US20140010723A1 - Exhaust gas purifying catalyst device - Google Patents
Exhaust gas purifying catalyst device Download PDFInfo
- Publication number
- US20140010723A1 US20140010723A1 US14/022,022 US201314022022A US2014010723A1 US 20140010723 A1 US20140010723 A1 US 20140010723A1 US 201314022022 A US201314022022 A US 201314022022A US 2014010723 A1 US2014010723 A1 US 2014010723A1
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- United States
- Prior art keywords
- catalyst
- catalyst carrier
- sheet
- exhaust gas
- gas purifying
- 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.)
- Abandoned
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 185
- 239000003863 metallic catalyst Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000000746 purification Methods 0.000 claims abstract description 4
- 239000000835 fiber Substances 0.000 claims description 25
- 239000000919 ceramic Substances 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 244000144992 flock Species 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000004804 winding Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 4
- 229910052774 Proactinium Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 229910052745 lead Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000001457 metallic cations Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
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- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
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- 230000000052 comparative effect Effects 0.000 description 1
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- 239000003365 glass fiber Substances 0.000 description 1
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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
- 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
- F01N3/2835—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support fibrous
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
-
- B01J35/56—
-
- B01J35/58—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- F01N3/2807—Metal other than sintered metal
- F01N3/281—Metallic honeycomb monoliths made of stacked or rolled sheets, foils or plates
-
- 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
- F01N2330/00—Structure of catalyst support or particle filter
- F01N2330/02—Metallic plates or honeycombs, e.g. superposed or rolled-up corrugated or otherwise deformed sheet metal
- F01N2330/04—Methods of manufacturing
-
- 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
- F01N3/2853—Arrangements for mounting catalyst support in housing, e.g. with means for compensating thermal expansion or vibration using mats or gaskets between catalyst body and housing
-
- 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
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49345—Catalytic device making
Definitions
- the present disclosure relates to exhaust gas purifying devices, for example, including a catalyst carrier member for carrying thereon a metallic catalyst for exhaust gas purification.
- An exhaust gas purifying catalyst device for purifying exhaust gas from an engine of a vehicle usually comprises a catalyst carrier member for carrying a noble metal catalyst such as platinum, rhodium, or palladium.
- a noble metal catalyst such as platinum, rhodium, or palladium.
- a metallic honeycomb structure having high durability against severe engine vibration and high exhaust gas temperatures has been used as a catalyst carrier for an applied catalyst layer.
- the surfaces of the metallic honeycomb structure are smooth, and thus adhesiveness of the catalyst layer to the metallic honeycomb structure can be insufficient. Therefore, the catalyst layer applied on the metallic carrier could be peeled therefrom.
- Various means of the prior arts for suppressing the peeling of the catalyst layer from the metallic carrier have been proposed.
- micro projections are formed on the surfaces of the metallic honeycomb structure for gripping the catalyst layer disclosed in Japanese Applications Nos. JP 2004-169111 and JP 08-299808, or a metallic oxide coating for gripping the catalyst layer is formed on the surfaces of the metallic honeycomb structure, as disclosed in Japanese Application No. JP 06-71185.
- aspects of the present disclosure provide an exhaust gas purifying catalyst device which has high durability against vibration and high temperatures and is able to suppress the peeling of a catalyst layer from a catalyst carrier member during use. Further, the device allows for easy recover the metallic catalyst after use.
- an exhaust gas purifying catalyst device can comprise a catalyst carrier member on which a metallic catalyst for exhaust gas purification is carried, wherein the catalyst carrier member can be formed of a sheet-like catalyst carrier made by a wet paper-making method.
- the metallic catalyst can be carried as a catalyst layer on surfaces of the sheet-like catalyst carrier after the sheet-like catalyst carrier has been baked.
- a sheet-like catalyst carrier can include ceramic powder and alumina-silica fibers.
- the ceramic powder can comprise alumina.
- the weight ratio of the alumina-silica fibers to the ceramic powder of alumina included in the catalyst carrier member can be within a range of 0.2-2.5.
- the baking temperature can be within a range of 1450-1550° C.
- the catalyst carrier member can be manufactured through: a sheet making step for paper-making the sheet-like catalyst carrier from flock formed by adding flocculant into slurry of water mingled with fibers and binder, a baking step for baking the sheet-like catalyst carrier obtained in the sheet making step, and a metallic catalyst applying step for applying the metallic catalyst onto the surfaces of the catalyst carrier member obtained in the baking step.
- the catalyst carrier member can have a honeycomb structure formed by adhering a corrugated sheet-like catalyst carrier onto at least one surface of a flat sheet-like catalyst carrier, and by winding them into a roll.
- the exhaust gas purifying catalyst device can comprise a catalyst carrier member which can be formed of a sheet-like catalyst carrier made by a wet paper-making method, and the metallic catalyst can be carried as a catalyst layer on surfaces of the catalyst carrier member after baking of catalyst carrier member, it is possible for the catalyst carrier member to have high durability against vibration and high temperatures, and to suppress the peeling of the catalyst layer from the catalyst carrier member during use. Further, the metallic catalyst can be easily recovered after use.
