WO2017164114A1 - Structure en nids d'abeilles et procédé de production de structure en nids d'abeilles - Google Patents

Structure en nids d'abeilles et procédé de production de structure en nids d'abeilles Download PDF

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Publication number
WO2017164114A1
WO2017164114A1 PCT/JP2017/010907 JP2017010907W WO2017164114A1 WO 2017164114 A1 WO2017164114 A1 WO 2017164114A1 JP 2017010907 W JP2017010907 W JP 2017010907W WO 2017164114 A1 WO2017164114 A1 WO 2017164114A1
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Prior art keywords
honeycomb
honeycomb structure
type zeolite
fired body
raw material
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PCT/JP2017/010907
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English (en)
Japanese (ja)
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真之助 後藤
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イビデン株式会社
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    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • 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
    • 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
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to a honeycomb structure and a method for manufacturing a honeycomb structure.
  • Hydrocarbon (HC) contained in exhaust gas discharged from a gasoline engine or the like is usually purified by oxidation using a honeycomb structure on which a three-way catalyst made of a noble metal such as platinum is supported.
  • a honeycomb structure on which a three-way catalyst made of a noble metal such as platinum is supported.
  • HC is not sufficiently purified at a temperature lower than that. Therefore, at a temperature where the exhaust gas temperature is low, such as immediately after the engine is started, HC is discharged without being purified even though the amount of HC discharged is large.
  • the exhaust gas temperature tends to be lowered, so that the HC purification rate is likely to decrease.
  • HC is adsorbed in a low temperature region until reaching the temperature at which the three-way catalyst is activated, and the adsorbed HC is released when the temperature becomes high, thereby improving the HC purification rate.
  • Techniques for making them disclosed are disclosed.
  • ⁇ -type zeolite containing Fe is used as the HC adsorbent.
  • Patent Document 2 as a method for producing a zeolite containing a metal such as Fe or Ni, after performing dealumination treatment on the zeolite with steaming and mineral acid, the obtained zeolite slurry is treated with an aqueous metal salt solution and A method for performing a treatment for increasing the pH is disclosed.
  • Patent Document 3 discloses that a metal-containing zeolite is used as an inorganic binder. A method of manufacturing a honeycomb structure by forming into a honeycomb shape with alumina and inorganic fibers is disclosed.
  • the HC adsorption amount and the HC release temperature are important. That is, it is important to adsorb a large amount of HC and adsorb HC to a temperature at which the three-way catalyst is activated, and a honeycomb structure having such characteristics is required.
  • the honeycomb structure when using a honeycomb structure, the honeycomb structure may be damaged due to volume shrinkage / expansion due to moisture adsorption / desorption, and it is also required to suppress such damage to the honeycomb structure. Yes.
  • the present invention has been made to solve the above problems, and an object of the present invention is to provide a honeycomb structure excellent in HC adsorption performance and hardly damaged during use, and a method for manufacturing the same.
  • a honeycomb structure of the present invention is a honeycomb structure including a honeycomb fired body in which a plurality of through holes are arranged in parallel in a longitudinal direction with partition walls interposed therebetween, and the honeycomb fired body includes CuO, ⁇ -type zeolite, and inorganic
  • the ⁇ -type zeolite has an SiO 2 / Al 2 O 3 molar ratio of 300 or more.
  • the honeycomb structure of the present invention a large amount of HC can be adsorbed up to a temperature at which the three-way catalyst is activated by coexisting CuO with ⁇ -type zeolite having a high SiO 2 / Al 2 O 3 molar ratio. Therefore, the honeycomb structure of the present invention is excellent in HC adsorption performance.
  • the high SiO 2 / Al 2 O 3 molar ratio of ⁇ -type zeolite means that the amount of Al in the ⁇ -type zeolite is small. Therefore, in the honeycomb structure of the present invention, damage to the honeycomb structure that occurs during use can be suppressed. Moisture is easily adsorbed on Al constituting the ⁇ -type zeolite. When moisture is adsorbed on Al, the skeleton structure of ⁇ -type zeolite is distorted, and the volume of ⁇ -type zeolite changes.
  • the amount of Al in the ⁇ -type zeolite is small as described above, it is difficult for moisture to be adsorbed on the ⁇ -type zeolite, and volume shrinkage / expansion due to moisture adsorption / desorption is suppressed. Conceivable.
