
前記セルのうち、前記特定開口セル以外のセルは、前記セルの前記第二端面における開口部の周縁に接する内接円の直径D2と、前記セルの前記第一端面における開口部の周縁に接する内接円の直径D1とが、|(1−(D1/D2))×100|<1の関係を満たし、且つ、前記セルの前記第二端面における開口部の周縁に接する内接円の直径D2と、前記第一端面から前記第二端面に向かう方向の直交する断面における前記セルの周縁に接する内接円の直径D3とが、|(1−(D3/D2))×100|<1の関係を満たす、通常セルであり、
前記ハニカム構造部を構成する前記複数のセルを区画形成している前記隔壁が一体成形品である、ハニカム構造体。 - 前記複数のセルのうち、前記ハニカム構造部の前記第一端面の面積の3〜70%の範囲に開口部を有するセルが、前記特定開口セルである、請求項1に記載のハニカム構造体。
- 前記特定開口セルは、前記内接円の直径D2と、前記内接円の直径D1とが、3≦|(1−(D1/D2))×100|≦70の関係を満たし、且つ、
前記内接円の直径D2と、前記開口変化部における前記内接円の直径D3とが、3≦|(1−(D3/D2))×100|≦70の関係を満たす、請求項1又は2に記載のハニカム構造体。 - 前記内接円の直径D2が、0.5〜2.2mmである、請求項1〜3のいずれか一項に記載のハニカム構造体。
- 前記隔壁の厚さが、40〜350μmである、請求項1〜4のいずれか一項に記載のハニカム構造体。
- 前記ハニカム構造部のセル密度が、30〜200個/cm2である、請求項1〜5のいずれか一項に記載のハニカム構造体。
- 前記隔壁が、コージェライト、炭化珪素、珪素−炭化珪素系複合材料、ムライト、アルミナ、チタン酸アルミニウム、窒化珪素、コージェライト化原料、リチウムアルミニウムシリケート、アルミニウムチタネート、及び炭化珪素−コージェライト系複合材料からなる群より選択される少なくとも1種を含む材料からなる、請求項1〜6のいずれか一項に記載のハニカム構造体。
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JP4947113B2 (ja) * | 2008-11-06 | 2012-06-06 | 株式会社デンソー | ハニカムフィルタ及びその製造方法 |
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JP5700516B2 (ja) | 2010-11-30 | 2015-04-15 | 日本碍子株式会社 | ハニカム構造体 |
JP2015131255A (ja) * | 2014-01-09 | 2015-07-23 | 日本碍子株式会社 | ハニカム構造体 |
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