- FIGS. 1A-B illustrate a schematic perspective view (A) and a plan view (B) showing an embodiment of a catalyst carrier member used for an exhaust gas purifying catalyst device of the present disclosure.
- FIG. 2 illustrates a schematic view showing an embodiment of a manufacturing process of a sheet-like catalyst carrier used for making a catalyst carrier member.
- FIGS. 3A-D illustrate schematic views showing an embodiment of manufacturing steps of a honeycomb catalyst carrier member used in an exhaust gas purifying catalyst device of the present disclosure.
- FIG. 4 illustrates a flowchart showing embodiments of manufacturing steps of a catalyst carrier member used in an exhaust gas purifying catalyst device of the present disclosure.
- FIG. 5 illustrates a graph for comparing the surface roughness of an embodiment of a catalyst carrier member of the present disclosure and those made of ceramics and metal of the prior art.
- FIG. 6 illustrates a graph for comparing a catalyst layer peeling rate of an embodiment of a catalyst carrier member of the present disclosure and that made of metal of the prior art.
- an aqueous solution can be prepared by adding ceramic powder, fibers, such as heat resisting fibers including alumina-silica fibers, inorganic binder, and a pore controlling agent into water to form a slurry in which said additives can be uniformly dispersed (slurry forming step S 1 ).
- flock can be formed by adding flocculant to the slurry (flock forming step S 2 ).
- sheet forming step S 3 sheet-like (paper-like) porous structure can be formed (sheet forming step S 3 ) by paper making the flock (wet paper-making method).
- the ceramic powder can comprise alumina
- the weight ratio of the alumina-silica fibers to the ceramic powder of alumina included in the catalyst carrier member 1 can be set within a range of 0.2-2.5.
- noble metal used as a metallic catalyst may not be contained in the raw material (water solution) used in paper-making process.
- the heat resisting fibers can comprise an amorphous ceramic formed by silica and alumina as main components, and can be formed into a sheet-like catalyst carrier P by a wet paper-making method.
- Other heat resisting fiber materials for example organic fibers such as Aramid fibers, may be used as well.
- they are chemically and physically stable and able to obtain a strong structure of entangled fibers in the paper-making step.
- the flocculant for forming the flock can include high-molecular flocculant and metallic cations, and can have a strong electric charge.
- the flocculant can neutralize the electric charges in an aqueous solution of fibers which can be separated from each other by repulsive forces, and can force the fibers to be entangled.
- the high-molecular flocculant can penetrate into spaces between fibers and act to increase the binding force.
- Alum, aluminum sulfate, or other materials containing Al 3+ cations in an aqueous solution can be used as metallic cations.
- a thickness of the sheet-like catalyst carrier P can be manufactured as shown in FIG. 2 by containing said flock, including fibers and binder (flock formed via the slurry forming step S 1 and flock forming step S 2 ), in a containing tank 2 , and by ladling out liquid in the tank 2 using a cylinder mould 3 (e.g. a cylindrical mesh member for transferring constant amount of slurry to a roller 4 ) rotated at a position near the liquid level.
- This sheet-like catalyst carrier P can be continuously transferred from the roller 4 to a roll press 5 and adjusted to a desired thickness by applying a pressure using the roll press 5 .
- the sheet-like catalyst carrier P can be pressed by the roll press 5 into a thickness (sheet forming step S 3 ), and can be continuously fed to a drying machine 6 and dried during transference therethrough (drying step S 4 ).
- the dried sheet-like catalyst carrier P can then be continuously wound up by a winding-up machine 7 .
- This sheet-like catalyst carrier P can then be formed into a honeycomb catalyst carrier member 1 ′ of porous structure by rolling a flat sheet-like catalyst carrier Pa and a corrugated sheet-like catalyst carrier together to form a honeycomb structure in a way described in detail below (forming step S 5 , see FIG. 3 ).
- the honeycomb catalyst carrier member 1 ′ can be baked to form the catalyst carrier member 1 having porous structure (baking step S 6 , see FIG. 1 ). In some embodiments, just after the baking step S 6 , no noble/catalyst metal has yet been applied to the catalyst carrier member 1 .
- the sheet-like catalyst carrier P wound by the winding-up machine 7 can be prepared into two kinds of sheets; one being a flat sheet-like catalyst carrier Pa and the other being a corrugated sheet-like catalyst carrier Pb as shown in FIG. 3( a ).
- a length of the corrugated sheet-like catalyst carrier Pb can be adhered by an adhesive, or other means, to at least one surface of the straight sheet-like catalyst carrier Pa as shown in FIG. 3( b ).
- adhered sheet-like catalyst carriers Pa, Pb can be wound as shown in FIG. 3( c ) to have a rolled honeycomb catalyst member 1 ′ prior to baking ( FIG. 3( d )).
