WO2017164110A1 - Honeycomb structure production method - Google Patents

Honeycomb structure production method 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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French (fr)
Japanese (ja)
Inventor
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

This honeycomb structure production method, for producing a honeycomb structure comprising a honeycomb fired body that has multiple through-holes separated by partition walls and arranged side-by-side in the length direction, is characterized by involving a molding step in which, by molding a raw material paste that contains a Cu source, a β-zeolite and an inorganic binder, a honeycomb molded body is prepared that has multiple through-holes separated by partition walls and arranged side-by-side in the length direction, and a firing step for producing a honeycomb fired body by firing the aforementioned honeycomb molded body, wherein a hydrothermal treatment is carried out before the molding step, after the firing step, or during the firing step.

Description

ハニカム構造体の製造方法Manufacturing method of honeycomb structure
本発明は、ハニカム構造体の製造方法に関する。 The present invention relates to a method for manufacturing a honeycomb structure.
ガソリンエンジン等から排出される排ガス中に含まれる炭化水素（ＨＣ）は、通常、白金等の貴金属からなる三元触媒が担持されたハニカム構造体を用いて酸化することによって浄化される。ＨＣを浄化するためには三元触媒が２００℃程度まで昇温される必要があり、それ以下の温度ではＨＣが充分に浄化されない。そのため、エンジン始動直後のように排ガス温度が低い温度では、ＨＣの排出量が多いにも関わらず、ＨＣが浄化されずに排出されてしまう。特に、将来的に燃費の向上が進むと、排ガス温度は低くなる傾向にあるため、ＨＣの浄化率が低下しやすくなると考えられる。 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. In order to purify HC, it is necessary to raise the temperature of the three-way catalyst to about 200 ° C., and 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. In particular, if the fuel efficiency is improved in the future, the exhaust gas temperature tends to be lowered, so that the HC purification rate is likely to decrease.
そこで、特許文献１のように、三元触媒が活性化する温度に達するまでの低温領域ではＨＣを吸着し、高温になったときに吸着したＨＣを放出することによって、ＨＣの浄化率を向上させる技術が開示されている。例えば、特許文献１では、ＨＣ吸着材として、Ｆｅを含むβ型ゼオライトが用いられている。 Therefore, as in Patent Document 1, 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. For example, in Patent Document 1, β-type zeolite containing Fe is used as the HC adsorbent.
特許文献２には、ＦｅやＮｉ等の金属を含有するゼオライトの製造方法として、ゼオライトに対してスチーミング及び鉱酸によって脱アルミニウム処理を行った後、得られたゼオライトスラリーに金属塩水溶液処理及びｐＨを上昇させる処理を施す方法が開示されている。 In 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.
また、ＨＣを吸着させるためではなく、還元剤の存在下に窒素酸化物（ＮＯｘ）を分解させるための固体触媒の製造方法として、特許文献３には、金属を含有するゼオライトを、無機バインダとしてのアルミナと無機繊維とともにハニカム状に成形することによりハニカム構造体を製造する方法が開示されている。 Further, as a method for producing a solid catalyst for decomposing nitrogen oxide (NOx) in the presence of a reducing agent, not for adsorbing HC, 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.
特開平１０－１９２６９９号公報Japanese Patent Laid-Open No. 10-192699 特開平５－１７８６１１号公報Japanese Patent Laid-Open No. 5-178611 特開２０１２－１８３５４１号公報JP 2012-183541 A
ＨＣの吸着を目的とするハニカム構造体においては、ＨＣの吸着量及びＨＣの放出温度が重要である。すなわち、ＨＣを多量に吸着すること、及び、三元触媒が活性化する温度までＨＣを吸着することが重要である。このような特性を有するハニカム構造体を簡便に製造することができる方法が求められているが、従来の製造方法では、ゼオライト粒子の製造及びハニカム構造体の製造に多数の工程が必要であった。 In a honeycomb structure intended for HC adsorption, 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. There is a need for a method that can easily manufacture a honeycomb structure having such characteristics, but the conventional manufacturing method requires a number of steps for the manufacture of zeolite particles and the manufacture of the honeycomb structure. .
また、ハニカム構造体の使用時には、水分の吸着／脱離による体積の収縮／膨張に起因してハニカム構造体が破損することがあり、このようなハニカム構造体の破損を抑えることも求められている。 Further, 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.
本発明は、上記の問題を解決するためになされたものであり、ＨＣの吸着性能に優れ、かつ、使用時に破損が生じ難いハニカム構造体の製造方法を提供することを目的とする。 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.
本発明のハニカム構造体の製造方法は、複数の貫通孔が隔壁を隔てて長手方向に並設されたハニカム焼成体を備えたハニカム構造体の製造方法であって、Ｃｕ源とβ型ゼオライトと無機バインダとを含む原料ペーストを成形することにより、複数の貫通孔が隔壁を隔てて長手方向に並設されたハニカム成形体を作製する成形工程と、上記ハニカム成形体を焼成することにより、ハニカム焼成体を作製する焼成工程と、を含み、上記成形工程の前、上記焼成工程の後、又は、上記焼成工程において、水熱処理が行われることを特徴とする。 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 β-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 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.
本発明のハニカム構造体の製造方法では、上記水熱処理は、上記成形工程の前に、上記Ｃｕ源及び上記β型ゼオライトを水熱処理する原料水熱処理工程において行われることが望ましい。この場合、上記原料水熱処理工程は、温度：８００～１０００℃、時間：１～２４時間、雰囲気：水蒸気濃度１～２０体積％で行われることが望ましい。 In the method for manufacturing a honeycomb structured body of the present invention, the hydrothermal treatment is preferably performed in a raw material hydrothermal treatment step of hydrothermally treating the Cu source and the β-type zeolite before the forming step. In this case, 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.
また、本発明のハニカム構造体の製造方法では、上記水熱処理は、上記焼成工程の後に、上記ハニカム焼成体を水熱処理するハニカム焼成体水熱処理工程において行われることが望ましい。この場合、上記ハニカム焼成体水熱処理工程は、温度：８００～１０００℃、時間：１～２４時間、雰囲気：水蒸気濃度１～２０体積％で行われることが望ましい。 In the method for manufacturing a honeycomb structured body of the present invention, it is desirable that the hydrothermal treatment is performed in a honeycomb fired body hydrothermal treatment step of hydrothermally treating the honeycomb fired body after the firing step. In this case, 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.
さらにまた、本発明のハニカム構造体の製造方法では、上記水熱処理は、上記焼成工程において、上記ハニカム成形体の焼成と同時に行われることが望ましい。この場合、上記焼成工程は、温度：８００～１０００℃、時間：１～２４時間、雰囲気：水蒸気濃度１～２０体積％で行われることが望ましい。 Furthermore, in the method for manufacturing a honeycomb structured body of the present invention, it is preferable that the hydrothermal treatment is performed simultaneously with the firing of the honeycomb formed body in the firing step. In this case, it is desirable that 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.