  • the honeycomb structure of the present invention preferably contains 1 to 7% by weight of Cu with respect to the ⁇ -type zeolite.
  • the amount of Cu contained in the honeycomb structure is in the above range, the effect of improving the HC adsorption performance and the effect of suppressing the volume shrinkage / expansion due to moisture adsorption / desorption can be sufficiently obtained.
  • the honeycomb fired body further includes inorganic fibers.
  • the strength of the honeycomb structure can be improved.
  • a three-way catalyst is supported on the surface of the partition wall. HC can be purified by the three-way catalyst.
  • a method for manufacturing a honeycomb structure of the present invention is a method for manufacturing a honeycomb structure including a honeycomb fired body in which a plurality of through-holes are arranged in parallel in the longitudinal direction with a partition wall therebetween, and includes a CuO source, ⁇ -type zeolite,
  • a raw material paste containing an inorganic binder By forming a raw material paste containing an inorganic binder, a forming step for producing a honeycomb formed body in which a plurality of through holes are arranged in parallel in the longitudinal direction with a partition wall therebetween, and by firing the honeycomb formed body, a honeycomb And a firing step for producing a fired body, wherein the ⁇ -type zeolite contained in the raw material paste has a SiO 2 / Al 2 O 3 molar ratio of 300 or more.
  • the amount of the CuO source contained in the raw material paste is preferably 1 to 7% by weight with respect to the ⁇ -type zeolite in terms of Cu.
  • the amount of the CuO source contained in the raw material paste is in the above range, the effect of improving the HC adsorption performance and the effect of suppressing the volume shrinkage / expansion due to moisture adsorption / desorption can be sufficiently obtained.
  • the raw material paste preferably further contains inorganic fibers.
  • the strength of the obtained honeycomb structure can be improved.
  • the method for manufacturing a honeycomb structure of the present invention preferably further includes a supporting step of supporting a three-way catalyst on the surface of the partition wall. HC can be purified by the three-way catalyst.
  • FIG. 1 is a perspective view schematically showing an example of the honeycomb structure of the present invention.
  • FIG. 2 is a perspective view schematically showing another example of the honeycomb structure of the present invention.
  • FIG. 3 is a perspective view schematically showing an example of a honeycomb fired body constituting the honeycomb structure shown in FIG.
  • FIG. 4 is a graph showing the relationship between temperature and hydrocarbon release.
  • FIG. 5 is a graph showing the results of Cu state analysis by H 2 -TPR measurement.
  • the honeycomb structure of the present invention includes a honeycomb fired body in which a plurality of through holes are arranged in parallel in the longitudinal direction with partition walls therebetween.
  • the honeycomb fired body is formed of an extrusion-molded body containing CuO, ⁇ -type zeolite, and an inorganic binder.
  • the honeycomb fired body is manufactured by extruding and firing a raw material paste containing a CuO source, ⁇ -type zeolite, and an inorganic binder.
  • the honeycomb structure of the present invention may include a single honeycomb fired body, or may include a plurality of honeycomb fired bodies bonded through an adhesive layer.
  • an outer peripheral coat layer is formed on the outer peripheral surface of the honeycomb fired body.
  • FIG. 1 is a perspective view schematically showing an example of the honeycomb structure of the present invention.
  • a honeycomb structure 10 shown in FIG. 1 includes a single honeycomb fired body 11 in which a plurality of through holes 11a are arranged in parallel in the longitudinal direction with a partition wall 11b interposed therebetween.
  • the honeycomb fired body 11 is made of an extrusion-molded body containing CuO, ⁇ -type zeolite, and an inorganic binder. Further, an outer peripheral coat layer 12 is formed on the outer peripheral surface of the honeycomb fired body 11.
  • FIG. 2 is a perspective view schematically showing another example of the honeycomb structure of the present invention.
  • FIG. 3 is a perspective view schematically showing an example of a honeycomb fired body constituting the honeycomb structure shown in FIG.
  • honeycomb fired bodies 21 in which a plurality of through holes 21 a are arranged in parallel in the longitudinal direction with partition walls 21 b interposed therebetween are bonded via an adhesive layer 23. Except for this, it has the same configuration as the honeycomb structure 10 shown in FIG. Furthermore, an outer peripheral coat layer 22 is formed on the outer peripheral surface of the honeycomb fired body 21.
