WO2011061836A1 - ハニカム構造体及び排ガス浄化装置 - Google Patents

ハニカム構造体及び排ガス浄化装置 Download PDF

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WO2011061836A1
WO2011061836A1 PCT/JP2009/069656 JP2009069656W WO2011061836A1 WO 2011061836 A1 WO2011061836 A1 WO 2011061836A1 JP 2009069656 W JP2009069656 W JP 2009069656W WO 2011061836 A1 WO2011061836 A1 WO 2011061836A1
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Prior art keywords
honeycomb structure
honeycomb
structure according
phosphate
zeolite
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PCT/JP2009/069656
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English (en)
French (fr)
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陽介 松川
真之助 後藤
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イビデン株式会社
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Priority to CN200980162507.4A priority Critical patent/CN102666430B/zh
Priority to PCT/JP2009/069656 priority patent/WO2011061836A1/ja
Priority to EP10175407.5A priority patent/EP2324920B1/en
Priority to US12/910,876 priority patent/US8658104B2/en
Publication of WO2011061836A1 publication Critical patent/WO2011061836A1/ja

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    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
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    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32—Ceramic
    • C04B2237/38—Fiber or whisker reinforced
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/02—Adding substances to exhaust gases the substance being ammonia or urea
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • F01N3/2066—Selective catalytic reduction [SCR]
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • F01N3/2825—Ceramics
    • F01N3/2828—Ceramic multi-channel monoliths, e.g. honeycombs

Definitions

  • the present invention relates to a honeycomb structure and an exhaust gas purification apparatus having the honeycomb structure.
  • an SCR Selective Catalytic Reduction system that uses ammonia to reduce NOx to nitrogen and water has been known as one of systems for purifying automobile exhaust gas.
  • zeolite is known as a material that adsorbs ammonia in the SCR system.
  • the honeycomb unit includes inorganic particles and inorganic fibers and / or whiskers, and the inorganic particles are one or more selected from the group consisting of alumina, silica, zirconia, titania, ceria, mullite, and zeolite.
  • a honeycomb structure is disclosed.
  • the present invention has been made in view of the above-described problems of the prior art, and an object of the present invention is to provide a honeycomb structure and an exhaust gas purification device that are excellent in NOx purification performance.
  • a honeycomb structure of the present invention includes a honeycomb unit including a phosphate-based zeolite and an inorganic binder, and a plurality of through holes arranged in parallel in a longitudinal direction with a partition wall therebetween.
  • the average pore diameter is 0.1 ⁇ m or more and 0.3 ⁇ m or less, and the porosity is 30% or more and 40% or less.
  • the phosphate zeolite is preferably at least one selected from the group consisting of SAPO, MeAPO, and MeAPSO. *
  • the SAPO is preferably one or more selected from the group consisting of SAPO-5, SAPO-11, and SAPO-34. *
  • the phosphate-based zeolite preferably includes zeolite ion-exchanged with Cu and / or Fe.
  • the inorganic binder is preferably a solid content contained in one or more selected from the group consisting of alumina sol, silica sol, titania sol, water glass, sepiolite, attapulgite and boehmite. *
  • the honeycomb unit preferably further includes inorganic fibers and / or scaly substances.
  • the inorganic fiber is at least one selected from the group consisting of alumina, silica, silicon carbide, silica alumina, glass, potassium titanate and aluminum borate, and the scaly substance includes glass, muscovite, alumina, silica and It is desirable to be at least one selected from the group consisting of zinc oxide.
  • the honeycomb structure of the present invention preferably includes a plurality of the honeycomb units.
  • the exhaust gas purification apparatus of the present invention has the honeycomb structure of the present invention.
  • FIG. Fig. 4 is a perspective view showing a honeycomb unit constituting the honeycomb structure of Fig. 3.
  • FIG. 1 shows an example of the honeycomb structure of the present invention.
  • the honeycomb structure 10 includes a phosphate-based zeolite as inorganic particles and an inorganic binder, and an outer peripheral surface of a single honeycomb unit 11 in which a plurality of through holes 11a are arranged in parallel in the longitudinal direction with a partition wall 11b interposed therebetween.
  • An outer peripheral coat layer 12 is formed on the outer periphery.
  • the average pore diameter of the macropores in the honeycomb unit 11 is 0.1 to 0.3 ⁇ m.
  • the average pore diameter of the macropores is less than 0.1 ⁇ m, the exhaust gas does not easily penetrate into the partition walls 11b, and thus the phosphate zeolite is not effectively used for the purification of NOx.
  • the average pore diameter of the macropores exceeds 0.3 ⁇ m, the number of pores in the honeycomb unit 11 is small, so that the exhaust gas hardly penetrates into the partition walls 11b, and the phosphate-based zeolite is used for purification of NOx. It will not be used effectively.
  • the pore size distribution of the honeycomb unit 11 includes a peak of micropores derived from phosphoric acid-based zeolite and a peak of macropores inside the partition walls 11b.
  • the porosity of the honeycomb unit 11 is 30 to 40%.
  • the porosity of the honeycomb unit 11 is less than 30%, the exhaust gas does not easily penetrate into the partition walls 11b, and thus the phosphate zeolite is not effectively used for purifying NOx.
  • the porosity of the honeycomb unit 11 exceeds 40%, the content of phosphate-based zeolite in the honeycomb unit 11 decreases, and the NOx purification rate decreases.
  • the average pore diameter and porosity of the honeycomb unit 11 can be measured using a mercury intrusion method.
  • phosphate zeolite examples include SAPO such as SAPO-5, SAPO-11, and SAPO-34; MeAPO; MeAPSO and the like.
  • the phosphate-based zeolite includes a phosphate-based zeolite ion-exchanged with Cu and / or Fe in consideration of NOx purification ability.
  • the phosphate-based zeolite may further include a phosphate-based zeolite that has not been ion-exchanged and a phosphate-based zeolite that has been ion-exchanged with a metal other than the above.
  • the phosphate zeolite ion-exchanged with Cu and / or Fe preferably has an ion exchange amount of 1.0 to 5.0% by mass.
  • the ion exchange amount of the phosphate zeolite is less than 1.0% by mass, the purification performance of NOx may be insufficient.
  • the ion exchange amount of the phosphate-based zeolite exceeds 5.0% by mass, the metal to be ion-exchanged may exist as an oxide and may not be ion-exchanged.
  • the average particle size of primary particles or secondary particles of phosphate zeolite is preferably 0.5 to 10 ⁇ m, and more preferably 1 to 5 ⁇ m.
  • the average particle size of the primary particles or secondary particles of the phosphate zeolite is less than 0.5 ⁇ m, the exhaust gas hardly penetrates into the partition wall 11b, and the phosphate zeolite is effective for purifying NOx. May not be used.
  • the average particle size of the primary particles or secondary particles of the phosphate-based zeolite exceeds 10 ⁇ m, the number of pores in the honeycomb unit 11 is reduced, so that the exhaust gas is less likely to penetrate into the partition walls 11b. In some cases, acid-based zeolites may not be effectively used for NOx purification.
  • the honeycomb unit 11 may further include zeolite other than phosphate zeolite such as ⁇ -type zeolite and ZSM-5-type zeolite.