本発明のハニカム構造体の製造方法では、ＨＣの吸着性能に優れたハニカム構造体を製造することができる。
水蒸気雰囲気中でβ型ゼオライトが高温に加熱されると、ゼオライト骨格からアルミニウム（Ａｌ）が抜ける「脱アルミニウム」が起こることが知られている。本発明のハニカム構造体の製造方法においては、成形工程前（原料水熱処理工程）における水熱処理、焼成工程後（ハニカム焼成体水熱処理工程）における水熱処理、又は、焼成工程における水蒸気雰囲気中での焼成（以下、これらをまとめて水蒸気雰囲気での熱処理という）によってβ型ゼオライトからＡｌが抜け、そのＡｌがＣｕと化合物を形成すると推測される。つまり、水蒸気雰囲気での熱処理によってβ型ゼオライトに担持されているＣｕの状態が変化し、その結果、β型ゼオライトがＨＣを吸着しやすい構造に変化するため、ＨＣの吸着性能が向上すると考えられる。 In the method for manufacturing a honeycomb structure of the present invention, a honeycomb structure having excellent HC adsorption performance can be manufactured.
It is known that when the β-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. In the method for manufacturing a honeycomb structure of the present invention, hydrothermal treatment before the forming step (raw material hydrothermal treatment step), hydrothermal treatment after the firing step (honeycomb fired body hydrothermal treatment step), or in a steam atmosphere in the firing step It is presumed that Al is released from the β-type zeolite by calcination (hereinafter collectively referred to as heat treatment in a steam atmosphere), and that Al forms a compound with Cu. In other words, the state of Cu supported on the β-type zeolite is changed by the heat treatment in the water vapor atmosphere, and as a result, the β-type zeolite is changed to a structure that easily adsorbs HC. .
また、本発明のハニカム構造体の製造方法では、使用時に破損が生じ難いハニカム構造体を製造することができる。
β型ゼオライトを構成するＡｌには水分が吸着しやすい。Ａｌに水分が吸着すると、β型ゼオライトの骨格構造に歪みが生じるため、β型ゼオライトの体積が変化する。本発明のハニカム構造体の製造方法においては、水蒸気雰囲気での熱処理によってβ型ゼオライトからＡｌが抜けるため、β型ゼオライトに水分が吸着しにくくなり、水分の吸着／脱離による体積の収縮／膨張が抑制されると推測される。その結果、使用時に生じるハニカム構造体の破損が抑制されると考えられる。 Further, according to 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 β-type zeolite. When moisture is adsorbed on Al, the skeleton structure of β-type zeolite is distorted, and the volume of β-type zeolite changes. In the method for manufacturing a honeycomb structure of the present invention, Al is released from β-type zeolite by heat treatment in a steam atmosphere, so that moisture is hardly adsorbed on β-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.
本発明のハニカム構造体の製造方法において、上記Ｃｕ源は、Ｃｕ化合物であることが望ましい。
上記の方法では、ハニカム成形体を作製する際、原料ペースト中にＣｕ化合物を加えるだけで、Ｃｕ源及びβ型ゼオライトを含むハニカム成形体を簡便に作製することができる。 In the method for manufacturing a honeycomb structured body of the present invention, the Cu source is preferably a Cu compound.
In the above method, when a honeycomb formed body is produced, a honeycomb formed body containing a Cu source and β-type zeolite can be easily produced simply by adding a Cu compound to the raw material paste.
本発明のハニカム構造体の製造方法において、上記原料ペーストに含まれる上記Ｃｕ化合物の量は、Ｃｕ換算で、上記β型ゼオライトに対して１～７重量％であることが望ましい。
原料ペーストに含まれるＣｕ化合物の量が上記範囲にある場合、水蒸気雰囲気での熱処理によってＨＣの吸着性能を向上させる効果、及び、水分の吸着／脱離による体積の収縮／膨張を抑制する効果が充分に得られる。 In the method for manufacturing a honeycomb structured body of the present invention, the amount of the Cu compound contained in the raw material paste is preferably 1 to 7% by weight with respect to the β-type zeolite in terms of Cu.
When 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.
本発明のハニカム構造体の製造方法において、上記Ｃｕ源は、Ｃｕイオンであり、上記Ｃｕ源及び上記β型ゼオライトとして、Ｃｕイオンによりイオン交換されたβ型ゼオライトを用いることが望ましい。
このように、予めＣｕイオンによりイオン交換されたβ型ゼオライトを用いた場合であっても、水蒸気雰囲気での熱処理によってＨＣの吸着性能を向上させることができ、かつ、水分の吸着／脱離による体積の収縮／膨張を抑制することができる。 In the method for manufacturing a honeycomb structured body of the present invention, the Cu source is Cu ions, and it is desirable to use β-type zeolite ion-exchanged with Cu ions as the Cu source and the β-type zeolite.
Thus, even when β-type zeolite ion-exchanged with Cu ions in advance is used, 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.
本発明のハニカム構造体の製造方法において、上記β型ゼオライトの上記Ｃｕイオンによりイオン交換されている量は、１～７重量％であることが望ましい。
β型ゼオライトのＣｕイオンによりイオン交換されている量が上記範囲にある場合、水蒸気雰囲気での熱処理によってＨＣの吸着性能を向上させる効果、及び、水分の吸着／脱離による体積の収縮／膨張を抑制する効果が充分に得られる。 In the method for manufacturing a honeycomb structure of the present invention, the amount of β-type zeolite ion-exchanged with the Cu ions is preferably 1 to 7% by weight.
When the amount of β-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.
本発明のハニカム構造体の製造方法において、上記β型ゼオライトのＳｉＯ２／Ａｌ２Ｏ３モル比は、１０～１５０であることが望ましい。
β型ゼオライトのＳｉＯ２／Ａｌ２Ｏ３モル比が上記範囲にある場合、水蒸気雰囲気での熱処理によってＨＣの吸着性能を向上させる効果、及び、水分の吸着／脱離による体積の収縮／膨張を抑制する効果が充分に得られる。 In the method for manufacturing a honeycomb structure of the present invention, the β-type zeolite preferably has a SiO 2 / Al 2 O 3 molar ratio of 10 to 150.
When the SiO 2 / Al 2 O 3 molar ratio of β-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.
本発明のハニカム構造体の製造方法において、上記原料ペーストは、無機繊維をさらに含むことが望ましい。この場合、得られるハニカム構造体の強度を向上させることができる。 In the method for manufacturing a honeycomb structured body of the present invention, the raw material paste preferably further contains inorganic fibers. In this case, the strength of the obtained honeycomb structure can be improved.
