WO2017164110A1 - Procédé de production de structure en nid d'abeilles - Google Patents

Procédé de production de structure en nid d'abeilles Download PDF

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Publication number
WO2017164110A1
WO2017164110A1 PCT/JP2017/010897 JP2017010897W WO2017164110A1 WO 2017164110 A1 WO2017164110 A1 WO 2017164110A1 JP 2017010897 W JP2017010897 W JP 2017010897W WO 2017164110 A1 WO2017164110 A1 WO 2017164110A1
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Prior art keywords
honeycomb
manufacturing
hydrothermal treatment
type zeolite
honeycomb structure
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PCT/JP2017/010897
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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
    • 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
    • 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
    • B01J35/56—
    • 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
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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 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.
  • the conventional manufacturing method requires a number of steps for the manufacture of zeolite particles and the manufacture of the honeycomb structure. .
  • 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-described problems, and an object of the present invention is to provide a method for manufacturing a honeycomb structure that is excellent in HC adsorption performance and hardly breaks during use.
  • 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 Cu source, a ⁇ -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 A firing process for producing a fired body, wherein hydrothermal treatment is performed before the molding process, after the firing process, or in the firing process.
  • the hydrothermal treatment is preferably performed in a raw material hydrothermal treatment step of hydrothermally treating the Cu source and the ⁇ -type zeolite before the forming step.
  • the raw material hydrothermal treatment step is desirably performed at a temperature of 800 to 1000 ° C., a time of 1 to 24 hours, and an atmosphere of a water vapor concentration of 1 to 20% by volume.
  • the hydrothermal treatment is performed in a honeycomb fired body hydrothermal treatment step of hydrothermally treating the honeycomb fired body after the firing step.
  • the honeycomb fired body hydrothermal treatment step is desirably performed at a temperature of 800 to 1000 ° C., a time of 1 to 24 hours, and an atmosphere of a water vapor concentration of 1 to 20% by volume.
  • the hydrothermal treatment is performed simultaneously with the firing of the honeycomb formed body in the firing step.
  • the firing step is performed at a temperature of 800 to 1000 ° C., a time of 1 to 24 hours, and an atmosphere of a water vapor concentration of 1 to 20% by volume.
  • a honeycomb structure having excellent HC adsorption performance can be manufactured. It is known that when the ⁇ -type zeolite is heated to a high temperature in a water vapor atmosphere, “dealuminization” occurs in which aluminum (Al) is removed from the zeolite skeleton.
  • hydrothermal treatment before the forming step raw material hydrothermal treatment step
  • hydrothermal treatment after the firing step honeycomb fired body hydrothermal treatment step
  • a steam atmosphere in the firing step It is presumed that Al is released from the ⁇ -type zeolite by calcination (hereinafter collectively referred to as heat treatment in a steam atmosphere), and that Al forms a compound with Cu.
  • heat treatment in a steam atmosphere the state of Cu supported on the ⁇ -type zeolite is changed by the heat treatment in the water vapor atmosphere, and as a result, the ⁇ -type zeolite is changed to a structure that easily adsorbs HC. .
  • the method for manufacturing a honeycomb structure of the present invention it is possible to manufacture a honeycomb structure that is hardly damaged during use. 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.
  • Al is released from ⁇ -type zeolite by heat treatment in a steam atmosphere, so that moisture is hardly adsorbed on ⁇ -type zeolite, and volume contraction / expansion due to moisture adsorption / desorption. Is estimated to be suppressed. As a result, it is considered that damage to the honeycomb structure that occurs during use is suppressed.
  • the Cu source is preferably a Cu compound.
  • a honeycomb formed body containing a Cu source and ⁇ -type zeolite can be easily produced simply by adding a Cu compound to the raw material paste.
  • the amount of the Cu compound 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 Cu compound contained in the raw material paste is in the above range, the effect of improving the adsorption performance of HC by heat treatment in a water vapor atmosphere and the effect of suppressing the volume shrinkage / expansion due to moisture adsorption / desorption Fully obtained.
  • the Cu source is Cu ions
  • the HC adsorption performance can be improved by heat treatment in a water vapor atmosphere, and the moisture adsorption / desorption can be performed. Volume shrinkage / expansion can be suppressed.
  • the amount of ⁇ -type zeolite ion-exchanged with the Cu ions is preferably 1 to 7% by weight.
  • the amount of ⁇ -type zeolite ion-exchanged by Cu ions is in the above range, the effect of improving the adsorption performance of HC by heat treatment in a steam atmosphere and the shrinkage / expansion of the volume due to moisture adsorption / desorption A sufficient suppression effect is obtained.
  • the ⁇ -type zeolite preferably has a SiO 2 / Al 2 O 3 molar ratio of 10 to 150.
  • SiO 2 / Al 2 O 3 molar ratio of ⁇ -type zeolite is in the above range, the effect of improving the adsorption performance of HC by heat treatment in a water vapor atmosphere and the volume shrinkage / expansion due to moisture adsorption / desorption A sufficient suppression effect is 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 a three-way catalyst.
  • FIG. 1 is a perspective view schematically showing an example of a honeycomb structure obtained by the manufacturing method of the present invention.
  • FIG. 2 is a perspective view schematically showing another example of the honeycomb structure obtained by the manufacturing method 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 relationship between the water absorption rate and the water absorption displacement amount.
  • a honeycomb structure obtained by the manufacturing method 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 Cu-containing ⁇ -type zeolite and an inorganic binder.
  • the honeycomb fired body is produced by extruding and firing a raw material paste containing a Cu source, ⁇ -type zeolite, and an inorganic binder.
  • the honeycomb structure obtained by the production method 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 a honeycomb structure obtained by the manufacturing method 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 a Cu-containing ⁇ -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 obtained by the manufacturing method 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 shape of the honeycomb structure obtained by the manufacturing method of the present invention is not limited to a columnar shape, but a prismatic shape, an elliptical columnar shape, a long cylindrical shape, a rounded chamfered prismatic shape (for example, a rounded chamfered triangular prism shape) ) And the like.
  • the shape of the through hole of the honeycomb fired body is not limited to a quadrangular prism shape, and may include a triangular prism shape, a hexagonal prism shape, and the like.
  • 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 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 Cu source, a ⁇ -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.
  • hydrothermal treatment is performed before the forming step, after the firing step, or in the firing step.
  • hydrothermal treatment step of hydrothermally treating the honeycomb fired body after the firing step will be described.
