JP5916310B2 - ハニカム触媒担体 - Google Patents
ハニカム触媒担体 Download PDFInfo
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- JP5916310B2 JP5916310B2 JP2011162726A JP2011162726A JP5916310B2 JP 5916310 B2 JP5916310 B2 JP 5916310B2 JP 2011162726 A JP2011162726 A JP 2011162726A JP 2011162726 A JP2011162726 A JP 2011162726A JP 5916310 B2 JP5916310 B2 JP 5916310B2
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- 239000003054 catalyst Substances 0.000 title claims description 217
- 238000005192 partition Methods 0.000 claims description 80
- 229910052878 cordierite Inorganic materials 0.000 claims description 14
- 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 14
- 229910000505 Al2TiO5 Inorganic materials 0.000 claims description 8
- 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
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical class [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
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- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical class O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical class [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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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
- B01D46/2425—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
- B01D46/2429—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material of the honeycomb walls or cells
-
- 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
- B01D46/2425—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
- B01D46/24491—Porosity
-
- 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
- B01D46/2425—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
- B01D46/24494—Thermal expansion coefficient, heat capacity or thermal conductivity
-
- 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
- B01D46/2451—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure
- B01D46/2455—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure of the whole honeycomb or segments
-
- 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
- B01D46/2451—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure
- B01D46/2482—Thickness, height, width, length or diameter
-
- 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
- B01D46/2451—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure
- B01D46/2484—Cell density, area or aspect ratio
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24149—Honeycomb-like
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Description
図1に示すように、本発明の一の実施形態のハニカム触媒担体100は、コージェライト又はアルミニウムチタネートを主成分とする多孔質体からなり、流体の流路となる複数のセル2を区画形成する隔壁1を備えたものである。図1においては、一方の端面11から他方の端面12まで延びる複数のセル2を区画形成する多孔質の隔壁1と、最外周に位置する外周壁3とを備えた筒状のハニカム触媒担体100の例を示す。ここで、図1は、本発明のハニカム触媒担体の一実施形態を模式的に示す斜視図である。
次に、本実施形態のハニカム触媒担体の製造方法について説明する。本実施形態のハニカム触媒担体の製造方法としては、セラミック原料を含有する成形原料を混合し混練して坏土を得る坏土調製工程と、得られた坏土をハニカム形状に成形してハニカム成形体を得る成形工程と、得られたハニカム成形体を乾燥し、焼成して、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備えたハニカム触媒担体を得る焼成工程とを備えた製造方法を挙げることができる。
まず、本実施形態のハニカム触媒担体を製造する際には、セラミック原料を含有する成形原料を混合し混練して坏土を得る(坏土調製工程)。セラミック原料としては、コージェライト化原料、又はアルミニウムチタネートを用いることが好ましい。なお、コージェライト化原料とは、シリカが42〜56質量%、アルミナが30〜45質量%、マグネシアが12〜16質量%の範囲に入る化学組成となるように配合されたセラミック原料であって、焼成されてコージェライトになるものである。
次に、得られた坏土をハニカム形状に成形してハニカム成形体を得る(成形工程)。坏土を成形してハニカム成形体を形成する方法としては特に制限はなく、押出成形、射出成形等の公知の成形方法を用いることができる。例えば、所望のセル形状、隔壁厚さ、セル密度を有する口金を用いて押出成形してハニカム成形体を形成する方法等を好適例として挙げることができる。口金の材質としては、摩耗し難い超硬合金が好ましい。
次に、得られたハニカム成形体を乾燥し、焼成して、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備えたハニカム触媒担体を得る(焼成工程)。このようにして、隔壁の気孔率が0.5%以上、10%以下であるハニカム触媒担体を得ることができる。
実施例1においては、まず、セラミック原料としてコージェライト化原料を用い、コージェライト化原料100質量部に対して、分散媒を35質量部、有機バインダを6質量部、分散剤を0.5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、平均粒子径が3μmのタルクを38.9質量部、平均粒子径が1μmのカオリンを40.7質量部、平均粒子径が0.3μmのアルミナを5.9質量部、及び平均粒子径が0.5μmのベーマイトを11.5質量部、用いた。平均粒子径は、各原料の粒子の分布におけるメジアン径(d50)のことである。
ハニカム触媒担体に燃焼ガスと室温空気とを交互に流し、ハニカム触媒担体にクラックが生じるか否かを調べて、耐熱衝撃性の評価を行った。燃焼ガスと室温空気の流量は、それぞれ3Nm3/minとした。燃焼ガスと室温空気の通気条件は、燃焼ガスを5分間流した後、室温空気を10分間流すことを10回繰り返すこととした。燃焼ガスの温度を上昇させていき、クラックが生じなかったもっとも高い温度を「耐熱衝撃温度」とした。また、「耐熱衝撃性の評価」における「評価」の欄は、耐熱衝撃温度が850℃以上の場合を、「OK(合格)」とし、耐熱衝撃温度が850℃未満の場合を、「NG(不合格)」とした。
端面の直径が106mm、セルの延びる方向の長さが114mmのハニカム触媒体に、三元触媒を担持し、ハニカム触媒担持体を作製した。三元触媒としては、白金(Pt)、ロジウム(Rh)、パラジウム(Pd)を質量比で1:0.5:4(Pt:Rh:Pd)の比率で含み、アルミナ及びセリアを主成分とするものを用いた。三元触媒の担持量は、ハニカム触媒担体の容積1リットル当たり200gとした。また、上記貴金属(Pt、Rh、Pd)の三元触媒中の含有量は、ハニカム触媒担体に三元触媒を担持した際に、ハニカム触媒担体の容積1リットル当たり2gとなる量とした。
「耐熱衝撃性の評価」及び「コールドスタートライトオフ時間の試験」の各評価が、共に「OK(合格)」である場合に、総合評価結果を「OK(合格)」とした。少なくともいずれか一方の評価結果が「NG(不合格)」である場合には、総合評価結果を「NG(不合格)」とした。
ハニカム触媒担体の、「気孔率(%)」、「隔壁厚さ(μm)」、「セル密度(セル/cm2)」、「セルピッチ(μm)」、「開口率(%)」、及び「隔壁の材料」を、表1に示すように変更した以外は、実施例1と同様の方法で、ハニカム触媒担体を作製した。作製したハニカム触媒担体について、実施例1と同様の方法で、「耐熱衝撃性の評価」及び「コールドスタートライトオフ時間の試験」を行った。また、それぞれの結果から各実施例のハニカム触媒担体についての「総合評価」を行った。結果を表2に示す。
Claims (3)
- コージェライト又はアルミニウムチタネートを95質量%以上含む多孔質体からなり、一方の端面から他方の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隔壁を備えた筒状のハニカム触媒担体(前記セルの端面又は内部を目封止する目封止部を有するものを除く)であって、
前記隔壁の気孔率が0.5%以上、10%以下であり、前記セルの延びる方向に垂直な断面における開口率が90%以上、95%以下であるハニカム触媒担体。 - セル密度が15セル/cm2以上、150セル/cm2以下であり、前記隔壁の厚さが25μm以上、100μm以下である請求項1に記載のハニカム触媒担体。
- 前記隔壁の、前記セルの延びる方向における熱膨張係数の200〜800℃における平均値が、1×10−6/K以下である請求項1又は2に記載のハニカム触媒担体。
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