- the honeycomb catalyst carrier member 1 ( FIG. 1 ) can be obtained by baking the honeycomb catalyst member 1 ′ ( FIG. 3( d )) obtained in the forming step S 5 e.g. at a temperature of 1450-1550° C. (baking step S 6 ).
- FIG. 5 shows comparative results of the surface roughness of an embodiment of a honeycomb catalyst carrier member 1 manufactured in accordance with the present disclosure, a ceramic honeycomb catalyst carrier member of the prior art, and a metallic honeycomb catalyst carrier member of the prior art. As can be seen from FIG. 5 , the surface roughness of the honeycomb catalyst carrier member 1 of the present disclosure is about 5.916 ( ⁇ m) (a central graph in FIG.
- those values of the ceramic honeycomb catalyst carrier member and the metallic honeycomb catalyst carrier member of the prior art are about 3.576 ( ⁇ m) (a left side graph in FIG. 5 ) and about 0.227 ( ⁇ m) (a right side graph in FIG. 5 ) respectively.
- the surface roughness of embodiments of a honeycomb catalyst carrier member 1 of the present disclosure is larger than those of the ceramic and metallic honeycomb catalyst carrier member of the prior art.
- the surface 1 a of the honeycomb catalyst carrier member 1 obtained through the baking step S 6 can then be formed with a catalyst layer to carry thereon the metallic catalyst of noble metals (e.g. platinum, rhodium, palladium, or other noble metals) (metallic catalyst carrying step S 7 ).
- the metallic catalyst carrying step S 7 the slurry, including the metallic catalyst and the binder, can be applied to the surface 1 a of the honeycomb catalyst carrier member 1 obtained through the baking step S 6 , and the honeycomb catalyst carrier member 1 can be heat treated at about 600° C. to solidify the binder and thus to secure the catalyst layer on the surface 1 a of the honeycomb catalyst carrier member 1 .
- honeycomb catalyst carrier member 1 of the present disclosure can be technically advantageous over the metallic catalyst carrier member of the prior art.
- Samples (outer diameter: 30 mm, length 20 mm) of embodiments of a honeycomb catalyst carrier member 1 of the present disclosure and the metallic catalyst carrier member of the prior art were made, and the slurry, including the metallic catalyst (noble metals as catalyst) and the binder, were applied to the surfaces of samples and both samples were heat treated at about 600° C. to solidify the binder and thus to secure the catalyst layer on the surfaces of the samples.
- the weight of the catalyst layer applied onto the surface of the catalyst carrier member of the present disclosure was 1.3572 (g) and that of the catalyst carrier member of the prior art was 2.0414 (g). These weights were obtained by calculating the weight of the catalyst layer by measuring differences in weight of the samples before and after the application of slurry and the heat treatment. Then both the samples were held in an electric furnace at 1000° C. for 10 minutes and taken out therefrom and cooled to a room temperature.
- a peeling test was performed by immersing both samples into a water tank of an ultrasonic vibrator (180 W, 42 Hz) and holding them in the water tank under application of ultrasonic vibration. This peeling test was repeated five times, and the peeling rate of the catalyst layer was calculated from weight variation before and after the peeling tests. As shown in FIG. 6 , the peeling rate of the catalyst layer of the catalyst carrier member 1 of the present disclosure was 2.61% and that of the metallic catalyst carrier member of the prior art was 6.71%. It can be found that the catalyst layer of the catalyst carrier member 1 of the present disclosure is able to remarkably reduce the peeling rate of the metallic catalyst layer as compared with that of the metallic catalyst carrier member of the prior art.
- the metallic catalyst layer can be carried on rough surfaces of the catalyst carrier member 1 formed of baked sheet-like catalyst carriers P (Pa, Pb) made by the wet paper-making method, it is possible to make an exhaust gas purifying catalyst device which has excellent durability against vibration and heat and is able to suppress peeling of the catalyst layer during use. Further, the metal catalyst can be easily recovered after use. That is, since the catalyst carrier member 1 of the present disclosure can be formed of sheet-like catalyst carriers P made by the wet paper-making method, and thus the surfaces of the catalyst carrier member 1 are roughened by fibers, the catalyst layer applied on the surfaces of the catalyst carrier member 1 can be held thereon for a long term.
- the catalyst carrier member 1 can be manufactured through a sheet making step S 3 for paper-making the sheet-like catalyst carrier P from flock formed by adding flocculant into slurry of water mingled with fibers and binder; a baking step S 6 for baking the sheet-like catalyst carrier P obtained in the sheet making step S 3 ; and a metallic catalyst applying step S 7 for applying the metallic catalyst onto the surfaces of the catalyst carrier member 1 obtained in the baking step S 6 , it is possible to have the exhaust gas purifying catalyst device which has excellent durability against vibration and heat, and is able to suppress peeling of the catalyst layer during use. Further, the metal catalyst can be easily recovered after use.
- the catalyst carrier member 1 can have a honeycomb structure formed by adhering a corrugated sheet-like catalyst carrier Pb onto at least one surface of a flat sheet-like catalyst carrier Pa and by winding them Pa, Pb to a roll, it is possible for the honeycomb structure to pass the flow of exhaust gas through the inside of the catalyst carrier member 1 and thus to perform the exhaust gas purifying operation.