本発明のハニカム構造体の製造方法は、上記隔壁の表面に三元触媒を担持させる担持工程をさらに含むことが望ましい。三元触媒によってＨＣを浄化することができる。 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.
図１は、本発明の製造方法により得られるハニカム構造体の一例を模式的に示す斜視図である。FIG. 1 is a perspective view schematically showing an example of a honeycomb structure obtained by the manufacturing method of the present invention. 図２は、本発明の製造方法により得られるハニカム構造体の別の一例を模式的に示す斜視図である。FIG. 2 is a perspective view schematically showing another example of the honeycomb structure obtained by the manufacturing method of the present invention. 図３は、図２に示すハニカム構造体を構成するハニカム焼成体の一例を模式的に示す斜視図である。FIG. 3 is a perspective view schematically showing an example of a honeycomb fired body constituting the honeycomb structure shown in FIG. 図４は、温度と炭化水素の放出量との関係を示すグラフである。FIG. 4 is a graph showing the relationship between temperature and hydrocarbon release. 図５は、吸水率と吸水変位量との関係を示すグラフである。FIG. 5 is a graph showing the relationship between the water absorption rate and the water absorption displacement amount.
（発明の詳細な説明）
［ハニカム構造体］
まず、本発明のハニカム構造体の製造方法により得られるハニカム構造体について説明する。 (Detailed description of the invention)
[Honeycomb structure]
First, a honeycomb structure obtained by the method for manufacturing a honeycomb structure of the present invention will be described.
本発明の製造方法により得られるハニカム構造体は、複数の貫通孔が隔壁を隔てて長手方向に並設されたハニカム焼成体を備えている。 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.
本発明の製造方法により得られるハニカム構造体において、ハニカム焼成体は、Ｃｕ含有β型ゼオライトと無機バインダとを含む押出成形体からなる。後述するように、ハニカム焼成体は、Ｃｕ源とβ型ゼオライトと無機バインダとを含む原料ペーストを押出成形した後、焼成することにより作製されている。 In the honeycomb structure obtained by the manufacturing method of the present invention, the honeycomb fired body is formed of an extrusion-molded body containing Cu-containing β-type zeolite and an inorganic binder. As will be described later, the honeycomb fired body is produced by extruding and firing a raw material paste containing a Cu source, β-type zeolite, and an inorganic binder.
本発明の製造方法により得られるハニカム構造体は、単一のハニカム焼成体を備えていてもよいし、接着層を介して接着された複数個のハニカム焼成体を備えていてもよい。 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.
本発明の製造方法により得られるハニカム構造体において、ハニカム焼成体の外周面には、外周コート層が形成されていることが望ましい。 In the honeycomb structure obtained by the manufacturing method of the present invention, it is desirable that an outer peripheral coat layer is formed on the outer peripheral surface of the honeycomb fired body.
図１は、本発明の製造方法により得られるハニカム構造体の一例を模式的に示す斜視図である。
図１に示すハニカム構造体１０は、複数の貫通孔１１ａが隔壁１１ｂを隔てて長手方向に並設された単一のハニカム焼成体１１を備えている。ハニカム焼成体１１は、Ｃｕ含有β型ゼオライトと無機バインダとを含む押出成形体からなる。さらに、ハニカム焼成体１１の外周面には、外周コート層１２が形成されている。 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 β-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.
図２は、本発明の製造方法により得られるハニカム構造体の別の一例を模式的に示す斜視図である。
図３は、図２に示すハニカム構造体を構成するハニカム焼成体の一例を模式的に示す斜視図である。 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.
図２に示すハニカム構造体２０は、複数の貫通孔２１ａが隔壁２１ｂを隔てて長手方向に並設されたハニカム焼成体２１（図３参照）が接着層２３を介して複数個接着されている以外は、図１に示すハニカム構造体１０と同一の構成を有する。さらに、ハニカム焼成体２１の外周面には、外周コート層２２が形成されている。 In the honeycomb structure 20 shown in FIG. 2, a plurality of honeycomb fired bodies 21 (see FIG. 3) 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.
なお、ハニカム構造体１０及び２０においては、それぞれ外周コート層１２及び２２が形成されていなくてもよい。 In the honeycomb structures 10 and 20, the outer peripheral coat layers 12 and 22 may not be formed, respectively.
本発明の製造方法により得られるハニカム構造体の形状としては、円柱状に限定されず、角柱状、楕円柱状、長円柱状、丸面取りされている角柱状（例えば、丸面取りされている三角柱状）等が挙げられる。 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.
本発明の製造方法により得られるハニカム構造体において、ハニカム焼成体の貫通孔の形状としては、四角柱状に限定されず、三角柱状、六角柱状等が挙げられる。 In the honeycomb structure obtained by the manufacturing method of the present invention, 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.
本発明の製造方法により得られるハニカム構造体において、ハニカム焼成体の長手方向に垂直な断面の貫通孔の密度は、３１～１５５個／ｃｍ２であることが望ましい。 In the honeycomb structure obtained by the manufacturing method of the present invention, 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 .
本発明の製造方法により得られるハニカム構造体において、ハニカム焼成体の隔壁の厚さは、０．１０～０．５０ｍｍであることが望ましく、０．２０～０．４０ｍｍであることがより望ましい。 In the honeycomb structure obtained by the manufacturing method of the present invention, 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.
本発明の製造方法により得られるハニカム構造体において、ハニカム焼成体の外周面に外周コート層が形成されている場合、外周コート層の厚さは、０．１～２．０ｍｍであることが望ましい。 In the honeycomb structure obtained by the manufacturing method of the present invention, when the outer peripheral coat layer is formed on the outer peripheral surface of the honeycomb fired body, the thickness of the outer peripheral coat layer is preferably 0.1 to 2.0 mm. .
［ハニカム構造体の製造方法］
次に、本発明のハニカム構造体の製造方法について説明する。
本発明のハニカム構造体の製造方法は、複数の貫通孔が隔壁を隔てて長手方向に並設されたハニカム焼成体を備えたハニカム構造体の製造方法であって、Ｃｕ源とβ型ゼオライトと無機バインダとを含む原料ペーストを成形することにより、複数の貫通孔が隔壁を隔てて長手方向に並設されたハニカム成形体を作製する成形工程と、上記ハニカム成形体を焼成することにより、ハニカム焼成体を作製する焼成工程と、を含む。 [Manufacturing method of honeycomb structure]
Next, the manufacturing method of the honeycomb structure of the present invention will be described.
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 β-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.
本発明のハニカム構造体の製造方法においては、上記成形工程の前、上記焼成工程の後、又は、上記焼成工程において、水熱処理が行われることを特徴とする。
以下、水熱処理が、焼成工程の後に、ハニカム焼成体を水熱処理するハニカム焼成体水熱処理工程において行われる場合について説明する。 In the method for manufacturing a honeycomb structure of the present invention, hydrothermal treatment is performed before the forming step, after the firing step, or in the firing step.