  • zeolite other than phosphate zeolite such as ⁇ -type zeolite and ZSM-5-type zeolite.
  • the honeycomb unit 11 preferably has a zeolite content of 230 to 360 g / L per apparent volume. If the zeolite content per apparent volume is less than 230 g / L, the apparent volume of the honeycomb unit 11 may have to be increased in order to improve the NOx purification rate. On the other hand, if the zeolite content per apparent volume exceeds 360 g / L, the strength of the honeycomb unit 11 may be insufficient, or the aperture ratio of the honeycomb unit 11 may be reduced.
  • the inorganic binder contained in the honeycomb unit 11 is not particularly limited, and examples thereof include solids contained in alumina sol, silica sol, titania sol, water glass, sepiolite, attapulgite, boehmite and the like, and two or more kinds may be used in combination.
  • the content of the inorganic binder in the honeycomb unit 11 is preferably 5 to 30% by mass, and more preferably 10 to 20% by mass. When the content of the inorganic binder is less than 5% by mass, the strength of the honeycomb unit 11 may be reduced. On the other hand, when the content of the inorganic binder exceeds 30% by mass, extrusion of the honeycomb unit 11 may be difficult.
  • the honeycomb unit 11 preferably further includes inorganic fibers and / or scaly substances in order to improve the strength.
  • the inorganic fibers contained in the honeycomb unit 11 are not particularly limited as long as the strength of the honeycomb unit 11 can be improved, but alumina, silica, silicon carbide, silica alumina, glass, potassium titanate, aluminum borate Etc., and two or more of them may be used in combination.
  • the aspect ratio of the inorganic fiber is preferably 2 to 1000, more preferably 5 to 800, and particularly preferably 10 to 500.
  • the aspect ratio of the inorganic fiber is less than 2, the effect of improving the strength of the honeycomb unit 11 may be reduced.
  • the aspect ratio of the inorganic fiber exceeds 1000, the mold is clogged when the honeycomb unit 11 is extruded, or the inorganic fiber breaks and the effect of improving the strength of the honeycomb unit 11 is small. There are times when it becomes.
  • the scaly substance contained in the honeycomb unit 11 is not particularly limited as long as the strength of the honeycomb unit 11 can be improved, and examples thereof include glass, muscovite, alumina, silica, zinc oxide, and the like. You may use together.
  • the content of inorganic fibers and scaly substances in the honeycomb unit 11 is preferably 3 to 50% by mass, more preferably 3 to 30% by mass, and particularly preferably 5 to 20% by mass.
  • the content of the inorganic fibers and the scaly substance is less than 3% by mass, the effect of improving the strength of the honeycomb unit 11 may be reduced.
  • the content of inorganic fibers and scaly substances exceeds 50% by mass, the content of phosphate zeolite in the honeycomb unit 11 may decrease, and the NOx purification rate may decrease.
  • the honeycomb unit 11 preferably has an opening ratio of a cross section perpendicular to the longitudinal direction of 50 to 75%. If the opening ratio of the cross section perpendicular to the longitudinal direction is less than 50%, the phosphate zeolite may not be effectively used for NOx purification. On the other hand, when the opening ratio of the cross section perpendicular to the longitudinal direction exceeds 75%, the strength of the honeycomb unit 11 may be insufficient.
  • the density of the through holes 11a having a cross section perpendicular to the longitudinal direction is preferably 31 to 124 / cm 2 . If the density of the through holes 11a of the cross section perpendicular to the longitudinal direction is less than 31 / cm 2, less likely to contact exhaust gas and phosphate-based zeolite, the purification rate of NOx may decrease. On the other hand, when the density of the through holes 11a having a cross section perpendicular to the longitudinal direction exceeds 124 holes / cm 2 , the pressure loss of the honeycomb structure 10 may increase.
  • the thickness of the partition wall 11b of the honeycomb unit 11 is preferably 0.10 to 0.50 mm, and more preferably 0.15 to 0.35 mm. If the thickness of the partition wall 11b is less than 0.10 mm, the strength of the honeycomb unit 11 may be reduced. On the other hand, when the thickness of the partition wall 11b exceeds 0.50 mm, the exhaust gas hardly penetrates into the partition wall 11b, and the phosphate zeolite may not be effectively used for NOx purification.
  • the outer peripheral coat layer 12 preferably has a thickness of 0.1 to 2 mm. If the thickness of the outer peripheral coat layer 12 is less than 0.1 mm, the effect of improving the strength of the honeycomb structure 10 may be insufficient. On the other hand, if the thickness of the outer peripheral coat layer 12 exceeds 2 mm, the content of phosphate-based zeolite per unit volume of the honeycomb structure 10 may decrease, and the NOx purification rate may decrease.
  • the honeycomb structure 10 has a cylindrical shape, but is not particularly limited, and may have a prismatic shape, an elliptical column shape, or the like. Moreover, although the shape of the through-hole 11a is a quadrangular prism shape, it is not specifically limited, A triangular prism shape, a hexagonal column shape, etc. may be sufficient.
  • Extrusion molding is performed using a paste to produce a raw cylindrical honeycomb formed body in which a plurality of through holes are arranged in parallel in the longitudinal direction with a partition wall therebetween. Thereby, even if the firing temperature is lowered, the cylindrical honeycomb unit 11 having sufficient strength can be obtained.
  • the inorganic binder contained in the raw material paste is added as alumina sol, silica sol, titania sol, water glass, sepiolite, attapulgite, boehmite, etc., and two or more kinds may be used in combination.
  • an organic binder, a dispersion medium, a molding aid and the like may be appropriately added to the raw material paste as necessary.
  • the organic binder is not particularly limited, and examples thereof include methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, polyethylene glycol, phenol resin, and epoxy resin, and two or more kinds may be used in combination.
  • the addition amount of the organic binder is preferably 1 to 10% with respect to the total mass of the zeolite other than the phosphate zeolite, the inorganic binder, the inorganic fiber, the scaly substance, and the phosphate zeolite.
  • the dispersion medium is not particularly limited, and examples thereof include water, organic solvents such as benzene, alcohols such as methanol, and the like.
  • the molding aid is not particularly limited, and examples thereof include ethylene glycol, dextrin, fatty acid, fatty acid soap, polyalcohol and the like, and two or more kinds may be used in combination.
  • the raw material paste it is preferable 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 obtained honeycomb formed body is dried using a dryer such as a microwave dryer, a hot air dryer, a dielectric dryer, a vacuum dryer, a vacuum dryer, or a freeze dryer.
  • a dryer such as a microwave dryer, a hot air dryer, a dielectric dryer, a vacuum dryer, a vacuum dryer, or a freeze dryer.
  • the obtained honeycomb formed body is degreased.
  • the degreasing conditions are not particularly limited and can be appropriately selected depending on the type and amount of the organic substance contained in the molded body, but it is preferably 400 ° C. for 2 hours.
  • the firing temperature is preferably 600 to 1200 ° C, more preferably 600 to 1000 ° C.
  • the firing temperature is less than 600 ° C.
  • the sintering does not proceed and the strength of the honeycomb unit 11 may be lowered.
  • the firing temperature exceeds 1200 ° C., sintering proceeds too much, and the reaction sites of the phosphate zeolite may decrease.