- the baking temperature can be within a range of 1450-1550° C. according to the present disclosure, it is possible to perform a perfect baking while avoiding melting of the catalyst carrier member 1 during the baking step S 6 .
- the noble metals to be carried in the metallic catalyst applying step S 7 may be other catalyst metals than platinum, rhodium and palladium.
- the sheet-like catalyst carrier P may be formed of other materials than ceramic powder and alumina-silica fibers, and ceramic powder other than alumina may be used.
- the weight ratio of the alumina-silica fibers to the ceramic powder of alumina included in the catalyst carrier member 1 may be other weight ratio than a range of 0.2-2.5.
- the present disclosure can be applied to other types of exhaust gas purifying device than that for a vehicle so long as it is formed of the sheet like catalyst structure on which surfaces metallic catalyst is carried by forming the catalyst layer after baking the sheet like catalyst structure made by the wet paper-making method.
Abstract
An exhaust gas purifying catalyst device, which can have high durability against vibration and high temperatures, can be configured to suppress the peeling of the catalyst layer from the catalyst carrier member during use. Additionally, the metallic catalyst can be easily recovered after use. According to the present disclosure, an exhaust gas purifying catalyst device can comprise a catalyst carrier member on which metallic catalyst for exhaust gas purification can be carried characterized in that the catalyst carrier member can be formed of a sheet-like catalyst carrier made by a wet paper-making method, and that the metallic catalyst can be carried as a catalyst layer on surfaces of the sheet-like catalyst carrier after the sheet-like catalyst carrier has been baked.
Description
- Any and all applications for which a foreign or domestic priority claim is identified in the Application Data Sheet as filed with the present application are hereby incorporated by reference under 37 CFR 1.57.
- 1. Field of the Inventions
- The present disclosure relates to exhaust gas purifying devices, for example, including a catalyst carrier member for carrying thereon a metallic catalyst for exhaust gas purification.
- 2. Description of the Related Art
- An exhaust gas purifying catalyst device for purifying exhaust gas from an engine of a vehicle usually comprises a catalyst carrier member for carrying a noble metal catalyst such as platinum, rhodium, or palladium. In general purpose engines such as motorcycles and portable electric generators, a metallic honeycomb structure having high durability against severe engine vibration and high exhaust gas temperatures has been used as a catalyst carrier for an applied catalyst layer.
- However, in the catalyst device having the metallic honeycomb structure of the prior art noted above, the surfaces of the metallic honeycomb structure are smooth, and thus adhesiveness of the catalyst layer to the metallic honeycomb structure can be insufficient. Therefore, the catalyst layer applied on the metallic carrier could be peeled therefrom. Various means of the prior arts for suppressing the peeling of the catalyst layer from the metallic carrier have been proposed.
- For example, micro projections are formed on the surfaces of the metallic honeycomb structure for gripping the catalyst layer disclosed in Japanese Applications Nos. JP 2004-169111 and JP 08-299808, or a metallic oxide coating for gripping the catalyst layer is formed on the surfaces of the metallic honeycomb structure, as disclosed in Japanese Application No. JP 06-71185.
- However, in the exhaust gas purifying catalyst device of the prior art publications noted above, since it is necessary to form a means for preventing peeling of the catalyst layer (e.g. micro projections or metallic oxide coating) on the catalyst carrier member, the overall number of manufacturing steps would be increased, and thus manufacturing costs would be increased. On the other hand, although it is possible to have a catalyst device for preventing peeling or separation of the metallic catalyst from the catalyst carrier member, it is very difficult to recover the metallic catalyst when the exhaust gas purifying catalyst device is scrapped after use. This is especially true when the catalyst carrier member is made of materials other than metal having high durability against vibration or high temperature, and where the metallic catalyst is contained within the catalyst carrier member.
- Aspects of the present disclosure provide an exhaust gas purifying catalyst device which has high durability against vibration and high temperatures and is able to suppress the peeling of a catalyst layer from a catalyst carrier member during use. Further, the device allows for easy recover the metallic catalyst after use.
- In some embodiments, an exhaust gas purifying catalyst device can comprise a catalyst carrier member on which a metallic catalyst for exhaust gas purification is carried, wherein the catalyst carrier member can be formed of a sheet-like catalyst carrier made by a wet paper-making method. The metallic catalyst can be carried as a catalyst layer on surfaces of the sheet-like catalyst carrier after the sheet-like catalyst carrier has been baked.
- In some embodiments, a sheet-like catalyst carrier can include ceramic powder and alumina-silica fibers.
- In some embodiments, the ceramic powder can comprise alumina.
- In some embodiments, the weight ratio of the alumina-silica fibers to the ceramic powder of alumina included in the catalyst carrier member can be within a range of 0.2-2.5.
- In some embodiments, the baking temperature can be within a range of 1450-1550° C.