  • the outer peripheral coat layers 12 and 22 may not be formed, respectively.
  • the ⁇ -type zeolite has a SiO 2 / Al 2 O 3 molar ratio of 300 or more.
  • the SiO 2 / Al 2 O 3 molar ratio is desirably 350 or more, and more desirably 400 or more. Further, the SiO 2 / Al 2 O 3 molar ratio is desirably 1000 or less, and more desirably 800 or less.
  • the SiO 2 / Al 2 O 3 molar ratio of ⁇ -type zeolite can be measured by fluorescent X-ray analysis (XRF).
  • beta type for SiO 2 / Al 2 O 3 molar ratio of the zeolite is not changed before and after sintering, the SiO 2 / Al 2 O 3 molar ratio of beta-type zeolite contained in the raw material paste, a honeycomb structure of the present invention
  • the ⁇ -type zeolite can also have a SiO 2 / Al 2 O 3 molar ratio.
  • the average particle size of ⁇ -type zeolite contained in the raw material paste is preferably 0.1 to 10 ⁇ m, and more preferably 0.5 to 5 ⁇ m.
  • the average particle size of ⁇ -type zeolite is the average particle size of primary particles measured using a laser diffraction / scattering particle size distribution analyzer (manufactured by Seishin Enterprises: Laser Micronizer LMS-30).
  • the amount of ⁇ -type zeolite contained in the raw material paste is preferably 25 to 60% by weight, more preferably 30 to 50% by weight.
  • the honeycomb structure of the present invention preferably contains 1 to 7% by weight of Cu with respect to ⁇ -type zeolite, and more preferably contains 2 to 4% by weight.
  • the Cu content in the honeycomb structure can be measured by fluorescent X-ray analysis (XRF). Further, the Cu content in the honeycomb structure can also be determined from the amount of CuO source contained in the raw material paste.
  • the ⁇ -type zeolite is preferably not ion-exchanged with Cu ions, and CuO is preferably supported on the surface of the ⁇ -type zeolite. Note that the state of Cu supported on the ⁇ -type zeolite can be analyzed from a peak obtained by performing H 2 -TPR measurement on the honeycomb structure.
  • the inorganic binder contained in the raw material paste is not particularly limited, and examples thereof include solids contained in alumina sol, silica sol, titania sol, water glass, sepiolite, attapulgite, boehmite, etc. You may use together.
  • the amount of the inorganic binder contained in the raw material paste is desirably 5 to 20% by weight, and more desirably 7 to 15% by weight.
  • the honeycomb fired body further includes inorganic fibers. That is, the raw material paste preferably further includes inorganic fibers.
  • the aspect ratio of the inorganic fiber is preferably 2 to 300, more preferably 5 to 200, and still more preferably 10 to 100.
  • the amount of inorganic fibers contained in the raw material paste is preferably 2 to 15% by weight, and more preferably 5 to 10% by weight.
  • the shape of the honeycomb structure of the present invention is not limited to a cylindrical shape, and examples thereof include a prismatic shape, an elliptical cylindrical shape, a long cylindrical shape, and a rounded chamfered prismatic shape (for example, a rounded chamfered triangular prism shape). .
  • the shape of the through hole of the honeycomb fired body is not limited to a quadrangular prism shape, and examples thereof include a triangular prism shape and a hexagonal prism shape.
  • the density of the through holes in the cross section perpendicular to the longitudinal direction of the honeycomb fired body is preferably 31 to 155 holes / cm 2 .
  • the thickness of the partition walls of the honeycomb fired body is preferably 0.10 to 0.50 mm, and more preferably 0.20 to 0.40 mm.
  • the thickness of the outer peripheral coat layer is preferably 0.1 to 2.0 mm.
  • a three-way catalyst refers to a catalyst that mainly purifies hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx).
  • Examples of the three-way catalyst include noble metals such as platinum, palladium, and rhodium.
  • noble metals such as platinum, palladium, and rhodium.
  • carrier which consists of heat resistant inorganic oxides, such as an alumina, can also be used as a three-way catalyst.
  • the supported amount of the three-way catalyst is preferably 0.1 to 15 g / L, and more preferably 1 to 10 g / L.
  • the supported amount of the three-way catalyst refers to the weight of the three-way catalyst per apparent volume of the honeycomb structure.