  • the outer peripheral coat layer paste is applied to the outer peripheral surface of the columnar honeycomb unit 11.
  • the outer periphery coating layer paste may further contain an organic binder.
  • an organic binder Polyvinyl alcohol, methylcellulose, ethylcellulose, carboxymethylcellulose, etc. are mentioned, You may use 2 or more types together.
  • the outer peripheral coat layer paste contains an organic binder, it is preferably degreased.
  • the degreasing conditions can be appropriately selected depending on the kind and amount of the organic matter, but it is preferably 20 minutes at 700 ° C.
  • the phosphate zeolite can be ion-exchanged by immersing the honeycomb unit 11 in an aqueous solution containing Cu ions or Fe ions. Moreover, you may use the raw material paste containing the phosphate type zeolite ion-exchanged with Cu and / or Fe.
  • FIG. 2 shows an example of the exhaust gas purifying apparatus of the present invention.
  • the exhaust gas purification apparatus 100 is obtained by canning the metal tube 30 in a state where the holding sealing material 20 is disposed on the outer peripheral portion of the honeycomb structure 10.
  • the exhaust gas purification apparatus 100 is provided with injection means (not shown) such as an injection nozzle for injecting ammonia or a precursor thereof upstream of the honeycomb structure 10 with respect to the direction in which the exhaust gas flows.
  • injection means such as an injection nozzle for injecting ammonia or a precursor thereof upstream of the honeycomb structure 10 with respect to the direction in which the exhaust gas flows.
  • injection means such as an injection nozzle for injecting ammonia or a precursor thereof upstream of the honeycomb structure 10 with respect to the direction in which the exhaust gas flows.
  • injection means such as an injection nozzle for injecting ammonia or a precursor thereof upstream of the honeycomb structure 10 with respect to the direction in which the exhaust gas flows.
  • ammonia is added to the exhaust gas.
  • FIG. 3 shows a modification of the honeycomb structure 10.
  • the honeycomb structure 10 ′ has a configuration in which a plurality of honeycomb units 11 (see FIG. 4) in which a plurality of through holes 11a are arranged in parallel in the longitudinal direction with a partition wall 11b therebetween are bonded via an adhesive layer 13. This is the same as the honeycomb structure 10.
  • the honeycomb unit 11 preferably has a cross-sectional area of a cross section perpendicular to the longitudinal direction of 5 to 50 cm 2 .
  • the cross-sectional area of the cross section perpendicular to the longitudinal direction is less than 5 cm 2 , the pressure loss of the honeycomb structure 10 ′ may increase.
  • the cross-sectional area of the cross section perpendicular to the longitudinal direction exceeds 50 cm 2 , the strength against thermal stress generated in the honeycomb unit 11 may be insufficient.
  • the adhesive layer 13 preferably has a thickness of 0.5 to 2 mm. If the thickness of the adhesive layer 13 is less than 0.5 mm, the adhesive strength may be insufficient. On the other hand, when the thickness of the adhesive layer 13 exceeds 2 mm, the pressure loss of the honeycomb structure 10 ′ may increase.
  • the shape of the honeycomb unit 11 excluding the honeycomb unit 11 located on the outer peripheral portion of the honeycomb structure 10 ′ is a quadrangular column shape, but is not particularly limited, and may be, for example, a hexagonal column shape.
  • honeycomb structure 10 Next, an example of a method for manufacturing the honeycomb structure 10 'will be described. First, in the same manner as the honeycomb structure 10, a quadrangular columnar honeycomb unit 11 is manufactured. Next, an adhesive layer paste is applied to the outer peripheral surface of the honeycomb unit 11, the honeycomb units 11 are sequentially bonded, and dried and solidified, whereby an aggregate of the honeycomb units 11 is manufactured.
  • a honeycomb unit 11 having a columnar shape may be manufactured by bonding the honeycomb units 11 having a cross-section formed in a fan shape or a square shape.
  • the adhesive layer paste is not particularly limited, and examples thereof include a mixture of inorganic binder and inorganic particles, a mixture of inorganic binder and inorganic fibers, a mixture of inorganic binder, inorganic particles, and inorganic fibers.
  • the adhesive layer paste may contain an organic binder. Although it does not specifically limit as an organic binder, Polyvinyl alcohol, methylcellulose, ethylcellulose, carboxymethylcellulose, etc. are mentioned, You may use 2 or more types together.
  • the outer peripheral coat layer paste is applied to the outer peripheral surface of the aggregate of the cylindrical honeycomb units 11.
  • the outer periphery coating layer paste is not particularly limited, it may contain the same material as the adhesive layer paste or may contain a different material. Further, the outer peripheral coat layer paste may have the same composition as the adhesive layer paste.
  • a cylindrical honeycomb structure 10 ′ is obtained.
  • an organic binder is contained in the adhesive layer paste and / or the outer peripheral coat layer paste, it is preferable to degrease.
  • the degreasing conditions can be appropriately selected depending on the kind and amount of the organic matter, but it is preferably 20 minutes at 700 ° C.
  • outer peripheral coat layer 12 may not be formed in the honeycomb structures 10 and 10 ′.
  • Example 1 First, SAPO 3100 g having an average particle diameter of 3.3 ⁇ m, 875 g boehmite, 485 g alumina fiber having an average fiber diameter of 100 ⁇ m, 380 g methylcellulose, 280 g oleic acid, ion-exchanged with 2.7% by mass with Cu And 2425 g of ion-exchanged water was mixed and kneaded to prepare a raw material paste 1.
  • the raw material paste 1 was extrusion-molded using an extruder, and a raw regular quadrangular prism-shaped honeycomb formed body was produced. Then, the honeycomb formed body was dried at 110 ° C. for 10 minutes using a microwave dryer and a hot air dryer, and then degreased at 400 ° C. for 5 hours. Next, the honeycomb unit 11 was fired at 700 ° C. for 2 hours to form a square prism-shaped honeycomb unit 11 having a side of 34.3 mm and a length of 150 mm.
  • the honeycomb unit 11 had a density of through-holes 11a of 93 / cm 2 , a partition wall 11b thickness of 0.23 mm, an average pore diameter of macropores of 0.20 ⁇ m, and a porosity of 35%.
  • the average pore diameter and porosity of the macropores were measured using a mercury porosimeter.
  • alumina fibers having an average fiber diameter of 0.5 ⁇ m and an average fiber length of 15 ⁇ m, 2500 g of silica glass, 17 g of carboxymethylcellulose, 600 g of silica sol having a solid content of 30% by mass, 167 g of polyvinyl alcohol, 167 g of surfactant, and 17 g of alumina balloon Were mixed and kneaded to prepare a heat-resistant adhesive layer paste.
  • the adhesive layer paste was applied so that the thickness of the adhesive layer was 2 mm, the 16 honeycomb units 11 were adhered, the adhesive layer paste was dried and solidified at 150 ° C. for 10 minutes, and then using a diamond cutter, The honeycomb unit 11 was assembled by cutting into a cylindrical shape so that the cross section perpendicular to the longitudinal direction was substantially point-symmetric.
  • the adhesive layer paste is used by using a microwave dryer and a hot air dryer.