- In some embodiments, the catalyst carrier member can be manufactured through: a sheet making step for paper-making the sheet-like catalyst carrier from flock formed by adding flocculant into slurry of water mingled with fibers and binder, a baking step for baking the sheet-like catalyst carrier obtained in the sheet making step, and a metallic catalyst applying step for applying the metallic catalyst onto the surfaces of the catalyst carrier member obtained in the baking step.
- In some embodiments, the catalyst carrier member can have a honeycomb structure formed by adhering a corrugated sheet-like catalyst carrier onto at least one surface of a flat sheet-like catalyst carrier, and by winding them into a roll.
- According to the present disclosure, since the exhaust gas purifying catalyst device can comprise a catalyst carrier member which can be formed of a sheet-like catalyst carrier made by a wet paper-making method, and the metallic catalyst can be carried as a catalyst layer on surfaces of the catalyst carrier member after baking of catalyst carrier member, it is possible for the catalyst carrier member to have high durability against vibration and high temperatures, and to suppress the peeling of the catalyst layer from the catalyst carrier member during use. Further, the metallic catalyst can be easily recovered after use.
-
FIGS. 1A-B illustrate a schematic perspective view (A) and a plan view (B) showing an embodiment of a catalyst carrier member used for an exhaust gas purifying catalyst device of the present disclosure. -
FIG. 2 illustrates a schematic view showing an embodiment of a manufacturing process of a sheet-like catalyst carrier used for making a catalyst carrier member. -
FIGS. 3A-D illustrate schematic views showing an embodiment of manufacturing steps of a honeycomb catalyst carrier member used in an exhaust gas purifying catalyst device of the present disclosure. -
FIG. 4 illustrates a flowchart showing embodiments of manufacturing steps of a catalyst carrier member used in an exhaust gas purifying catalyst device of the present disclosure. -
FIG. 5 illustrates a graph for comparing the surface roughness of an embodiment of a catalyst carrier member of the present disclosure and those made of ceramics and metal of the prior art. -
FIG. 6 illustrates a graph for comparing a catalyst layer peeling rate of an embodiment of a catalyst carrier member of the present disclosure and that made of metal of the prior art. - Several embodiments of the present disclosure are described more in detail below with reference to the accompanied drawings.
- The exhaust gas purifying catalyst device of the present disclosure can be used for purifying exhaust gas discharged from general purpose engines such as, for example, motorcycles and portable electric generators, and can comprise a cylindrical
catalyst carrier member 1, or catalyst carrier, having a honeycomb structure. Thecatalyst carrier member 1 can be manufactured by first making a sheet-like, or paper-like, catalyst carrier P using a wet paper-making method (a so-called “outturn machining method”, seeFIG. 2 ), then by forming the obtained sheet-like catalyst carrier P into a rolled configuration having a honeycomb structure, followed by baking the rolled catalyst carrier and by applying catalyst layers on the surfaces of the rolled honeycomb carrier structure. - The method for manufacturing the exhaust gas purifying
device 1 of the present disclosure is described below with reference to a flowchart ofFIG. 4 . - First, an aqueous solution can be prepared by adding ceramic powder, fibers, such as heat resisting fibers including alumina-silica fibers, inorganic binder, and a pore controlling agent into water to form a slurry in which said additives can be uniformly dispersed (slurry forming step S1). Then, flock can be formed by adding flocculant to the slurry (flock forming step S2). Following, a sheet-like (paper-like) porous structure can be formed (sheet forming step S3) by paper making the flock (wet paper-making method).
- In the present disclosure, the ceramic powder can comprise alumina, and the weight ratio of the alumina-silica fibers to the ceramic powder of alumina included in the catalyst carrier member 1 (weight ratio of the alumina-silica fibers/ceramics powder comprising alumina) can be set within a range of 0.2-2.5. According to the present disclosure, in some embodiments noble metal used as a metallic catalyst may not be contained in the raw material (water solution) used in paper-making process.
- The heat resisting fibers can comprise an amorphous ceramic formed by silica and alumina as main components, and can be formed into a sheet-like catalyst carrier P by a wet paper-making method. Other heat resisting fiber materials, for example organic fibers such as Aramid fibers, may be used as well. Preferably, they are chemically and physically stable and able to obtain a strong structure of entangled fibers in the paper-making step. In addition, it is also possible to form the paper-like catalyst carrier P of glass fibers or carbon fibers. These fibers can have high heat resistance and chemically and physically stable properties after the wet paper-making method.
- The flocculant for forming the flock can include high-molecular flocculant and metallic cations, and can have a strong electric charge. Thus, the flocculant can neutralize the electric charges in an aqueous solution of fibers which can be separated from each other by repulsive forces, and can force the fibers to be entangled. The high-molecular flocculant can penetrate into spaces between fibers and act to increase the binding force. Alum, aluminum sulfate, or other materials containing Al3+ cations in an aqueous solution can be used as metallic cations.