  • a raw material paste containing a Cu 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 using a raw material paste containing a Cu source, ⁇ -type zeolite, and an inorganic binder, and further containing inorganic fibers and the like as necessary.
  • the Cu source is preferably a Cu compound.
  • the raw material paste includes a Cu compound, ⁇ -type zeolite, and an inorganic binder.
  • the Cu compound include copper oxide, copper nitrate, copper acetate, and copper sulfate. Among these, copper oxide is desirable.
  • the amount of the Cu compound contained in the raw material paste is preferably 1 to 7% by weight and preferably 2 to 4% by weight with respect to ⁇ -type zeolite in terms of Cu. More desirable.
  • the Cu source is Cu ions
  • ⁇ -type zeolite ion-exchanged with Cu ions may be used as the Cu source and ⁇ -type zeolite.
  • the raw material paste contains ⁇ -type zeolite ion-exchanged with Cu ions and an inorganic binder.
  • the amount of ⁇ -type zeolite ion-exchanged with Cu ions is preferably 1 to 7% by weight, and more preferably 2 to 4% by weight.
  • the SiO 2 / Al 2 O 3 molar ratio of ⁇ -type zeolite is preferably 10 to 150, more preferably 20 to 100, and more preferably 30 to 70. More desirable.
  • the SiO 2 / Al 2 O 3 molar ratio of the ⁇ -type zeolite raw material can be measured by fluorescent X-ray analysis (XRF).
  • XRF fluorescent X-ray analysis
  • the SiO 2 / Al 2 O 3 molar ratio of ⁇ -type zeolite can be measured by 29 Si-NMR.
  • the SiO 2 / Al 2 O 3 molar ratio is the SiO of the ⁇ -type zeolite before being ion-exchanged with Cu ions. It means 2 / Al 2 O 3 molar ratio.
  • the average particle size of ⁇ -type zeolite 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, and more preferably 30 to 50% by weight.
  • the inorganic binder is not particularly limited, but includes solids contained in alumina sol, silica sol, titania sol, water glass, sepiolite, attapulgite, boehmite, etc. May be.
  • 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 raw material paste preferably further contains 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 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 fired body is hydrothermally treated.
  • hydrothermal treatment refers to a treatment in which a gas containing water vapor is circulated in a through hole and heated at a high temperature.
  • the temperature of the honeycomb fired body hydrothermal treatment step is desirably 800 to 1000 ° C., and more desirably 800 to 900 ° C.
  • the honeycomb fired body hydrothermal treatment time is preferably 1 to 24 hours, more preferably 5 to 15 hours.
  • the atmosphere of the honeycomb fired body hydrothermal treatment step is preferably a water vapor concentration of 1 to 20% by volume, and more preferably a water vapor concentration of 5 to 15% by volume.
  • the hydrothermal treatment is performed in the honeycomb fired body hydrothermal treatment step after the firing step, instead of the raw material water for hydrothermally treating the Cu source and the ⁇ -type zeolite before the molding step. You may perform in a heat processing process.
  • the hydrothermal treatment is performed in the raw material hydrothermal treatment step, the conditions of the forming step and the firing step are the same as those when the hydrothermal treatment is performed after the firing step.
  • the hydrothermal treatment in the raw material hydrothermal treatment step refers to a treatment in which an object and water (including the case of water vapor) are enclosed in a pressure vessel and heated under high temperature and high pressure.
  • the temperature of the raw material hydrothermal treatment step is desirably 800 to 1000 ° C., and more desirably 800 to 900 ° C.
  • the raw material hydrothermal treatment time is preferably 1 to 24 hours, and more preferably 5 to 15 hours.
  • the atmosphere of the raw material hydrothermal treatment step is preferably a water vapor concentration of 1 to 20% by volume, and more preferably a water vapor concentration of 5 to 15% by volume.
  • the hydrothermal treatment is performed in the firing step instead of being performed in the honeycomb fired body hydrothermal treatment step after the firing step or in the raw material hydrothermal treatment step before the forming step. It may be performed simultaneously with the body firing.
  • the hydrothermal treatment is performed in the firing step, the conditions for the molding step are the same as when the hydrothermal treatment is performed after the firing step.
  • the temperature of the firing step is desirably 800 to 1000 ° C., and more desirably 800 to 900 ° C.
  • the firing step time is preferably 1 to 24 hours, and more preferably 5 to 15 hours.
  • the atmosphere of the firing step is desirably a water vapor concentration of 1 to 20% by volume, and a water vapor concentration of 5 to 15% by volume. More desirable.
  • 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.
  • a three-way catalyst refers to a catalyst that mainly purifies hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx).
  • the three-way catalyst include 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.
  • 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.
  • the honeycomb structure includes an outer peripheral coat layer
  • 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 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.
  • 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 Cu source, 40 parts by weight of ⁇ -type zeolite (SiO 2 / Al 2 O 3 molar ratio: 40, 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: 40, 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 ⁇ m and
  • 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.
  • the obtained honeycomb fired body was hydrothermally treated under the conditions of a water vapor concentration of 10% by volume and 850 ° C. for 10 hours.
  • the SiO 2 / Al 2 O 3 molar ratio of ⁇ -type zeolite was 250.
  • the SiO 2 / Al 2 O 3 molar ratio of ⁇ -type zeolite was measured by 29 Si-NMR.
  • an evaluation sample of Example 1 was obtained.
  • Comparative Example 1 In Comparative Example 1, a honeycomb fired body was produced under the same conditions as in Example 1, and no hydrothermal treatment was performed. Thus, an evaluation sample of Comparative Example 1 was obtained.
  • Comparative Example 2 In Comparative Example 2, a honeycomb fired body was produced using a raw material paste not containing a Cu source as described below, and the honeycomb fired body was not subjected to hydrothermal treatment.
  • 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.
  • 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 Comparative Example 1, hydrocarbons were released on the high temperature side compared to Comparative Example 2, but the amount of released hydrocarbons was small. Further, in Example 1, although not as much as Comparative Example 1, hydrocarbons are released on the high temperature side compared to Comparative Example 2, and a larger amount of hydrocarbons are released than Comparative Examples 1 and 2. It was confirmed. From the above results, it is possible to produce a honeycomb fired body using a raw material paste containing a Cu source and to perform a hydrothermal treatment of the honeycomb fired body to produce a honeycomb structure excellent in hydrocarbon adsorption performance. It is considered possible.
  • Example 1 and Comparative Example 2 were immersed in water, the volume change rate [%] when the water absorption rate was set to a predetermined value was determined, and the value was taken as the water absorption displacement amount.
  • the water absorption was 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).
  • FIG. 5 is a graph showing the relationship between the water absorption rate and the water absorption displacement amount. From FIG. 5, it was confirmed that in Example 1, the amount of water absorption displacement was smaller than in Comparative Example 2. From this result, by manufacturing a honeycomb fired body using a raw material paste containing a Cu source and performing a hydrothermal treatment of the honeycomb fired body, it becomes difficult to adsorb moisture to the ⁇ -type zeolite, and moisture adsorption / desorption It is thought that the shrinkage / expansion of the volume due to is suppressed.