  • the apparent volume of the honeycomb structure is a volume including the void volume, and includes the volume of the outer peripheral coat layer and / or the adhesive layer.
  • a method for manufacturing a honeycomb structure of the present invention is a method for manufacturing a honeycomb structure including a honeycomb fired body in which a plurality of through-holes are arranged in parallel in the longitudinal direction with a partition wall therebetween, and includes a CuO source, ⁇ -type zeolite, By forming a raw material paste containing an inorganic binder, a forming step for producing a honeycomb formed body in which a plurality of through holes are arranged in parallel in the longitudinal direction with a partition wall therebetween, and by firing the honeycomb formed body, a honeycomb And a firing step for producing a fired body.
  • a raw material paste containing a CuO source, ⁇ -type zeolite, and an inorganic binder is formed, so that a plurality of through holes are arranged in parallel in the longitudinal direction with a partition wall therebetween.
  • a honeycomb formed body is produced. Specifically, a honeycomb formed body is manufactured by extrusion molding using a raw material paste containing a CuO source, ⁇ -type zeolite, and an inorganic binder, and further containing inorganic fibers and the like as necessary.
  • the ⁇ 2 -type zeolite contained in the raw material paste has a SiO 2 / Al 2 O 3 molar ratio of 300 or more. Since the structure of ⁇ -type zeolite has already been described, its detailed description is omitted. Moreover, since it is as having already demonstrated the inorganic binder, inorganic fiber, etc. which are contained in a raw material paste, the detailed description is abbreviate
  • Examples of the CuO source include copper oxide, copper nitrate, copper acetate, and copper sulfate. Among these, copper oxide is desirable.
  • the amount of the CuO source contained in the raw material paste is preferably 1 to 7% by weight with respect to ⁇ -type zeolite in terms of Cu, and is preferably 2 to 4% by weight. It is more desirable.
  • the raw material paste may further contain an organic binder, a dispersion medium, a molding aid and the like as necessary.
  • Methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, polyethyleneglycol, a phenol resin, an epoxy resin etc. are mentioned, You may use 2 or more types together.
  • Alcohol such as water
  • organic solvents such as benzene, methanol, etc.
  • the raw material paste When preparing the raw material paste, it is desirable to mix and knead, and it may be mixed using a mixer, an attritor or the like, or may be kneaded using a kneader or the like.
  • the honeycomb formed body can be dried to produce a honeycomb dried body. desirable.
  • a dryer such as a microwave dryer, hot air dryer, dielectric dryer, vacuum dryer, vacuum dryer, freeze dryer, etc.
  • honeycomb formed body and the honeycomb dried body before the firing step are collectively referred to as a honeycomb formed body.
  • the honeycomb fired body is fired to produce a honeycomb fired body.
  • this process performs degreasing and firing of the honeycomb formed body, it can also be referred to as a “degreasing / firing process”, but it is referred to as a “firing process” for convenience.
  • the temperature of the firing step is desirably 600 to 1000 ° C., and more desirably 600 to 800 ° C.
  • the firing process time is preferably 1 to 10 hours, and more preferably 1.5 to 5 hours.
  • the atmosphere of the firing step is not particularly limited, but it is desirable that the oxygen concentration is 1 to 10% by volume.
  • the honeycomb structure of the present invention can be manufactured.
  • the method for manufacturing a honeycomb structure of the present invention preferably further includes a supporting step of supporting a three-way catalyst on the surface of the partition wall.
  • Examples of the method for supporting the three-way catalyst on the surface of the partition wall include a method in which the honeycomb fired body or the honeycomb structure is immersed in a slurry containing the three-way catalyst, and then heated up and heated.
  • a three-way catalyst may be supported on the surface of the partition wall of the honeycomb fired body before forming the outer peripheral coat layer, or the honeycomb fired body after forming the outer peripheral coat layer or A three-way catalyst may be supported on the surface of the partition walls of the honeycomb structure.
  • the three-way catalyst may be supported on the surface of the partition walls of the honeycomb fired body before forming the adhesive layer, or the honeycomb fired body or honeycomb after forming the adhesive layer A three-way catalyst may be supported on the surface of the partition walls of the structure.
  • the supported amount of the three-way catalyst is preferably 0.1 to 15 g / L, and more preferably 1 to 10 g / L.