  • a microwave dryer and a hot air dryer was dried and solidified at 150 ° C. for 10 minutes and degreased at 400 ° C. for 2 hours to produce a cylindrical honeycomb structure 10 ′ having a diameter of 143.8 mm and a height of 150 mm.
  • the honeycomb structure 10 ′ is canned to the metal pipe (shell) 30 to produce an exhaust gas purification device (see FIG. 2). .
  • Example 2 SAPO 3100 g having an average particle diameter of 1.3 ⁇ m, 895 g of boehmite, 485 g of alumina fibers having an average fiber length of 100 ⁇ m, 420 g of methyl cellulose, 280 g of oleic acid, and ions ion-exchanged with Cu by 2.7% by mass
  • the raw material paste 2 was prepared by mixing and kneading 2600 g of exchange water.
  • a honeycomb structure 10 ′ and an exhaust gas purification device were produced in the same manner as in Example 1 except that the raw material paste 2 was used instead of the raw material paste 1.
  • the honeycomb unit 11 had an average pore diameter of macropores of 0.10 ⁇ m and a porosity of 35%.
  • SAPO 3100 g having an average particle diameter of 5.0 ⁇ m, boehmite 895 g, average fiber diameter 6 ⁇ m, average fiber length 100 ⁇ m alumina fiber 485 g, methylcellulose 350 g, oleic acid 280 g, and ions
  • the raw material paste 3 was prepared by mixing and kneading 2250 g of exchange water.
  • a honeycomb structure 10 ′ and an exhaust gas purification device were produced in the same manner as in Example 1 except that the raw material paste 3 was used instead of the raw material paste 1.
  • the honeycomb unit 11 had an average pore diameter of macropores of 0.30 ⁇ m and a porosity of 35%.
  • Example 4 SAPO 3100 g having an average particle size of 3.3 ⁇ m, 895 g boehmite, 485 g alumina fiber having an average fiber length of 100 ⁇ m, 350 g of methyl cellulose, 280 g of oleic acid and ions ionic exchanged with Cu by 2.7% by mass
  • the raw material paste 4 was produced by mixing and kneading 2250 g of exchange water.
  • a honeycomb structure 10 ′ and an exhaust gas purification device were produced in the same manner as in Example 1 except that the raw material paste 4 was used instead of the raw material paste 1.
  • the honeycomb unit 11 had an average pore diameter of macropores of 0.20 ⁇ m and a porosity of 30%.
  • Example 5 SAPO 3100 g having an average particle size of 3.3 ⁇ m, 895 g boehmite, 485 g of alumina fibers having an average fiber length of 100 ⁇ m, 420 g of methyl cellulose, 280 g of oleic acid and ions ion-exchanged with Cu by 2.7% by mass
  • the raw material paste 5 was prepared by mixing and kneading 2600 g of exchange water.
  • a honeycomb structure 10 ′ and an exhaust gas purification device were produced in the same manner as in Example 1 except that the raw material paste 5 was used instead of the raw material paste 1.
  • the honeycomb unit 11 had an average pore diameter of macropores of 0.20 ⁇ m and a porosity of 40%.
  • a honeycomb structure 10 ′ and an exhaust gas purification device were produced in the same manner as in Example 1 except that the raw material paste 6 was used instead of the raw material paste 1.
  • the honeycomb unit 11 had an average pore diameter of macro pores of 0.08 ⁇ m and a porosity of 32%.
  • a honeycomb structure 10 ′ and an exhaust gas purification device were produced in the same manner as in Example 1 except that the raw material paste 7 was used instead of the raw material paste 1.
  • the honeycomb unit 11 had an average pore diameter of macropores of 0.35 ⁇ m and a porosity of 38%.