Abstract

L'invention concerne un procédé de production de structure en nid d'abeilles, pour produire une structure en nid d'abeilles comprenant un corps cuit en nid d'abeilles qui a de multiples trous traversants séparés par des cloisons et disposés côte à côte dans la direction de longueur, qui est caractérisé en ce qu'il comprend une étape de moulage dans laquelle, par moulage d'une pâte de matière première qui contient une source de Cu, une β-zéolite et un liant inorganique, un corps moulé en nid d'abeilles est préparé, qui a de multiples trous traversants séparés par des cloisons et disposés côte à côte dans la direction de longueur, et une étape de cuisson pour produire un corps cuit en nid d'abeilles par cuisson dudit corps moulé en nid d'abeilles, un traitement hydrothermique étant réalisé avant l'étape de moulage, après l'étape de cuisson ou pendant l'étape de cuisson.
PCT/JP2017/010897 2016-03-22 2017-03-17 Procédé de production de structure en nid d'abeilles WO2017164110A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016057268A JP2017170299A (ja) 2016-03-22 2016-03-22 ハニカム構造体の製造方法
JP2016-057268 2016-03-22

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008080194A (ja) * 2006-09-26 2008-04-10 Tosoh Corp β型ゼオライトからなる炭化水素吸着剤
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
JP2011207749A (ja) * 2010-03-12 2011-10-20 Ngk Insulators Ltd ゼオライト構造体及びその製造方法
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 (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008080194A (ja) * 2006-09-26 2008-04-10 Tosoh Corp β型ゼオライトからなる炭化水素吸着剤
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
JP2011207749A (ja) * 2010-03-12 2011-10-20 Ngk Insulators Ltd ゼオライト構造体及びその製造方法
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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