Hereinafter, a case where the hydrothermal treatment is performed in the honeycomb fired body hydrothermal treatment step of hydrothermally treating the honeycomb fired body after the firing step will be described.
（成形工程）
本発明のハニカム構造体の製造方法において、成形工程では、Ｃｕ源とβ型ゼオライトと無機バインダとを含む原料ペーストを成形することにより、複数の貫通孔が隔壁を隔てて長手方向に並設されたハニカム成形体を作製する。具体的には、Ｃｕ源とβ型ゼオライトと無機バインダとを含み、必要に応じて、無機繊維等をさらに含む原料ペーストを用いて押出成形することにより、ハニカム成形体を作製する。 (Molding process)
In the method for manufacturing a honeycomb structure of the present invention, in the forming step, a raw material paste containing a Cu source, β-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, β-type zeolite, and an inorganic binder, and further containing inorganic fibers and the like as necessary.
本発明のハニカム構造体の製造方法において、Ｃｕ源は、Ｃｕ化合物であることが望ましい。この場合、原料ペーストは、Ｃｕ化合物とβ型ゼオライトと無機バインダとを含む。
Ｃｕ化合物としては、酸化銅、硝酸銅、酢酸銅、硫酸銅等が挙げられる。これらの中では、酸化銅が望ましい。 In the method for manufacturing a honeycomb structured body of the present invention, the Cu source is preferably a Cu compound. In this case, the raw material paste includes a Cu compound, β-type zeolite, and an inorganic binder.
Examples of the Cu compound include copper oxide, copper nitrate, copper acetate, and copper sulfate. Among these, copper oxide is desirable.
Ｃｕ源がＣｕ化合物である場合、原料ペーストに含まれるＣｕ化合物の量は、Ｃｕ換算で、β型ゼオライトに対して１～７重量％であることが望ましく、２～４重量％であることがより望ましい。 When the Cu source is a Cu compound, 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 β-type zeolite in terms of Cu. More desirable.
本発明のハニカム構造体の製造方法において、Ｃｕ源は、Ｃｕイオンであり、Ｃｕ源及びβ型ゼオライトとして、Ｃｕイオンによりイオン交換されたβ型ゼオライトを用いてもよい。この場合、原料ペーストは、Ｃｕイオンによりイオン交換されたβ型ゼオライトと無機バインダとを含む。 In the method for manufacturing a honeycomb structure of the present invention, the Cu source is Cu ions, and β-type zeolite ion-exchanged with Cu ions may be used as the Cu source and β-type zeolite. In this case, the raw material paste contains β-type zeolite ion-exchanged with Cu ions and an inorganic binder.
Ｃｕ源がＣｕイオンである場合、β型ゼオライトのＣｕイオンによりイオン交換されている量は、１～７重量％であることが望ましく、２～４重量％であることがより望ましい。 When the Cu source is Cu ions, the amount of β-type zeolite ion-exchanged with Cu ions is preferably 1 to 7% by weight, and more preferably 2 to 4% by weight.
本発明のハニカム構造体の製造方法において、β型ゼオライトのＳｉＯ２／Ａｌ２Ｏ３モル比は、１０～１５０であることが望ましく、２０～１００であることがより望ましく、３０～７０であることがさらに望ましい。
β型ゼオライト原料のＳｉＯ２／Ａｌ２Ｏ３モル比は、蛍光Ｘ線分析（ＸＲＦ）により測定することができる。ハニカム構造体にバインダなどのＡｌ分が含まれる場合、β型ゼオライトのＳｉＯ２／Ａｌ２Ｏ３モル比は、２９Ｓｉ－ＮＭＲにより測定することができる。
なお、Ｃｕ源及びβ型ゼオライトとして、Ｃｕイオンによりイオン交換されたβ型ゼオライトを用いる場合、上記ＳｉＯ２／Ａｌ２Ｏ３モル比は、Ｃｕイオンによりイオン交換される前のβ型ゼオライトのＳｉＯ２／Ａｌ２Ｏ３モル比を意味する。 In the method for manufacturing a honeycomb structure of the present invention, the SiO 2 / Al 2 O 3 molar ratio of β-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 β-type zeolite raw material can be measured by fluorescent X-ray analysis (XRF). When the honeycomb structure contains Al such as a binder, the SiO 2 / Al 2 O 3 molar ratio of β-type zeolite can be measured by 29 Si-NMR.
When β-type zeolite ion-exchanged with Cu ions is used as the Cu source and β-type zeolite, the SiO 2 / Al 2 O 3 molar ratio is the SiO of the β-type zeolite before being ion-exchanged with Cu ions. It means 2 / Al 2 O 3 molar ratio.
本発明のハニカム構造体の製造方法において、β型ゼオライトの平均粒子径は、０．１～１０μｍであることが望ましく、０．５～５μｍであることがより望ましい。
β型ゼオライトの平均粒子径は、レーザー回折・散乱式粒度分布測定器（セイシン企業製：レーザーマイクロンサイザー　ＬＭＳ－３０）を用いて測定した一次粒子の平均粒子径である。 In the method for manufacturing a honeycomb structure of the present invention, the average particle size of β-type zeolite is preferably 0.1 to 10 μm, and more preferably 0.5 to 5 μm.
The average particle size of β-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).
本発明のハニカム構造体の製造方法において、原料ペーストに含まれるβ型ゼオライトの量は、２５～６０重量％であることが望ましく、３０～５０重量％であることがより望ましい。 In the method for manufacturing a honeycomb structured body of the present invention, the amount of β-type zeolite contained in the raw material paste is preferably 25 to 60% by weight, and more preferably 30 to 50% by weight.
本発明のハニカム構造体の製造方法において、無機バインダとしては、特に限定されないが、アルミナゾル、シリカゾル、チタニアゾル、水ガラス、セピオライト、アタパルジャイト、ベーマイト等に含まれる固形分が挙げられ、二種以上併用してもよい。 In the method for manufacturing a honeycomb structure of the present invention, 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.
本発明のハニカム構造体の製造方法において、原料ペーストに含まれる無機バインダの量は、５～２０重量％であることが望ましく、７～１５重量％であることがより望ましい。 In the method for manufacturing a honeycomb structure of the present invention, 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.
本発明のハニカム構造体の製造方法において、上記原料ペーストは、無機繊維をさらに含むことが望ましい。 In the method for manufacturing a honeycomb structured body of the present invention, the raw material paste preferably further contains inorganic fibers.
無機繊維を構成する材料としては、特に限定されないが、アルミナ、シリカ、炭化ケイ素、シリカアルミナ、ガラス、チタン酸カリウム、ホウ酸アルミニウム等が挙げられ、二種以上併用してもよい。 Although it does not specifically limit as a material which comprises inorganic fiber, Alumina, silica, silicon carbide, silica alumina, glass, potassium titanate, aluminum borate, etc. are mentioned, You may use 2 or more types together.