  • a honeycomb structure 10 ′ and an exhaust gas purification device were manufactured in the same manner as in Example 1 except that the raw material paste 8 was used instead of the raw material paste 1.
  • the honeycomb unit 11 had an average pore diameter of macropores of 0.20 ⁇ m and a porosity of 43%.
  • the NOx purification rate [%] represented by The constituent components of the simulated gas are 175 ppm of nitric oxide, 175 ppm of nitrogen dioxide, 350 ppm of ammonia, 14% by volume of oxygen, 5% by volume of carbon dioxide, 10% by volume of water, and nitrogen (balance). The measurement results are shown in Table 1.
  • the honeycomb unit 11 has an average pore diameter of 0.1 to 0.3 ⁇ m and a porosity of 30 to 40%. It is considered that the NOx purification performance is excellent.
  • honeycomb structure 10 ′ is shown, but it is considered that the same effect can be obtained with the honeycomb structure 10.

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Abstract

　本発明のハニカム構造体は、リン酸塩系ゼオライトと、無機バインダとを含み、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ユニットを有し、前記ハニカムユニットは、マクロ気孔の平均気孔径が０．１μｍ以上０．３μｍ以下であり、気孔率が３０％以上４０％以下である。

Description

ハニカム構造体及び排ガス浄化装置
　本発明は、ハニカム構造体及びハニカム構造体を有する排ガス浄化装置に関する。
　従来、自動車の排ガスを浄化するシステムの一つとして、アンモニアを用いて、ＮＯｘを窒素と水に還元するＳＣＲ（Ｓｅｌｅｃｔｉｖｅ　Ｃａｔａｌｙｔｉｃ　Ｒｅｄｕｃｔｉｏｎ）システムが知られている。
　また、ＳＣＲシステムにおいて、アンモニアを吸着する材料として、ゼオライトが知られている。
　特許文献１には、ハニカムユニットが無機粒子と、無機繊維及び／又はウィスカを含んでなり、無機粒子は、アルミナ、シリカ、ジルコニア、チタニア、セリア、ムライト及びゼオライトからなる群より選択される一種以上であるハニカム構造体が開示されている。
国際公開第０６／１３７１４９号パンフレット
　しかしながら、特許文献１のハニカム構造体において、無機粒子がゼオライトである場合よりも高いＮＯｘの浄化性能が求められている。
　本発明は、上記の従来技術が有する問題に鑑み、ＮＯｘの浄化性能に優れるハニカム構造体及び排ガス浄化装置を提供することを目的とする。
　本発明のハニカム構造体は、リン酸塩系ゼオライトと、無機バインダとを含み、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ユニットを有し、前記ハニカムユニットは、マクロ気孔の平均気孔径が０．１μｍ以上０．３μｍ以下であり、気孔率が３０％以上４０％以下である。
前記リン酸塩系ゼオライトは、ＳＡＰＯ、ＭｅＡＰＯ及びＭｅＡＰＳＯからなる群より選択される一種以上であることが望ましい。　
前記ＳＡＰＯは、ＳＡＰＯ－５、ＳＡＰＯ－１１及びＳＡＰＯ－３４からなる群より選択される一種以上であることを特徴とすることが望ましい。　
前記リン酸塩系ゼオライトは、Ｃｕ及び／又はＦｅでイオン交換されているゼオライトを含むことが望ましい。　
前記無機バインダは、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、アタパルジャイト及びベーマイトからなる群より選択される一種以上に含まれる固形分であることが望ましい。　
前記ハニカムユニットは、無機繊維及び／又は鱗片状物質をさらに含むことが望ましい。　
前記無機繊維は、アルミナ、シリカ、炭化ケイ素、シリカアルミナ、ガラス、チタン酸カリウム及びホウ酸アルミニウムからなる群より選択される一種以上であり、鱗片状物質は、ガラス、白雲母、アルミナ、シリカ及び酸化亜鉛からなる群より選択される一種以上であることが望ましい。
　本発明のハニカム構造体は、前記ハニカムユニットを複数有することが望ましい。
本発明の排ガス浄化装置は、本発明のハニカム構造体を有する。
　本発明によれば、ＮＯｘの浄化性能に優れるハニカム構造体及び排ガス浄化装置を提供することができる。
本発明のハニカム構造体の一例を示す斜視図である。 本発明の排ガス浄化装置の一例を示す断面図である。 図１のハニカム構造体の変形例を示す斜視図である。 図３のハニカム構造体を構成するハニカムユニットを示す斜視図である。
　次に、本発明を実施するための形態を図面と共に説明する。
　図１に、本発明のハニカム構造体の一例を示す。ハニカム構造体１０は、無機粒子としてのリン酸塩系ゼオライトと、無機バインダとを含み、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ユニット１１の外周面に外周コート層１２が形成されている。
　ハニカムユニット１１のマクロ気孔の平均気孔径は、０．１～０．３μｍである。マクロ気孔の平均気孔径が０．１μｍ未満であると、排ガスが隔壁１１ｂの内部まで浸透しにくいため、リン酸塩系ゼオライトがＮＯｘの浄化に有効に利用されなくなる。一方、マクロ気孔の平均気孔径が０．３μｍを超えると、ハニカムユニット１１中の気孔の数が少ないため、排ガスが隔壁１１ｂの内部まで浸透しにくくなり、リン酸塩系ゼオライトがＮＯｘの浄化に有効に利用されなくなる。
　このとき、ハニカムユニット１１の気孔径分布には、リン酸系ゼオライト由来のミクロ気孔のピークと隔壁１１ｂの内部のマクロ気孔のピークが存在する。
　ハニカムユニット１１の気孔率は、３０～４０％である。ハニカムユニット１１の気孔率が３０％未満であると、排ガスが隔壁１１ｂの内部まで浸透しにくいため、リン酸塩系ゼオライトがＮＯｘの浄化に有効に利用されなくなる。一方、ハニカムユニット１１の気孔率が４０％を超えると、ハニカムユニット１１中のリン酸塩系ゼオライトの含有量が少なくなるため、ＮＯｘの浄化率が低下する。
　なお、ハニカムユニット１１の平均気孔径及び気孔率は、水銀圧入法を用いて測定することができる。
リン酸塩系ゼオライトとしては、ＳＡＰＯ－５、ＳＡＰＯ－１１、ＳＡＰＯ－３４等のＳＡＰＯ；ＭｅＡＰＯ；ＭｅＡＰＳＯ等が挙げられる。
　リン酸塩系ゼオライトは、ＮＯｘ浄化能を考慮すると、Ｃｕ及び／又はＦｅでイオン交換されているリン酸塩系ゼオライトを含むことが好ましい。なお、リン酸塩系ゼオライトは、イオン交換されていないリン酸塩系ゼオライト、上記以外の金属でイオン交換されたリン酸塩系ゼオライトをさらに含んでもよい。