- According to the present disclosure, a thickness of the sheet-like catalyst carrier P can be manufactured as shown in
FIG. 2 by containing said flock, including fibers and binder (flock formed via the slurry forming step S1 and flock forming step S2), in a containingtank 2, and by ladling out liquid in thetank 2 using a cylinder mould 3 (e.g. a cylindrical mesh member for transferring constant amount of slurry to a roller 4) rotated at a position near the liquid level. This sheet-like catalyst carrier P can be continuously transferred from theroller 4 to aroll press 5 and adjusted to a desired thickness by applying a pressure using theroll press 5. - The sheet-like catalyst carrier P can be pressed by the
roll press 5 into a thickness (sheet forming step S3), and can be continuously fed to adrying machine 6 and dried during transference therethrough (drying step S4). The dried sheet-like catalyst carrier P can then be continuously wound up by a winding-upmachine 7. Thus an amount of the sheet-like catalyst carrier P can be obtained. This sheet-like catalyst carrier P can then be formed into a honeycombcatalyst carrier member 1′ of porous structure by rolling a flat sheet-like catalyst carrier Pa and a corrugated sheet-like catalyst carrier together to form a honeycomb structure in a way described in detail below (forming step S5, seeFIG. 3 ). Finally, the honeycombcatalyst carrier member 1′ can be baked to form thecatalyst carrier member 1 having porous structure (baking step S6, seeFIG. 1 ). In some embodiments, just after the baking step S6, no noble/catalyst metal has yet been applied to thecatalyst carrier member 1. - In the forming step S5, the sheet-like catalyst carrier P wound by the winding-up
machine 7 can be prepared into two kinds of sheets; one being a flat sheet-like catalyst carrier Pa and the other being a corrugated sheet-like catalyst carrier Pb as shown inFIG. 3( a). A length of the corrugated sheet-like catalyst carrier Pb can be adhered by an adhesive, or other means, to at least one surface of the straight sheet-like catalyst carrier Pa as shown inFIG. 3( b). Then, adhered sheet-like catalyst carriers Pa, Pb can be wound as shown inFIG. 3( c) to have a rolledhoneycomb catalyst member 1′ prior to baking (FIG. 3( d)). - The honeycomb catalyst carrier member 1 (
FIG. 1 ) can be obtained by baking thehoneycomb catalyst member 1′ (FIG. 3( d)) obtained in the forming step S5 e.g. at a temperature of 1450-1550° C. (baking step S6).FIG. 5 shows comparative results of the surface roughness of an embodiment of a honeycombcatalyst carrier member 1 manufactured in accordance with the present disclosure, a ceramic honeycomb catalyst carrier member of the prior art, and a metallic honeycomb catalyst carrier member of the prior art. As can be seen fromFIG. 5 , the surface roughness of the honeycombcatalyst carrier member 1 of the present disclosure is about 5.916 (μm) (a central graph inFIG. 5) and on the other hand, those values of the ceramic honeycomb catalyst carrier member and the metallic honeycomb catalyst carrier member of the prior art are about 3.576 (μm) (a left side graph inFIG. 5 ) and about 0.227 (μm) (a right side graph inFIG. 5 ) respectively. As shown, the surface roughness of embodiments of a honeycombcatalyst carrier member 1 of the present disclosure is larger than those of the ceramic and metallic honeycomb catalyst carrier member of the prior art. - The surface 1 a of the honeycomb
catalyst carrier member 1 obtained through the baking step S6 can then be formed with a catalyst layer to carry thereon the metallic catalyst of noble metals (e.g. platinum, rhodium, palladium, or other noble metals) (metallic catalyst carrying step S7). In the metallic catalyst carrying step S7, the slurry, including the metallic catalyst and the binder, can be applied to the surface 1 a of the honeycombcatalyst carrier member 1 obtained through the baking step S6, and the honeycombcatalyst carrier member 1 can be heat treated at about 600° C. to solidify the binder and thus to secure the catalyst layer on the surface 1 a of the honeycombcatalyst carrier member 1. - The honeycomb
catalyst carrier member 1 of the present disclosure can be technically advantageous over the metallic catalyst carrier member of the prior art. Samples (outer diameter: 30 mm, length 20 mm) of embodiments of a honeycombcatalyst carrier member 1 of the present disclosure and the metallic catalyst carrier member of the prior art were made, and the slurry, including the metallic catalyst (noble metals as catalyst) and the binder, were applied to the surfaces of samples and both samples were heat treated at about 600° C. to solidify the binder and thus to secure the catalyst layer on the surfaces of the samples. - The weight of the catalyst layer applied onto the surface of the catalyst carrier member of the present disclosure was 1.3572 (g) and that of the catalyst carrier member of the prior art was 2.0414 (g).These weights were obtained by calculating the weight of the catalyst layer by measuring differences in weight of the samples before and after the application of slurry and the heat treatment. Then both the samples were held in an electric furnace at 1000° C. for 10 minutes and taken out therefrom and cooled to a room temperature.