  • the outer peripheral coat layer is formed on the outer peripheral surface of the honeycomb fired body, the outer peripheral coat layer is coated with the outer peripheral coat layer paste on the outer peripheral surface excluding both end faces. Thereafter, it can be formed by drying and solidifying.
  • the honeycomb structured body in which a plurality of honeycomb fired bodies are bonded via an adhesive layer has an adhesive layer paste on the outer peripheral surface excluding both end faces of the plurality of honeycomb fired bodies. After applying and adhering, it can be produced by drying and solidifying.
  • Example 1 1 part by weight of CuO (average particle diameter: 2 ⁇ m) as a CuO source, 40 parts by weight of ⁇ -type zeolite (SiO 2 / Al 2 O 3 molar ratio: 440, average particle diameter: 2 ⁇ m), and boehmite as an inorganic binder 7.5 parts by weight of alumina fibers having an average fiber diameter of 3 ⁇ m and an average fiber length of 120 ⁇ m, 5 parts by weight of methyl cellulose as an organic binder, 5 parts by weight of oleic acid as a molding aid, and 31 parts of ion-exchanged water Part by weight was mixed and kneaded to prepare a raw material paste.
  • CuO average particle diameter: 2 ⁇ m
  • ⁇ -type zeolite SiO 2 / Al 2 O 3 molar ratio: 440, average particle diameter: 2 ⁇ m
  • boehmite as an inorganic binder 7.5 parts by weight of alumina fibers having an average fiber diameter of 3
  • the raw material paste was extruded using an extruder, and a regular quadrangular prism-shaped honeycomb formed body was produced.
  • the honeycomb molded body was dried for 17 minutes at an output of 40 kW and a reduced pressure of 6.7 kPa using a vacuum microwave dryer, and then degreased and fired at 700 ° C. for 3 hours and 40 minutes to produce a honeycomb fired body.
  • the honeycomb fired body had a regular square pillar shape with a side of 33 mm and a length of 43 mm, a density of through holes of 62 holes / cm 2 , and a partition wall thickness of 0.36 mm.
  • Comparative Example 1 a honeycomb fired body was manufactured using a raw material paste not including a CuO source as follows.
  • a raw material paste was prepared by mixing and kneading 7.5 parts by weight of alumina fibers, 5 parts by weight of methylcellulose as an organic binder, 5 parts by weight of oleic acid and 32 parts by weight of ion-exchanged water as a molding aid.
  • the raw material paste was extruded using an extruder, and a regular quadrangular prism-shaped honeycomb formed body was produced.
  • the honeycomb molded body was dried for 17 minutes at an output of 40 kW and a reduced pressure of 6.7 kPa using a vacuum microwave dryer, and then degreased and fired at 700 ° C. for 3 hours and 40 minutes to produce a honeycomb fired body.
  • the honeycomb fired body had a regular square pillar shape with a side of 33 mm and a length of 43 mm, a density of through holes of 62 holes / cm 2 , and a partition wall thickness of 0.36 mm.
  • Comparative Example 2 In Comparative Example 2, a honeycomb fired body was manufactured in the same manner as in Example 1 except that a raw material paste containing ⁇ -type zeolite having a SiO 2 / Al 2 O 3 molar ratio of 40 was used. Thus, an evaluation sample of Comparative Example 2 was obtained.
  • Example 1 the evaluation sample of Comparative Example 1 and Comparative Example 2 450 ° C. in an N 2 gas atmosphere, after maintaining for 30 minutes, in an N 2 gas atmosphere containing CO 0.3 vol% 450 Hold at 2 ° C. for 2 minutes.
  • a gas containing 1125 ppmC of propylene, 375 ppmC of propane, 0.2% by volume of CO, 10% by volume of H 2 O, 20% by volume of O 2 and the balance being N 2 Hydrocarbon (HC) propylene and propane were adsorbed by flowing at 30 ° C. for 30 seconds.
  • HC N 2 Hydrocarbon
  • the gas was switched to a gas containing 10% by volume of H 2 O and the balance being N 2 , and the temperature was raised to 450 ° C. at a rate of 60 ° C./min.
  • the total hydrocarbon (THC) of the gas flowing out from the evaluation sample was measured, and the value was used as the amount of hydrocarbon released from the evaluation sample.