　Ｃｕ及び／又はＦｅでイオン交換されたリン酸塩系ゼオライトは、イオン交換量が１．０～５．０質量％であることが好ましい。リン酸塩系ゼオライトのイオン交換量が１．０質量％未満であると、ＮＯｘの浄化性能が不十分となることがある。一方、リン酸塩系ゼオライトのイオン交換量が５．０質量％を超えると、イオン交換されるべき金属が酸化物として存在して、イオン交換されないことがある。
　リン酸塩系ゼオライトの一次粒子又は二次粒子の平均粒径は、０．５～１０μｍであることが好ましく、１～５μｍがさらに好ましい。リン酸塩系ゼオライトの一次粒子又は二次粒子の平均粒径が０．５μｍ未満であると、排ガスが隔壁１１ｂの内部まで浸透しにくくなって、リン酸塩系ゼオライトがＮＯｘの浄化に有効に利用されなくなることがある。一方、リン酸塩系ゼオライトの一次粒子又は二次粒子の平均粒径が１０μｍを超えると、ハニカムユニット１１中の気孔の数が少なくなるため、排ガスが隔壁１１ｂの内部まで浸透しにくくなり、リン酸塩系ゼオライトがＮＯｘの浄化に有効に利用されなくなることがある。
　ハニカムユニット１１は、β型ゼオライト、ＺＳＭ－５型ゼオライト等のリン酸塩系ゼオライト以外のゼオライトをさらに含んでもよい。
　ハニカムユニット１１は、見掛けの体積当たりのゼオライトの含有量が２３０～３６０ｇ／Ｌであることが好ましい。見掛けの体積当たりのゼオライトの含有量が２３０ｇ／Ｌ未満であると、ＮＯｘの浄化率を向上させるためにハニカムユニット１１の見掛けの体積を大きくしなければならないことがある。一方、見掛けの体積当たりのゼオライトの含有量が３６０ｇ／Ｌを超えると、ハニカムユニット１１の強度が不十分になること又はハニカムユニット１１の開口率が小さくなることがある。
　ハニカムユニット１１に含まれる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。
　ハニカムユニット１１の無機バインダの含有量は、５～３０質量％であることが好ましく、１０～２０質量％がさらに好ましい。無機バインダの含有量が５質量％未満であると、ハニカムユニット１１の強度が低下することがある。一方、無機バインダの含有量が３０質量％を超えると、ハニカムユニット１１の押出成形が困難になることがある。
　ハニカムユニット１１は、強度を向上させるために、無機繊維及び／又は鱗片状物質をさらに含むことが好ましい。
　ハニカムユニット１１に含まれる無機繊維としては、ハニカムユニット１１の強度を向上させることが可能であれば、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。
　無機繊維のアスペクト比は、２～１０００であることが好ましく、５～８００がさらに好ましく、１０～５００が特に好ましい。無機繊維のアスペクト比が２未満であると、ハニカムユニット１１の強度を向上させる効果が小さくなることがある。一方、無機繊維のアスペクト比が１０００を超えると、ハニカムユニット１１を押出成形する際に金型に目詰まり等が発生したり、無機繊維が折れて、ハニカムユニット１１の強度を向上させる効果が小さくなったりすることがある。
　ハニカムユニット１１に含まれる鱗片状物質としては、ハニカムユニット１１の強度を向上させることが可能であれば、特に限定されないが、ガラス、白雲母、アルミナ、シリカ、酸化亜鉛等が挙げられ、二種以上併用してもよい。
　ハニカムユニット１１の無機繊維及び鱗片状物質の含有量は、３～５０質量％であることが好ましく、３～３０質量％がさらに好ましく、５～２０質量％が特に好ましい。無機繊維及び鱗片状物質の含有量が３質量％未満であると、ハニカムユニット１１の強度を向上させる効果が小さくなることがある。一方、無機繊維及び鱗片状物質の含有量が５０質量％を超えると、ハニカムユニット１１中のリン酸塩系ゼオライトの含有量が低下して、ＮＯｘの浄化率が低下することがある。
　ハニカムユニット１１は、長手方向に垂直な断面の開口率が５０～７５％であることが好ましい。長手方向に垂直な断面の開口率が５０％未満であると、リン酸塩系ゼオライトがＮＯｘの浄化に有効に利用されなくなることがある。一方、長手方向に垂直な断面の開口率が７５％を超えると、ハニカムユニット１１の強度が不十分となることがある。
　ハニカムユニット１１は、長手方向に垂直な断面の貫通孔１１ａの密度が３１～１２４個／ｃｍ２であることが好ましい。長手方向に垂直な断面の貫通孔１１ａの密度が３１個／ｃｍ２未満であると、排ガスとリン酸塩系ゼオライトが接触しにくくなって、ＮＯｘの浄化率が低下することがある。一方、長手方向に垂直な断面の貫通孔１１ａの密度が１２４個／ｃｍ２を超えると、ハニカム構造体１０の圧力損失が増大することがある。
　ハニカムユニット１１の隔壁１１ｂの厚さは、０．１０～０．５０ｍｍであることが好ましく、０．１５～０．３５ｍｍがさらに好ましい。隔壁１１ｂの厚さが０．１０ｍｍ未満であると、ハニカムユニット１１の強度が低下することがある。一方、隔壁１１ｂの厚さが０．５０ｍｍを超えると、排ガスが隔壁１１ｂの内部まで浸透しにくくなって、リン酸塩系ゼオライトがＮＯｘの浄化に有効に利用されなくなることがある。
　外周コート層１２は、厚さが０．１～２ｍｍであることが好ましい。外周コート層１２の厚さが０．１ｍｍ未満であると、ハニカム構造体１０の強度を向上させる効果が不十分になることがある。一方、外周コート層１２の厚さが２ｍｍを超えると、ハニカム構造体１０の単位体積当たりのリン酸塩系ゼオライトの含有量が低下して、ＮＯｘの浄化率が低下することがある。
　ハニカム構造体１０は、円柱状であるが、特に限定されず、角柱状、楕円柱状等であってもよい。また、貫通孔１１ａの形状は、四角柱状であるが、特に限定されず、三角柱状、六角柱状等であってもよい。
　次に、ハニカム構造体１０の製造方法の一例について説明する。まず、リン酸塩系ゼオライト及び無機バインダを含み、必要に応じて、無機繊維及び／又は鱗片状物質、β型ゼオライト、ＺＳＭ－５型ゼオライト等のリン酸塩系ゼオライト以外のゼオライトをさらに含む原料ペーストを用いて押出成形し、複数の貫通孔が隔壁を隔てて長手方向に並設された生の円柱状のハニカム成形体を作製する。これにより、焼成温度を低くしても、十分な強度を有する円柱状のハニカムユニット１１が得られる。
　なお、原料ペーストに含まれる無機バインダは、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、ベーマイト等として添加されており、二種以上併用されていてもよい。
　また、原料ペーストには、有機バインダ、分散媒、成形助剤等を、必要に応じて、適宜添加してもよい。
　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。なお、有機バインダの添加量は、リン酸塩系ゼオライト、無機バインダ、無機繊維、鱗片状物質及びリン酸塩系ゼオライト以外のゼオライトの総質量に対して、１～１０％であることが好ましい。
　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。
　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。
　原料ペーストを調製する際には、混合混練することが好ましく、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。
　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、得られたハニカム成形体を乾燥する。
　さらに、得られたハニカム成形体を脱脂する。脱脂条件は、特に限定されず、成形体に含まれる有機物の種類や量によって適宜選択することができるが、４００℃で２時間であることが好ましい。
　次に、得られたハニカム成形体を焼成することにより、円柱状のハニカムユニット１１が得られる。焼成温度は、６００～１２００℃であることが好ましく、６００～１０００℃がさらに好ましい。焼成温度が６００℃未満であると、焼結が進行せず、ハニカムユニット１１の強度が低くなることがある。一方、焼成温度が１２００℃を超えると、焼結が進行しすぎて、リン酸塩系ゼオライトの反応サイトが減少することがある。