無機繊維のアスペクト比は、２～３００であることが望ましく、５～２００であることがより望ましく、１０～１００であることがさらに望ましい。 The aspect ratio of the inorganic fiber is preferably 2 to 300, more preferably 5 to 200, and still more preferably 10 to 100.
本発明のハニカム構造体の製造方法において、原料ペーストに含まれる無機繊維の量は、２～１５重量％であることが望ましく、５～１０重量％であることがより望ましい。 In the method for manufacturing a honeycomb structure of the present invention, 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.
本発明のハニカム構造体の製造方法において、原料ペーストは、必要に応じて、有機バインダ、分散媒、成形助剤等をさらに含んでいてもよい。 In the method for manufacturing a honeycomb structured body of the present invention, the raw material paste may further contain an organic binder, a dispersion medium, a molding aid, and the like as necessary.
有機バインダとしては、特に限定されないが、メチルセルロース、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ポリエチレングリコール、フェノール樹脂、エポキシ樹脂等が挙げられ、二種以上併用してもよい。 Although it does not specifically limit as an organic binder, Methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, polyethyleneglycol, a phenol resin, an epoxy resin etc. are mentioned, You may use 2 or more types together.
分散媒としては、特に限定されないが、水、ベンゼン等の有機溶媒、メタノール等のアルコール等が挙げられ、二種以上併用してもよい。 Although it does not specifically limit as a dispersion medium, Alcohol, such as water, organic solvents, such as benzene, methanol, etc. are mentioned, You may use 2 or more types together.
成形助剤としては、特に限定されないが、エチレングリコール、デキストリン、脂肪酸、脂肪酸石鹸、ポリアルコール等が挙げられ、二種以上併用してもよい。 Although it does not specifically limit as a shaping | molding adjuvant, Ethylene glycol, dextrin, a fatty acid, fatty acid soap, a polyalcohol etc. are mentioned, You may use together 2 or more types.
原料ペーストを調製する際には、混合混練することが望ましく、ミキサー、アトライタ等を用いて混合してもよく、ニーダー等を用いて混練してもよい。 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.
次に、マイクロ波乾燥機、熱風乾燥機、誘電乾燥機、減圧乾燥機、真空乾燥機、凍結乾燥機等の乾燥機を用いて、ハニカム成形体を乾燥してハニカム乾燥体を作製することが望ましい。 Next, using a dryer such as a microwave dryer, hot air dryer, dielectric dryer, vacuum dryer, vacuum dryer, freeze dryer, etc., the honeycomb formed body can be dried to produce a honeycomb dried body. desirable.
本明細書においては、焼成工程を行う前のハニカム成形体及びハニカム乾燥体をまとめてハニカム成形体とも呼ぶ。 In the present specification, the honeycomb formed body and the honeycomb dried body before the firing step are collectively referred to as a honeycomb formed body.
（焼成工程）
本発明のハニカム構造体の製造方法において、焼成工程では、ハニカム成形体を焼成することにより、ハニカム焼成体を作製する。なお、この工程は、ハニカム成形体の脱脂及び焼成が行われるため、「脱脂・焼成工程」ということもできるが、便宜上「焼成工程」という。 (Baking process)
In the method for manufacturing a honeycomb structure of the present invention, in the firing step, the honeycomb fired body is fired to produce a honeycomb fired body. In addition, since 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.
焼成工程の温度は、６００～１０００℃であることが望ましく、６００～８００℃であることがより望ましい。また、焼成工程の時間は、１～１０時間であることが望ましく、１．５～５時間であることがより望ましい。焼成工程の雰囲気は特に限定されないが、酸素濃度が１～１０体積％であることが望ましい。 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.
（ハニカム焼成体水熱処理工程）
本発明のハニカム構造体の製造方法において、ハニカム焼成体水熱処理工程では、ハニカム焼成体を水熱処理する。
本明細書において、水熱処理とは、水蒸気を含むガスを貫通孔内に流通させ、高温で加熱する処理をいう。 (Honeycomb fired body hydrothermal treatment process)
In the method for manufacturing a honeycomb structured body of the present invention, in the honeycomb fired body hydrothermal treatment step, the honeycomb fired body is hydrothermally treated.
In this specification, 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.
本発明のハニカム構造体の製造方法において、ハニカム焼成体水熱処理工程の温度は、８００～１０００℃が望ましく、８００～９００℃がより望ましい。 In the method for manufacturing a honeycomb structured body of the present invention, the temperature of the honeycomb fired body hydrothermal treatment step is desirably 800 to 1000 ° C., and more desirably 800 to 900 ° C.
本発明のハニカム構造体の製造方法において、ハニカム焼成体水熱処理工程の時間は、１～２４時間が望ましく、５～１５時間がより望ましい。 In the method for manufacturing a honeycomb structure of the present invention, the honeycomb fired body hydrothermal treatment time is preferably 1 to 24 hours, more preferably 5 to 15 hours.
本発明のハニカム構造体の製造方法において、ハニカム焼成体水熱処理工程の雰囲気は、水蒸気濃度が１～２０体積％であることが望ましく、水蒸気濃度が５～１５体積％であることがより望ましい。 In the method for manufacturing a honeycomb structure of the present invention, 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.
（原料水熱処理工程）
本発明のハニカム構造体の製造方法では、水熱処理は、焼成工程の後のハニカム焼成体水熱処理工程において行われる代わりに、成形工程の前に、Ｃｕ源及びβ型ゼオライトを水熱処理する原料水熱処理工程において行われてもよい。
水熱処理が原料水熱処理工程において行われる場合、成形工程及び焼成工程の条件は、水熱処理を焼成工程の後に行う場合と同様である。ただし、原料水熱処理工程での水熱処理とは、対象物と水（水蒸気の場合を含む）を圧力容器内に封入し、高温高圧下で加熱する処理をいう。 (Raw material hydrothermal treatment process)
In the method for manufacturing a honeycomb structure of the present invention, 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 β-type zeolite before the molding step. You may perform in a heat processing process.
When 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. However, 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.
本発明のハニカム構造体の製造方法において、原料水熱処理工程の温度は、８００～１０００℃が望ましく、８００～９００℃がより望ましい。 In the method for manufacturing a honeycomb structured body of the present invention, the temperature of the raw material hydrothermal treatment step is desirably 800 to 1000 ° C., and more desirably 800 to 900 ° C.
本発明のハニカム構造体の製造方法において、原料水熱処理工程の時間は、１～２４時間が望ましく、５～１５時間がより望ましい。 In the method for manufacturing a honeycomb structure of the present invention, the raw material hydrothermal treatment time is preferably 1 to 24 hours, and more preferably 5 to 15 hours.