  • FIG. 4 is a graph showing the relationship between temperature and hydrocarbon release. From FIG. 4, it was confirmed that in Example 1, hydrocarbons were released on the high temperature side as compared with Comparative Example 1, and the amount of released hydrocarbons increased significantly. Further, in Example 1, it was confirmed that hydrocarbons were released on the high temperature side as compared with Comparative Example 2, and that the amount of released hydrocarbons was large. From the above results, it is considered that by making CuO coexist in ⁇ -type zeolite having a high SiO 2 / Al 2 O 3 molar ratio, a honeycomb structure excellent in hydrocarbon adsorption performance can be obtained.
  • Example 1 [Cu state analysis by H 2 -TPR measurement] Using a catalyst analyzer (manufactured by Microtrack Bell: BELCAT-A), as a pretreatment, the sample for evaluation of Example 1 was held in a He gas atmosphere at 210 ° C. for 2 hours, then cooled to 50 ° C., The temperature was raised to 1000 ° C. at a rate of 10 ° C./min in an atmosphere of H 2 : 4.95% by volume (the rest being Ar). At that time, changes in the amount of gas flowing out from the evaluation sample were measured with a thermal conductivity detector (TCD) and plotted.
  • TCD thermal conductivity detector
  • FIG. 5 is a graph showing the results of Cu state analysis by H 2 -TPR measurement. From FIG. 5, in Example 1, it was confirmed that the maximum peak exists in 200 degreeC vicinity. This peak is considered to be a peak derived from CuO that is not ion-exchanged and is deposited on the surface of the ⁇ -type zeolite. From this result, in Example 1, it is considered that ⁇ -type zeolite is not ion-exchanged by Cu ions, and CuO is supported on the surface of ⁇ -type zeolite.
  • Example 1 The samples for evaluation of Example 1 and Comparative Example 2 are immersed in water, the volume change rate [%] when the water absorption rate is set to a predetermined value is obtained, and the value is taken as the water absorption displacement amount.
  • the water absorption is calculated by measuring the weight at the time of absolutely dry and the weight at the time of water absorption using an electronic balance (HR202i manufactured by A & D). As a result, in Example 1, it can be confirmed that the amount of water absorption displacement is smaller than that in Comparative Example 2.

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Abstract

Cette structure en nids d'abeilles, comprenant un corps cuit en nid d'abeilles qui comporte de multiples orifices traversants séparés par des parois de séparation et agencés côte à côte dans la direction de la longueur, est caractérisée en ce que le corps cuit en nid d'abeilles comprend un corps moulé par extrusion qui contient du CuO, de la zéolithe β et un liant inorganique, et en ce que le rapport molaire SiO2/Al2O3 de la zéolithe β est supérieur ou égal à 300.
PCT/JP2017/010907 2016-03-22 2017-03-17 Structure en nids d'abeilles et procédé de production de structure en nids d'abeilles WO2017164114A1 (fr)

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JP2016-057270 2016-03-22
JP2016057270A JP2017170301A (ja) 2016-03-22 2016-03-22 ハニカム構造体及びハニカム構造体の製造方法

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11228128A (ja) * 1997-11-07 1999-08-24 Ngk Insulators Ltd 高耐熱性β−ゼオライト及びそれを用いた自動車排ガス浄化用吸着材
JP2011125846A (ja) * 2009-11-19 2011-06-30 Ibiden Co Ltd ハニカム構造体及び排ガス浄化装置
JP2012213754A (ja) * 2011-03-29 2012-11-08 Ibiden Co Ltd ハニカム構造体及び排ガス浄化装置
WO2015145181A1 (fr) * 2014-03-27 2015-10-01 Johnson Matthey Public Limited Company Procédé de fabrication d'un catalyseur et catalyseur en tant que tel

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11228128A (ja) * 1997-11-07 1999-08-24 Ngk Insulators Ltd 高耐熱性β−ゼオライト及びそれを用いた自動車排ガス浄化用吸着材
JP2011125846A (ja) * 2009-11-19 2011-06-30 Ibiden Co Ltd ハニカム構造体及び排ガス浄化装置
JP2012213754A (ja) * 2011-03-29 2012-11-08 Ibiden Co Ltd ハニカム構造体及び排ガス浄化装置
WO2015145181A1 (fr) * 2014-03-27 2015-10-01 Johnson Matthey Public Limited Company Procédé de fabrication d'un catalyseur et catalyseur en tant que tel

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