　次に、円柱状のハニカムユニット１１の外周面に外周コート層用ペーストを塗布する。
　外周コート層用ペーストとしては、特に限定されないが、無機バインダ及び無機粒子の混合物、無機バインダ及び無機繊維の混合物、無機バインダ、無機粒子及び無機繊維の混合物等が挙げられる。
　また、外周コート層用ペーストは、有機バインダをさらに含有してもよい。有機バインダとしては、特に限定されないが、ポリビニルアルコール、メチルセルロース、エチルセルロース、カルボキシメチルセルロース等が挙げられ、二種以上併用してもよい。
　次に、外周コート層用ペーストが塗布されたハニカムユニット１１を乾燥固化することにより、円柱状のハニカム構造体１０が得られる。このとき、外周コート層用ペーストに有機バインダが含まれている場合は、脱脂することが好ましい。脱脂条件は、有機物の種類や量によって適宜選択することができるが、７００℃で２０分間であることが好ましい。
　なお、ハニカムユニット１１をＣｕイオン又はＦｅイオンを含有する水溶液中に浸漬することにより、リン酸塩系ゼオライトをイオン交換することができる。また、Ｃｕ及び／又はＦｅでイオン交換されたリン酸塩系ゼオライトを含む原料ペーストを用いてもよい。
　図２に、本発明の排ガス浄化装置の一例を示す。排ガス浄化装置１００は、ハニカム構造体１０の外周部に保持シール材２０を配置した状態で、金属管３０にキャニングすることにより得られる。また、排ガス浄化装置１００には、排ガスの流れる方向に対して、ハニカム構造体１０の上流側に、アンモニア又はその前駆体を噴射する噴射ノズル等の噴射手段（不図示）が設けられている。これにより、排ガスにアンモニアが添加され、その結果、ハニカムユニット１１に含まれるリン酸塩系ゼオライト上で、排ガス中に含まれるＮＯｘが還元される。このとき、アンモニア又はその前駆体の貯蔵安定性を考慮すると、アンモニアの前駆体として、尿素水を用いることが好ましい。なお、尿素水は、排ガス中で加熱されることにより、加水分解し、アンモニアが発生する。
　図３に、ハニカム構造体１０の変形例を示す。なお、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ハニカムユニット１１（図４参照）が接着層１３を介して複数個接着されている以外は、ハニカム構造体１０と同様である。
　ハニカムユニット１１は、長手方向に垂直な断面の断面積が５～５０ｃｍ２であることが好ましい。長手方向に垂直な断面の断面積が５ｃｍ２未満であると、ハニカム構造体１０’の圧力損失が増大することがある。一方、長手方向に垂直な断面の断面積が５０ｃｍ２を超えると、ハニカムユニット１１に発生する熱応力に対する強度が不十分になることがある。
　接着層１３は、厚さが０．５～２ｍｍであることが好ましい。接着層１３の厚さが０．５ｍｍ未満であると、接着強度が不十分になることがある。一方、接着層１３の厚さが２ｍｍを超えると、ハニカム構造体１０’の圧力損失が増大することがある。
　また、ハニカム構造体１０’の外周部に位置するハニカムユニット１１を除くハニカムユニット１１の形状は、四角柱状であるが、特に限定されず、例えば、六角柱状等であってもよい。
　次に、ハニカム構造体１０’の製造方法の一例について説明する。まず、ハニカム構造体１０と同様にして、四角柱状のハニカムユニット１１を作製する。次に、ハニカムユニット１１の外周面に接着層用ペーストを塗布して、ハニカムユニット１１を順次接着させ、乾燥固化することにより、ハニカムユニット１１の集合体を作製する。
　このとき、ハニカムユニット１１の集合体を作製した後に、円柱状に切削加工し、研磨してもよい。また、断面が扇形状や正方形状に成形されたハニカムユニット１１を接着させて円柱状のハニカムユニット１１の集合体を作製してもよい。
　接着層用ペーストとしては、特に限定されないが、無機バインダ及び無機粒子の混合物、無機バインダ及び無機繊維の混合物、無機バインダ、無機粒子及び無機繊維の混合物等が挙げられる。
　また、接着層用ペーストは、有機バインダを含有してもよい。有機バインダとしては、特に限定されないが、ポリビニルアルコール、メチルセルロース、エチルセルロース、カルボキシメチルセルロース等が挙げられ、二種以上併用してもよい。
　次に、円柱状のハニカムユニット１１の集合体の外周面に外周コート層用ペーストを塗布する。外周コート層用ペーストは、特に限定されないが、接着層用ペーストと同じ材料を含有してもよいし、異なる材料を含有してもよい。また、外周コート層用ペーストは、接着層用ペーストと同一の組成であってもよい。
　次に、外周コート層用ペーストが塗布されたハニカムユニット１１の集合体を乾燥固化することにより、円柱状のハニカム構造体１０’が得られる。このとき、接着層用ペースト及び／又は外周コート層用ペーストに有機バインダが含まれている場合は、脱脂することが好ましい。脱脂条件は、有機物の種類や量によって適宜選択することができるが、７００℃で２０分間であることが好ましい。
　なお、ハニカム構造体１０及び１０’は、外周コート層１２が形成されていなくてもよい。
　［実施例１］
　まず、Ｃｕで２．７質量％イオン交換された、平均粒径が３．３μｍであるＳＡＰＯ３１００ｇ、ベーマイト８９５ｇ、平均繊維径が６μｍ、平均繊維長が１００μｍのアルミナ繊維４８５ｇ、メチルセルロース３８０ｇ、オレイン酸２８０ｇ及びイオン交換水２４２５ｇを混合混練して、原料ペースト１を作製した。
　次に、押出成形機を用いて、原料ペースト１を押出成形し、生の正四角柱状のハニカム成形体を作製した。そして、マイクロ波乾燥機及び熱風乾燥機を用いて、ハニカム成形体を１１０℃で１０分間乾燥させた後、４００℃で５時間脱脂した。次に、７００℃で２時間焼成し、一辺が３４．３ｍｍ、長さが１５０ｍｍの正四角柱状のハニカムユニット１１を作製した。
　ハニカムユニット１１は、貫通孔１１ａの密度が９３個／ｃｍ２、隔壁１１ｂの厚さが０．２３ｍｍ、マクロ気孔の平均気孔径が０．２０μｍ、気孔率が３５％であった。ここで、マクロ気孔の平均気孔径及び気孔率は、水銀ポロシメーターを用いて測定した。
　次に、平均繊維径が０．５μｍ、平均繊維長が１５μｍのアルミナ繊維７６７ｇ、シリカガラス２５００ｇ、カルボキシメチルセルロース１７ｇ、固形分３０質量％のシリカゾル６００ｇ、ポリビニルアルコール１６７ｇ、界面活性剤１６７ｇ及びアルミナバルーン１７ｇを混合混練して、耐熱性の接着層用ペーストを作製した。
　接着層の厚さが２ｍｍになるように接着層用ペーストを塗布して、ハニカムユニット１１を１６個接着させ、接着層用ペーストを１５０℃で１０分間乾燥固化した後、ダイヤモンドカッターを用いて、長手方向に垂直な断面が略点対称になるように円柱状に切削加工し、ハニカムユニット１１の集合体を作製した。
　さらに、ハニカムユニット１１の集合体の外周面に、外周コート層の厚さが１ｍｍになるように接着層用ペーストを塗布した後、マイクロ波乾燥機及び熱風乾燥機を用いて、接着層用ペーストを１５０℃で１０分間乾燥固化し、４００℃で２時間脱脂して、直径１４３．８ｍｍ、高さ１５０ｍｍの円柱状のハニカム構造体１０’を作製した。
　次に、ハニカム構造体１０’の外周部に保持シール材（無機繊維からなるマット）２０を配置した状態で、金属管（シェル）３０にキャニングし、排ガス浄化装置を作製した（図２参照）。
　［実施例２］
　Ｃｕで２．７質量％イオン交換された、平均粒径が１．３μｍであるＳＡＰＯ３１００ｇ、ベーマイト８９５ｇ、平均繊維径が６μｍ、平均繊維長が１００μｍのアルミナ繊維４８５ｇ、メチルセルロース４２０ｇ、オレイン酸２８０ｇ及びイオン交換水２６００ｇを混合混練して、原料ペースト２を作製した。
　原料ペースト１の代わりに、原料ペースト２を用いた以外は、実施例１と同様にして、ハニカム構造体１０’及び排ガス浄化装置を作製した。
　なお、ハニカムユニット１１は、マクロ気孔の平均気孔径が０．１０μｍ、気孔率が３５％であった。
　［実施例３］