- A peeling test was performed by immersing both samples into a water tank of an ultrasonic vibrator (180 W, 42 Hz) and holding them in the water tank under application of ultrasonic vibration. This peeling test was repeated five times, and the peeling rate of the catalyst layer was calculated from weight variation before and after the peeling tests. As shown in
FIG. 6 , the peeling rate of the catalyst layer of thecatalyst carrier member 1 of the present disclosure was 2.61% and that of the metallic catalyst carrier member of the prior art was 6.71%. It can be found that the catalyst layer of thecatalyst carrier member 1 of the present disclosure is able to remarkably reduce the peeling rate of the metallic catalyst layer as compared with that of the metallic catalyst carrier member of the prior art. - According to the present disclosure, since the metallic catalyst layer can be carried on rough surfaces of the
catalyst carrier member 1 formed of baked sheet-like catalyst carriers P (Pa, Pb) made by the wet paper-making method, it is possible to make an exhaust gas purifying catalyst device which has excellent durability against vibration and heat and is able to suppress peeling of the catalyst layer during use. Further, the metal catalyst can be easily recovered after use. That is, since thecatalyst carrier member 1 of the present disclosure can be formed of sheet-like catalyst carriers P made by the wet paper-making method, and thus the surfaces of thecatalyst carrier member 1 are roughened by fibers, the catalyst layer applied on the surfaces of thecatalyst carrier member 1 can be held thereon for a long term. - In addition, since the
catalyst carrier member 1 can be manufactured through a sheet making step S3 for paper-making the sheet-like catalyst carrier P from flock formed by adding flocculant into slurry of water mingled with fibers and binder; a baking step S6 for baking the sheet-like catalyst carrier P obtained in the sheet making step S3; and a metallic catalyst applying step S7 for applying the metallic catalyst onto the surfaces of thecatalyst carrier member 1 obtained in the baking step S6, it is possible to have the exhaust gas purifying catalyst device which has excellent durability against vibration and heat, and is able to suppress peeling of the catalyst layer during use. Further, the metal catalyst can be easily recovered after use. - Furthermore, since the
catalyst carrier member 1 can have a honeycomb structure formed by adhering a corrugated sheet-like catalyst carrier Pb onto at least one surface of a flat sheet-like catalyst carrier Pa and by winding them Pa, Pb to a roll, it is possible for the honeycomb structure to pass the flow of exhaust gas through the inside of thecatalyst carrier member 1 and thus to perform the exhaust gas purifying operation. In addition, since the baking temperature can be within a range of 1450-1550° C. according to the present disclosure, it is possible to perform a perfect baking while avoiding melting of thecatalyst carrier member 1 during the baking step S6. - The present disclosure has been described with reference to several embodiments. Obviously, modifications and alternations will occur to those of ordinary skill in the art upon reading and understanding the preceding detailed description. It is intended that the present disclosure be construed as including all such alternations and modifications insofar as they come within the scope of the appended claims or the equivalents thereof. For example, the noble metals to be carried in the metallic catalyst applying step S7 may be other catalyst metals than platinum, rhodium and palladium. In addition, the sheet-like catalyst carrier P may be formed of other materials than ceramic powder and alumina-silica fibers, and ceramic powder other than alumina may be used. Furthermore, the weight ratio of the alumina-silica fibers to the ceramic powder of alumina included in the
catalyst carrier member 1 may be other weight ratio than a range of 0.2-2.5. - The present disclosure can be applied to other types of exhaust gas purifying device than that for a vehicle so long as it is formed of the sheet like catalyst structure on which surfaces metallic catalyst is carried by forming the catalyst layer after baking the sheet like catalyst structure made by the wet paper-making method.
Claims (12)
1. An exhaust gas purifying catalyst device comprising:
a catalyst carrier member on which metallic catalyst for exhaust gas purification is carried;
wherein the catalyst carrier member is formed of a sheet-like catalyst carrier made by a wet paper-making method; and
wherein the metallic catalyst is carried as a catalyst layer on surfaces of the sheet-like catalyst carrier after the sheet-like catalyst carrier has been baked.
2. An exhaust gas purifying catalyst device of claim 1 , wherein the sheet-like catalyst carrier comprises ceramic powder and alumina-silica fibers.
3. An exhaust gas purifying catalyst device of claim 1 , wherein the ceramic powder comprises alumina.
4. An exhaust gas purifying catalyst device of claim 3 , wherein the weight ratio of the alumina-silica fibers to the ceramic powder of alumina is within a range of 0.2-2.5.
5. An exhaust gas purifying catalyst device claim 1 , wherein the baking temperature is within a range of 1450-1550° C.
6. An exhaust gas purifying catalyst device of claim 1 , wherein the catalyst carrier member is manufactured through a sheet making step for paper-making the sheet-like catalyst carrier from flock formed by adding flocculant into slurry of predetermined amount of water mingled with predetermined fibers and binder; a baking step for baking the sheet-like catalyst carrier obtained in the sheet making step; and a metallic catalyst applying step for applying the metallic catalyst onto the surfaces of the catalyst carrier member obtained in the baking step.