本発明のハニカム構造体の製造方法において、原料水熱処理工程の雰囲気は、水蒸気濃度が１～２０体積％であることが望ましく、水蒸気濃度が５～１５体積％であることがより望ましい。 In the method for manufacturing a honeycomb structured body of the present invention, 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.
（焼成工程における水蒸気雰囲気中での焼成）
本発明のハニカム構造体の製造方法では、水熱処理は、焼成工程の後のハニカム焼成体水熱処理工程、又は、成形工程の前の原料水熱処理工程において行われる代わりに、焼成工程において、ハニカム成形体の焼成と同時に行われてもよい。
水熱処理が焼成工程において行われる場合、成形工程の条件は、水熱処理を焼成工程の後に行う場合と同様である。 (Firing in a steam atmosphere in the firing process)
In the method for manufacturing a honeycomb structured body of the present invention, 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.
When 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.
本発明のハニカム構造体の製造方法において、水熱処理が焼成工程において行われる場合、焼成工程の温度は、８００～１０００℃が望ましく、８００～９００℃がより望ましい。 In the method for manufacturing a honeycomb structure of the present invention, when hydrothermal treatment is performed in the firing step, the temperature of the firing step is desirably 800 to 1000 ° C., and more desirably 800 to 900 ° C.
本発明のハニカム構造体の製造方法において、水熱処理が焼成工程において行われる場合、焼成工程の時間は、１～２４時間が望ましく、５～１５時間がより望ましい。 In the method for manufacturing a honeycomb structure of the present invention, when hydrothermal treatment is performed in the firing step, the firing step time is preferably 1 to 24 hours, and more preferably 5 to 15 hours.
本発明のハニカム構造体の製造方法において、水熱処理が焼成工程において行われる場合、焼成工程の雰囲気は、水蒸気濃度が１～２０体積％であることが望ましく、水蒸気濃度が５～１５体積％であることがより望ましい。 In the method for manufacturing a honeycomb structure of the present invention, when the hydrothermal treatment is performed in the firing step, 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.
（担持工程）
本発明のハニカム構造体の製造方法は、上記隔壁の表面に三元触媒を担持させる担持工程をさらに含むことが望ましい。
三元触媒とは、主に炭化水素（ＨＣ）、一酸化炭素（ＣＯ）及び窒素酸化物（ＮＯｘ）を浄化する触媒をいう。三元触媒としては、例えば、白金、パラジウム、ロジウム等の貴金属が挙げられる。また、これらの貴金属をアルミナ等の耐熱性無機酸化物からなる担体に担持させたものを三元触媒として用いることもできる。 (Supporting process)
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). Examples of the three-way catalyst include noble metals such as platinum, palladium, and rhodium. Moreover, what carried | supported these noble metals on the support | carrier which consists of heat resistant inorganic oxides, such as an alumina, can also be used as a three-way catalyst.
隔壁の表面に三元触媒を担持する方法としては、例えば、三元触媒を含むスラリーにハニカム焼成体又はハニカム構造体を浸漬した後、引き上げて加熱する方法等が挙げられる。
ハニカム構造体が外周コート層を備える場合、外周コート層を形成する前のハニカム焼成体の隔壁の表面に三元触媒を担持してもよいし、外周コート層を形成した後のハニカム焼成体又はハニカム構造体の隔壁の表面に三元触媒を担持してもよい。また、ハニカム構造体が接着層を備える場合、接着層を形成する前のハニカム焼成体の隔壁の表面に三元触媒を担持してもよいし、接着層を形成した後のハニカム焼成体又はハニカム構造体の隔壁の表面に三元触媒を担持してもよい。 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.
When 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. When the honeycomb structure includes an adhesive layer, 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.
本発明のハニカム構造体の製造方法において、担持工程では、三元触媒の担持量が０．１～１５ｇ／Ｌであることが望ましく、１～１０ｇ／Ｌであることがより望ましい。
本明細書において、三元触媒の担持量とは、ハニカム構造体の見掛けの体積当たりの三元触媒の重量をいう。なお、ハニカム構造体の見掛けの体積は、空隙の体積を含む体積であり、外周コート層及び／又は接着層の体積を含むこととする。 In the method for manufacturing a honeycomb structured body of the present invention, in the supporting step, the supported amount of the three-way catalyst is preferably 0.1 to 15 g / L, and more preferably 1 to 10 g / L.
In this specification, 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.
（その他の工程）
本発明のハニカム構造体の製造方法において、ハニカム焼成体の外周面に外周コート層を形成する場合、外周コート層は、ハニカム焼成体の両端面を除く外周面に外周コート層用ペーストを塗布した後、乾燥固化することにより形成することができる。 (Other processes)
In the method for manufacturing a honeycomb structured body of the present invention, when 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.
本発明のハニカム構造体の製造方法において、複数個のハニカム焼成体が接着層を介して接着されてなるハニカム構造体は、複数個のハニカム焼成体の両端面を除く外周面に接着層用ペーストを塗布して、接着させた後、乾燥固化することにより作製することができる。 In the method for manufacturing a honeycomb structured body according to the present invention, 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.
（実施例）
以下、本発明をより具体的に開示した実施例を示す。なお、本発明は、以下の実施例のみに限定されるものではない。 (Example)
Examples in which the present invention is disclosed more specifically are shown below. In addition, this invention is not limited only to a following example.
［評価用サンプルの作製］
（実施例１）
Ｃｕ源としてＣｕＯ（平均粒子径：２μｍ）を１重量部、β型ゼオライト（ＳｉＯ２／Ａｌ２Ｏ３モル比：４０、平均粒子径：２μｍ）を４０重量部、無機バインダとしてベーマイトを１０．５重量部、平均繊維径が３μｍ、平均繊維長が１２０μｍのアルミナ繊維を７．５重量部、有機バインダとしてメチルセルロースを５重量部、成形助剤としてオレイン酸を５重量部及びイオン交換水を３１重量部混合混練して、原料ペーストを作製した。 [Preparation of sample for evaluation]
Example 1
1 part by weight of CuO (average particle diameter: 2 μm) as a Cu source, 40 parts by weight of β-type zeolite (SiO 2 / Al 2 O 3 molar ratio: 40, average particle diameter: 2 μm), and boehmite as an inorganic binder 7.5 parts by weight of alumina fibers having an average fiber diameter of 3 μm and an average fiber length of 120 μm, 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.
押出成形機を用いて、原料ペーストを押出成形して、正四角柱状のハニカム成形体を作製した。そして、減圧マイクロ波乾燥機を用いて、ハニカム成形体を出力４０ｋＷ、減圧６．７ｋＰａで１７分間乾燥させた後、７００℃で３時間４０分脱脂・焼成することにより、ハニカム焼成体を作製した。ハニカム焼成体は、一辺が３３ｍｍ、長さが４３ｍｍの正四角柱状であり、貫通孔の密度が６２個／ｃｍ２、隔壁の厚さが０．３６ｍｍであった。 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.