　Ｃｕで２．７質量％イオン交換された、平均粒径が５．０μｍであるＳＡＰＯ３１００ｇ、ベーマイト８９５ｇ、平均繊維径が６μｍ、平均繊維長が１００μｍのアルミナ繊維４８５ｇ、メチルセルロース３５０ｇ、オレイン酸２８０ｇ及びイオン交換水２２５０ｇを混合混練して、原料ペースト３を作製した。
　原料ペースト１の代わりに、原料ペースト３を用いた以外は、実施例１と同様にして、ハニカム構造体１０’及び排ガス浄化装置を作製した。
　なお、ハニカムユニット１１は、マクロ気孔の平均気孔径が０．３０μｍ、気孔率が３５％であった。
　［実施例４］
　Ｃｕで２．７質量％イオン交換された、平均粒径が３．３μｍであるＳＡＰＯ３１００ｇ、ベーマイト８９５ｇ、平均繊維径が６μｍ、平均繊維長が１００μｍのアルミナ繊維４８５ｇ、メチルセルロース３５０ｇ、オレイン酸２８０ｇ及びイオン交換水２２５０ｇを混合混練して、原料ペースト４を作製した。
　原料ペースト１の代わりに、原料ペースト４を用いた以外は、実施例１と同様にして、ハニカム構造体１０’及び排ガス浄化装置を作製した。
　なお、ハニカムユニット１１は、マクロ気孔の平均気孔径が０．２０μｍ、気孔率が３０％であった。
　［実施例５］
　Ｃｕで２．７質量％イオン交換された、平均粒径が３．３μｍであるＳＡＰＯ３１００ｇ、ベーマイト８９５ｇ、平均繊維径が６μｍ、平均繊維長が１００μｍのアルミナ繊維４８５ｇ、メチルセルロース４２０ｇ、オレイン酸２８０ｇ及びイオン交換水２６００ｇを混合混練して、原料ペースト５を作製した。
　原料ペースト１の代わりに、原料ペースト５を用いた以外は、実施例１と同様にして、ハニカム構造体１０’及び排ガス浄化装置を作製した。
　なお、ハニカムユニット１１は、マクロ気孔の平均気孔径が０．２０μｍ、気孔率が４０％であった。
　［比較例１］
　Ｃｕで２．７質量％イオン交換された、平均粒径が１．３μｍであるＳＡＰＯ３１００ｇ、ベーマイト８９５ｇ、平均繊維径が６μｍ、平均繊維長が１００μｍのアルミナ繊維４８５ｇ、メチルセルロース３８０ｇ、オレイン酸２８０ｇ及びイオン交換水２４２５ｇを混合混練して、原料ペースト６を作製した。
　原料ペースト１の代わりに、原料ペースト６を用いた以外は、実施例１と同様にして、ハニカム構造体１０’及び排ガス浄化装置を作製した。
　なお、ハニカムユニット１１は、マクロ気孔の平均気孔径が０．０８μｍ、気孔率が３２％であった。
　［比較例２］
　Ｃｕで２．７質量％イオン交換された、平均粒径が５．５μｍであるＳＡＰＯ３１００ｇ、ベーマイト８９５ｇ、平均繊維径が６μｍ、平均繊維長が１００μｍのアルミナ繊維４８５ｇ、メチルセルロース３５０ｇ、オレイン酸２８０ｇ及びイオン交換水２２５０ｇを混合混練して、原料ペースト７を作製した。
　原料ペースト１の代わりに、原料ペースト７を用いた以外は、実施例１と同様にして、ハニカム構造体１０’及び排ガス浄化装置を作製した。
　なお、ハニカムユニット１１は、マクロ気孔の平均気孔径が０．３５μｍ、気孔率が３８％であった。
　［比較例３］
　Ｃｕで２．７質量％イオン交換された、平均粒径が３．３μｍであるＳＡＰＯ３１００ｇ、ベーマイト８９５ｇ、平均繊維径が６μｍ、平均繊維長が１００μｍのアルミナ繊維４８５ｇ、メチルセルロース４５０ｇ、オレイン酸２８０ｇ及びイオン交換水２７４０ｇを混合混練して、原料ペースト８を作製した。
　原料ペースト１の代わりに、原料ペースト８を用いた以外は、実施例１と同様にして、ハニカム構造体１０’及び排ガス浄化装置を作製した。
　なお、ハニカムユニット１１は、マクロ気孔の平均気孔径が０．２０μｍ、気孔率が４３％であった。
　［ＮＯｘの浄化率の測定］
　実施例１～５及び比較例１～３で作製したハニカム構造体１０’から、一辺が３４．３ｍｍ、長さが４０ｍｍの正四角柱状のハニカムユニット１１の一部を切り出し、評価用の試料とした。
　各評価用の試料に、１５０℃の模擬ガスを空間速度（ＳＶ）３５０００／ｈｒで流しながら、触媒評価装置ＳＩＧＵ（堀場製作所社製）を用いて、評価用の試料から流出する一酸化窒素（ＮＯ）の流出量を測定し、式
　（ＮＯの流入量－ＮＯの流出量）／（ＮＯの流入量）×１００
で表されるＮＯｘの浄化率［％］を測定した。なお、模擬ガスの構成成分は、一酸化窒素１７５ｐｐｍ、二酸化窒素１７５ｐｐｍ、アンモニア３５０ｐｐｍ、酸素１４体積％、二酸化炭素５体積％、水１０体積％、窒素（ｂａｌａｎｃｅ）である。測定結果を表１に示す。
Figure JPOXMLDOC01-appb-T000001
  
表１より、実施例１～５で作製したハニカム構造体１０’から切り出した評価用の試料は、ＮＯｘの浄化率が高いことがわかる。
　以上のことから、ハニカムユニット１１は、マクロ気孔の平均気孔径が０．１～０．３μｍであり、気孔率が３０～４０％であることにより、ハニカム構造体１０’及び排ガス浄化装置は、ＮＯｘの浄化性能に優れると考えられる。
　なお、本実施例では、ハニカム構造体１０’について示したが、ハニカム構造体１０についても同様の効果が得られると考えられる。
　１０、１０’　　ハニカム構造体
　１１　　ハニカムユニット
　１１ａ　　貫通孔
　１１ｂ　　隔壁
　１２　　外周コート層
　１３　　接着層
　２０　　保持シール材
　３０　　金属管
　１００　　排ガス浄化装置

Claims (9)

  1. 　リン酸塩系ゼオライトと、無機バインダとを含み、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ユニットを有するハニカム構造体であって、
    　前記ハニカムユニットは、マクロ気孔の平均気孔径が０．１μｍ以上０．３μｍ以下であり、気孔率が３０％以上４０％以下であることを特徴とするハニカム構造体。
  2. 前記リン酸塩系ゼオライトは、ＳＡＰＯ、ＭｅＡＰＯ及びＭｅＡＰＳＯからなる群より選択される一種以上であることを特徴とする請求項１に記載のハニカム構造体。
  3. 前記ＳＡＰＯは、ＳＡＰＯ－５、ＳＡＰＯ－１１及びＳＡＰＯ－３４からなる群より選択される一種以上であることを特徴とすることを特徴とする請求項２に記載のハニカム構造体。
  4. 前記リン酸塩系ゼオライトは、Ｃｕ及び／又はＦｅでイオン交換されているゼオライトを含むことを特徴とする請求項１乃至３のいずれか一項に記載のハニカム構造体。
  5. 　前記無機バインダは、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、アタパルジャイト及びベーマイトからなる群より選択される一種以上に含まれる固形分であることを特徴とする請求項１乃至４のいずれか一項に記載のハニカム構造体。
  6. 　前記ハニカムユニットは、無機繊維及び／又は鱗片状物質をさらに含むことを特徴とする請求項１乃至５のいずれか一項に記載のハニカム構造体。
  7. 前記無機繊維は、アルミナ、シリカ、炭化ケイ素、シリカアルミナ、ガラス、チタン酸カリウム及びホウ酸アルミニウムからなる群より選択される一種以上であり、　鱗片状物質は、ガラス、白雲母、アルミナ、シリカ及び酸化亜鉛からなる群より選択される一種以上であることを特徴とする請求項６に記載のハニカム構造体。
  8. 前記ハニカムユニットを複数有することを特徴とする請求項１乃至７のいずれか一項に記載のハニカム構造体。
  9. 請求項１乃至８のいずれか一項に記載のハニカム構造体を有することを特徴とする排ガス浄化装置。
PCT/JP2009/069656 2009-11-19 2009-11-19 ハニカム構造体及び排ガス浄化装置 WO2011061836A1 (ja)

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EP10175407.5A EP2324920B1 (en) 2009-11-19 2010-09-06 Honeycomb structural body and exhaust gas conversion apparatus
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