7. An exhaust gas purifying catalyst device of claim 1 , wherein the catalyst carrier member has a honeycomb structure formed by adhering a corrugated sheet-like catalyst carrier onto at least one surface of a flat sheet-like catalyst carrier and by winding them to a roll.
8. A method for forming an exhaust gas purifying catalyst device comprising:
manufacturing a sheet-like catalyst carrier from flock through a wet paper-making step;
baking the sheet-like catalyst carrier; and
applying a metallic catalyst to the surface of the baked sheet-like catalyst carrier.
9. A method of claim 8 , wherein the sheet-like catalyst carrier comprises ceramic powder and alumina-silica fibers.
10. A method of claim 9 , wherein the ceramic powder comprises alumina.
11. An exhaust gas purifying catalyst device of claim 10 , wherein the weight ratio of the alumina-silica fibers to the ceramic powder of alumina is within a range of 0.2-2.5.
12. A method of claim 8 , wherein the baking temperature is within a range of 1450-1550° C.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011052654A JP5872179B2 (en) | 2011-03-10 | 2011-03-10 | Method for producing catalyst carrier for exhaust gas purification |
JP2011-052654 | 2011-03-10 | ||
PCT/JP2012/056171 WO2012121387A1 (en) | 2011-03-10 | 2012-03-09 | Exhaust gas cleaning catalyst support |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/056171 Continuation WO2012121387A1 (en) | 2011-03-10 | 2012-03-09 | Exhaust gas cleaning catalyst support |
Publications (1)
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US20140010723A1 true US20140010723A1 (en) | 2014-01-09 |
Family
ID=46798338
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US14/022,022 Abandoned US20140010723A1 (en) | 2011-03-10 | 2013-09-09 | Exhaust gas purifying catalyst device |
Country Status (5)
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US (1) | US20140010723A1 (en) |
JP (1) | JP5872179B2 (en) |
CN (1) | CN103415342B (en) |
DE (1) | DE112012001175B4 (en) |
WO (1) | WO2012121387A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11131229B2 (en) * | 2017-03-27 | 2021-09-28 | Vitesco Technologies GmbH | Method for producing a honeycomb body |
Families Citing this family (2)
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CN108940374A (en) * | 2018-06-11 | 2018-12-07 | 陕西科技大学 | The preparation method and application of fiber composite film catalyst |
EP3795251A4 (en) * | 2019-03-26 | 2021-06-09 | Sakura Kogyo Co., Ltd. | Catalyst layer forming material, catalyst device constituent material, catalyst device, and production methods thereof |
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JP3751994B2 (en) | 1995-05-12 | 2006-03-08 | 新日本製鐵株式会社 | Metal carrier for catalysts with excellent oxidation resistance and durability |
JPH10290921A (en) * | 1997-04-22 | 1998-11-04 | Matsushita Electric Ind Co Ltd | Deodorizing catalyst filter and deodorizing device using the same |
MXPA04000118A (en) | 2001-07-06 | 2004-06-03 | 3M Innovative Properties Co | Inorganic fiber substrates for exhaust systems and methods of making same. |
JP3953944B2 (en) | 2002-11-20 | 2007-08-08 | 新日鉄マテリアルズ株式会社 | Metal foil and honeycomb structure |
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JP2008178857A (en) * | 2006-04-20 | 2008-08-07 | Ibiden Co Ltd | Honeycomb structure, production method for honeycomb structure, casing and exhaust emission control device |
JP2010255615A (en) * | 2009-03-30 | 2010-11-11 | Nissan Motor Co Ltd | Fiber filter for exhaust emission control, exhaust emission control system for diesel engine and exhaust emission control system for gasoline engine |
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2011
- 2011-03-10 JP JP2011052654A patent/JP5872179B2/en active Active
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2012
- 2012-03-09 DE DE112012001175.9T patent/DE112012001175B4/en active Active
- 2012-03-09 WO PCT/JP2012/056171 patent/WO2012121387A1/en active Application Filing
- 2012-03-09 CN CN201280012610.2A patent/CN103415342B/en active Active
-
2013
- 2013-09-09 US US14/022,022 patent/US20140010723A1/en not_active Abandoned
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US7052532B1 (en) * | 2000-03-09 | 2006-05-30 | 3M Innovative Properties Company | High temperature nanofilter, system and method |
US20060068159A1 (en) * | 2003-06-23 | 2006-03-30 | Teruo Komori | Honeycomb structure |
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US11131229B2 (en) * | 2017-03-27 | 2021-09-28 | Vitesco Technologies GmbH | Method for producing a honeycomb body |
Also Published As
Publication number | Publication date |
---|---|
WO2012121387A1 (en) | 2012-09-13 |
DE112012001175T5 (en) | 2013-12-05 |
DE112012001175B4 (en) | 2023-04-20 |
JP2012187502A (en) | 2012-10-04 |
CN103415342A (en) | 2013-11-27 |
JP5872179B2 (en) | 2016-03-01 |
CN103415342B (en) | 2015-11-25 |
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