得られたハニカム焼成体を、水蒸気濃度１０体積％、８５０℃、１０時間の条件で水熱処理を行った。水熱処理後のハニカム焼成体において、β型ゼオライトのＳｉＯ２／Ａｌ２Ｏ３モル比は２５０であった。β型ゼオライトのＳｉＯ２／Ａｌ２Ｏ３モル比は２９Ｓｉ－ＮＭＲにより測定した。以上により、実施例１の評価用サンプルを得た。 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. In the honeycomb fired body after the hydrothermal treatment, the SiO 2 / Al 2 O 3 molar ratio of β-type zeolite was 250. The SiO 2 / Al 2 O 3 molar ratio of β-type zeolite was measured by 29 Si-NMR. Thus, an evaluation sample of Example 1 was obtained.
（比較例１）
比較例１では、実施例１と同様の条件でハニカム焼成体を作製し、水熱処理を行わなかった。以上により、比較例１の評価用サンプルを得た。 (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.
（比較例２）
比較例２では、以下のように、Ｃｕ源を含まない原料ペーストを用いてハニカム焼成体を作製し、また、ハニカム焼成体の水熱処理を行わなかった。 (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.
β型ゼオライト（ＳｉＯ２／Ａｌ２Ｏ３モル比：４０、平均粒子径：２μｍ）を４０重量部、無機バインダとしてベーマイトを１０．５重量部、平均繊維径が３μｍ、平均繊維長が１２０μｍのアルミナ繊維を７．５重量部、有機バインダとしてメチルセルロースを５重量部、成形助剤としてオレイン酸を５重量部及びイオン交換水を３２重量部混合混練して、原料ペーストを作製した。 40 parts by weight of β-type zeolite (SiO 2 / Al 2 O 3 molar ratio: 40, average particle diameter: 2 μm), 10.5 parts by weight of boehmite as an inorganic binder, an average fiber diameter of 3 μm, and an average fiber length of 120 μm 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.
押出成形機を用いて、原料ペーストを押出成形して、正四角柱状のハニカム成形体を作製した。そして、減圧マイクロ波乾燥機を用いて、ハニカム成形体を出力４０ｋＷ、減圧６．７ｋＰａで１７分間乾燥させた後、７００℃で３時間４０分脱脂・焼成することにより、ハニカム焼成体を作製した。ハニカム焼成体は、一辺が３３ｍｍ、長さが４３ｍｍの正四角柱状であり、貫通孔の密度が６２個／ｃｍ２、隔壁の厚さが０．３６ｍｍであった。以上により、比較例２の評価用サンプルを得た。 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. Thus, an evaluation sample of Comparative Example 2 was obtained.
［炭化水素の放出量の測定］
前処理として、実施例１、比較例１及び比較例２の評価用サンプルをＮ２ガス雰囲気中で４５０℃、３０分間保持した後、ＣＯを０．３体積％含むＮ２ガス雰囲気中で４５０℃、２分間保持した。前処理後の評価用サンプルに対し、プロピレンを１１２５ｐｐｍＣ、プロパンを３７５ｐｐｍＣ、ＣＯを０．２体積％、Ｈ２Ｏを１０体積％、Ｏ２を２０体積％含み、残部がＮ２であるガスを３０℃で３０秒間流通させることにより、炭化水素（ＨＣ）であるプロピレン及びプロパンを吸着させた。その後、Ｈ２Ｏを１０体積％含み、残部がＮ２であるガスに切り替え、６０℃／分の速度で４５０℃まで昇温した。その際、評価用サンプルから流出するガスの全炭化水素（ＴＨＣ）を測定し、その値を評価用サンプルからの炭化水素の放出量とした。 [Measurement of hydrocarbon emissions]
As a pretreatment, 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. With respect to the sample for evaluation after the pretreatment, 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. Thereafter, 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. At that time, 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.
図４は、温度と炭化水素の放出量との関係を示すグラフである。
図４より、比較例１では、比較例２に比べて高温側で炭化水素が放出されるものの、炭化水素の放出量は少ないことが確認された。また、実施例１では、比較例１ほどではないが比較例２に比べて高温側で炭化水素が放出されること、及び、比較例１及び比較例２に比べて炭化水素の放出量が多いことが確認された。
以上の結果から、Ｃｕ源を含む原料ペーストを用いてハニカム焼成体を作製し、かつ、ハニカム焼成体の水熱処理を行うことにより、炭化水素の吸着性能に優れたハニカム構造体を製造することができると考えられる。 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.
［吸水変位量の測定］
実施例１及び比較例２の評価用サンプルを水に浸漬し、吸水率を所定の値としたときの体積変化率［％］を求め、その値を吸水変位量とした。吸水率は、電子天秤（Ａ＆Ｄ製　ＨＲ２０２ｉ）を用いて、絶乾時の重量と吸水時の重量とを測定することにより算出した。 [Measurement of water absorption displacement]
The samples for evaluation of 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).
図５は、吸水率と吸水変位量との関係を示すグラフである。
図５より、実施例１では、比較例２に比べて吸水変位量が小さいことが確認された。この結果から、Ｃｕ源を含む原料ペーストを用いてハニカム焼成体を作製し、かつ、ハニカム焼成体の水熱処理を行うことにより、β型ゼオライトに水分が吸着しにくくなり、水分の吸着／脱離による体積の収縮／膨張が抑制されると考えられる。 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 β-type zeolite, and moisture adsorption / desorption It is thought that the shrinkage / expansion of the volume due to is suppressed.
　１０，２０　　　ハニカム構造体
　１１，２１　　　ハニカム焼成体
　１１ａ，２１ａ　貫通孔
　１１ｂ，２１ｂ　隔壁
　１２，２２　　　外周コート層
　２３　　　　　　接着層 DESCRIPTION OF SYMBOLS 10,20 Honeycomb structure 11,21 Honeycomb fired body 11a, 21a Through- hole 11b, 21b Partition 12, 22, Outer peripheral coat layer 23 Adhesive layer

Claims (14)

  1. 複数の貫通孔が隔壁を隔てて長手方向に並設されたハニカム焼成体を備えたハニカム構造体の製造方法であって、
    Ｃｕ源とβ型ゼオライトと無機バインダとを含む原料ペーストを成形することにより、複数の貫通孔が隔壁を隔てて長手方向に並設されたハニカム成形体を作製する成形工程と、
    前記ハニカム成形体を焼成することにより、ハニカム焼成体を作製する焼成工程と、
    を含み、
    前記成形工程の前、前記焼成工程の後、又は、前記焼成工程において、水熱処理が行われることを特徴とするハニカム構造体の製造方法。     A method for manufacturing a honeycomb structure including a honeycomb fired body in which a plurality of through holes are arranged in parallel in a longitudinal direction with a partition wall therebetween,
    A forming step of forming a honeycomb formed body in which a plurality of through holes are arranged in parallel in the longitudinal direction with partition walls formed by forming a raw material paste containing a Cu source, β-type zeolite, and an inorganic binder,
    A firing step for producing a honeycomb fired body by firing the honeycomb formed body,
    Including
    A method for manufacturing a honeycomb structured body, wherein hydrothermal treatment is performed before the forming step, after the firing step, or in the firing step.
  2. 前記水熱処理は、前記成形工程の前に、前記Ｃｕ源及び前記β型ゼオライトを水熱処理する原料水熱処理工程において行われる請求項１に記載のハニカム構造体の製造方法。 The method for manufacturing a honeycomb structure according to claim 1, wherein the hydrothermal treatment is performed in a raw material hydrothermal treatment step of hydrothermally treating the Cu source and the β-type zeolite before the forming step.
  3. 前記原料水熱処理工程が、温度：８００～１０００℃、時間：１～２４時間、雰囲気：水蒸気濃度１～２０体積％で行われる請求項２に記載のハニカム構造体の製造方法。 The method for manufacturing a honeycomb structured body according to claim 2, wherein the raw hydrothermal treatment 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.
  4. 前記水熱処理は、前記焼成工程の後に、前記ハニカム焼成体を水熱処理するハニカム焼成体水熱処理工程において行われる請求項１に記載のハニカム構造体の製造方法。 The method for manufacturing a honeycomb structured body according to claim 1, wherein the hydrothermal treatment is performed in a honeycomb fired body hydrothermal treatment step of hydrothermally treating the honeycomb fired body after the firing step.
  5. 前記ハニカム焼成体水熱処理工程が、温度：８００～１０００℃、時間：１～２４時間、雰囲気：水蒸気濃度１～２０体積％で行われる請求項４に記載のハニカム構造体の製造方法。 The method for manufacturing a honeycomb structured body according to claim 4, wherein the honeycomb fired body hydrothermal treatment 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.
  6. 前記水熱処理は、前記焼成工程において、前記ハニカム成形体の焼成と同時に行われる請求項１に記載のハニカム構造体の製造方法。 The method for manufacturing a honeycomb structured body according to claim 1, wherein the hydrothermal treatment is performed simultaneously with the firing of the honeycomb formed body in the firing step.
  7. 前記焼成工程が、温度：８００～１０００℃、時間：１～２４時間、雰囲気：水蒸気濃度１～２０体積％で行われる請求項６に記載のハニカム構造体の製造方法。 The method for manufacturing a honeycomb structured body according to claim 6, wherein 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.
  8. 前記Ｃｕ源は、Ｃｕ化合物である請求項１～７のいずれか１項に記載のハニカム構造体の製造方法。 The method for manufacturing a honeycomb structured body according to any one of claims 1 to 7, wherein the Cu source is a Cu compound.
  9. 前記原料ペーストに含まれる前記Ｃｕ化合物の量は、Ｃｕ換算で、前記β型ゼオライトに対して１～７重量％である請求項８に記載のハニカム構造体の製造方法。 The method for manufacturing a honeycomb structured body according to claim 8, wherein an amount of the Cu compound contained in the raw material paste is 1 to 7% by weight with respect to the β-type zeolite in terms of Cu.
  10. 前記Ｃｕ源は、Ｃｕイオンであり、
    前記Ｃｕ源及び前記β型ゼオライトとして、Ｃｕイオンによりイオン交換されたβ型ゼオライトを用いる請求項１～７のいずれか１項に記載のハニカム構造体の製造方法。     The Cu source is Cu ions,
    The method for manufacturing a honeycomb structured body according to any one of claims 1 to 7, wherein β-type zeolite ion-exchanged with Cu ions is used as the Cu source and the β-type zeolite.
  11. 前記β型ゼオライトの前記Ｃｕイオンによりイオン交換されている量は、１～７重量％である請求項１０に記載のハニカム構造体の製造方法。 The method for manufacturing a honeycomb structured body according to claim 10, wherein an amount of the β-type zeolite ion-exchanged by the Cu ions is 1 to 7% by weight.
  12. 前記β型ゼオライトのＳｉＯ２／Ａｌ２Ｏ３モル比は、１０～１５０である請求項１～１１のいずれか１項に記載のハニカム構造体の製造方法。 The method for manufacturing a honeycomb structured body according to any one of claims 1 to 11, wherein the β-type zeolite has a SiO 2 / Al 2 O 3 molar ratio of 10 to 150.
  13. 前記原料ペーストは、無機繊維をさらに含む請求項１～１２のいずれか１項に記載のハニカム構造体の製造方法。 The method for manufacturing a honeycomb structured body according to any one of claims 1 to 12, wherein the raw material paste further includes inorganic fibers.
  14. 前記隔壁の表面に三元触媒を担持させる担持工程をさらに含む請求項１～１３のいずれか１項に記載のハニカム構造体の製造方法。 The method for manufacturing a honeycomb structured body according to any one of claims 1 to 13, further comprising a supporting step of supporting a three-way catalyst on a surface of the partition wall.
PCT/JP2017/010897 2016-03-22 2017-03-17 Honeycomb structure production method WO2017164110A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008080194A (en) * 2006-09-26 2008-04-10 Tosoh Corp Hydrocarbon adsorbent composed of beta-type zeolite
JP2011125846A (en) * 2009-11-19 2011-06-30 Ibiden Co Ltd Honeycomb structure and apparatus for cleaning exhaust gas
JP2011207749A (en) * 2010-03-12 2011-10-20 Ngk Insulators Ltd Zeolite structure and method for producing the same
JP2012213754A (en) * 2011-03-29 2012-11-08 Ibiden Co Ltd Honeycomb structure and exhaust gas-cleaning device
WO2015145181A1 (en) * 2014-03-27 2015-10-01 Johnson Matthey Public Limited Company Process for producing a catalyst and catalyst as such

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008080194A (en) * 2006-09-26 2008-04-10 Tosoh Corp Hydrocarbon adsorbent composed of beta-type zeolite
JP2011125846A (en) * 2009-11-19 2011-06-30 Ibiden Co Ltd Honeycomb structure and apparatus for cleaning exhaust gas
JP2011207749A (en) * 2010-03-12 2011-10-20 Ngk Insulators Ltd Zeolite structure and method for producing the same
JP2012213754A (en) * 2011-03-29 2012-11-08 Ibiden Co Ltd Honeycomb structure and exhaust gas-cleaning device
WO2015145181A1 (en) * 2014-03-27 2015-10-01 Johnson Matthey Public Limited Company Process for producing a catalyst and catalyst as such

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