WO2011061841A1 - 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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Publication number
WO2011061841A1
WO2011061841A1 PCT/JP2009/069661 JP2009069661W WO2011061841A1 WO 2011061841 A1 WO2011061841 A1 WO 2011061841A1 JP 2009069661 W JP2009069661 W JP 2009069661W WO 2011061841 A1 WO2011061841 A1 WO 2011061841A1
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Prior art keywords
honeycomb structure
honeycomb
zeolite
exhaust gas
honeycomb unit
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PCT/JP2009/069661
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English (en)
French (fr)
Inventor
雅文 国枝
吉村　健
敏行 宮下
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イビデン株式会社
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Priority to PCT/JP2009/069661 priority Critical patent/WO2011061841A1/ja
Priority to CN200980162508.9A priority patent/CN102665910B/zh
Priority to EP10174634A priority patent/EP2324916A1/en
Priority to US12/891,710 priority patent/US8691157B2/en
Publication of WO2011061841A1 publication Critical patent/WO2011061841A1/ja
Priority to US14/184,079 priority patent/US8961886B2/en

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    • F01N3/023—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles
    • F01N3/0231—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles using special exhaust apparatus upstream of the filter for producing nitrogen dioxide, e.g. for continuous filter regeneration systems [CRT]
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    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
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    • F01N3/033—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
    • F01N3/035—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors, e.g. catalysed diesel particulate filters
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    • 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]

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.
  • Patent Document 1 as a method of treating exhaust gas generated by a stationary combustion source equipped with an SCR system, an ammonia emission is exposed to a noble metal catalyst on the downstream side of the SCR system.
  • a method is disclosed in which gaseous ammonia is reacted with oxygen to produce a reaction product having a higher oxidation state of nitrogen.
  • the honeycomb unit includes inorganic particles and inorganic fibers and / or whiskers, and the inorganic particles are selected from the group consisting of alumina, silica, zirconia, titania, ceria, mullite, and zeolite.
  • the inorganic particles are selected from the group consisting of alumina, silica, zirconia, titania, ceria, mullite, and zeolite.
  • honeycomb structures are disclosed.
  • Patent Document 1 has a problem that the arrangement space of the SCR system is increased because a noble metal catalyst is provided as a separate component on the downstream side of the SCR system.
  • the present invention provides a honeycomb structure capable of suppressing ammonia slip while suppressing NOx purification performance and suppressing an increase in the arrangement space of the SCR system.
  • An object is to provide an exhaust gas purification device.
  • the honeycomb structure of the present invention includes a honeycomb unit including a zeolite and an inorganic binder, and a plurality of through holes arranged in parallel in the longitudinal direction with a partition wall therebetween.
  • the noble metal catalyst is supported only in a region from 1.5% to 20% of the entire length from one end.
  • the zeolite is preferably ⁇ -type zeolite, ZSM-5-type zeolite, or phosphate-based zeolite. *
  • 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 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 purifying apparatus of the present invention has the honeycomb structure of the present invention, and the region on which the noble metal catalyst is supported is disposed on the downstream side with respect to the flow direction of the exhaust gas.
  • the exhaust gas purifying apparatus of the present invention is desirably used for an SCR system of a diesel engine.
  • the present invention it is possible to provide a honeycomb structure and an exhaust gas purifying apparatus capable of suppressing ammonia slip while suppressing NOx purification performance and suppressing an increase in the arrangement space of the SCR system. it can.
  • FIG. Fig. 4 is a perspective view showing a honeycomb unit constituting the honeycomb structure of Fig. 3. It is a figure which shows the evaluation method of an Example and a comparative example.
  • FIG. 1 shows an example of the honeycomb structure of the present invention.
  • the honeycomb structure 10 includes zeolite as inorganic particles and an inorganic binder, and an outer peripheral coating layer is formed on the 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. 12 is formed.
  • the honeycomb unit 11 has the noble metal catalyst supported only in the region A which is 1.5 to 20% of the entire length from one end in the longitudinal direction.
  • the region A in which the noble metal catalyst of the honeycomb unit 11 is supported is referred to as the region A of the honeycomb unit 11.
  • the exhaust gas purification device 100 can be obtained by performing canning on 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.
  • ammonia is added to the exhaust gas, and as a result, NOx contained in the exhaust gas is reduced on the zeolite contained in the honeycomb unit 11.
  • urea water is hydrolyzed and heated by being heated in the exhaust gas.
  • the area A of the honeycomb unit 11 is less than 1.5% of the total length from one end with respect to the longitudinal direction of the honeycomb unit 11, the effect of suppressing ammonia slip becomes insufficient.
  • the area A of the honeycomb unit 11 exceeds 20% of the total length from one end with respect to the longitudinal direction of the honeycomb unit 11, the NOx purification rate decreases.
  • the noble metal catalyst supported on the honeycomb unit 11 is not particularly limited as long as it can oxidize ammonia, and platinum, palladium, rhodium, and the like may be used, and two or more kinds may be used in combination.
  • the zeolite contained in the honeycomb unit 11 is not particularly limited, and examples thereof include ⁇ -type zeolite, ZSM-5-type zeolite, phosphate zeolite, and the like, and two or more kinds may be used in combination. Among them, phosphate zeolite is preferable because of its high NOx purification ability.
  • phosphate zeolite examples include SAPO such as SAPO-5, SAPO-11, and SAPO-34; MeAPO; MeAPSO and the like.
  • the zeolite preferably contains zeolite ion-exchanged with Cu and / or Fe in consideration of NOx purification ability.
  • the zeolite may further include zeolite that has not been ion-exchanged and zeolite that has been ion-exchanged with a metal other than those described above.
  • the zeolite ion-exchanged with Cu and / or Fe preferably has an ion exchange amount of 1.0 to 5.0% by mass. If the ion exchange amount is less than 1.0% by mass, the NOx purification performance may be insufficient, and if it exceeds 5.0% by mass, the metal to be ion exchanged exists as an oxide, Ion exchange may not occur.
  • the average particle diameter of the primary particles or secondary particles of the zeolite is preferably 0.5 to 10 ⁇ m, and more preferably 1 to 5 ⁇ m. If the average particle diameter of the primary particles or secondary particles of the zeolite is less than 0.5 ⁇ m, the exhaust gas hardly penetrates into the partition walls 11b, and the zeolite may not be effectively used for NOx purification. On the other hand, when the average particle size of the primary particles or secondary particles of the zeolite exceeds 10 ⁇ m, the number of pores in the honeycomb unit 11 decreases, so that the exhaust gas hardly penetrates into the partition walls 11b, and the zeolite purifies NOx. May not be used effectively.
  • 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 honeycomb unit 11 preferably has an inorganic binder content of 5 to 30% by mass, more preferably 10 to 20% by mass.
  • the content of the inorganic binder is less than 5% by mass, the strength of the honeycomb unit 11 may be reduced, and when it 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 the inorganic fibers and the scaly substance exceeds 50% by mass, the content of zeolite in the honeycomb unit 11 may decrease, and the NOx purification rate may decrease.
  • the honeycomb unit 11 preferably has a porosity of 25 to 40%. If the porosity of the honeycomb unit 11 is less than 25%, the exhaust gas hardly penetrates into the partition walls 11b, and the zeolite may not be effectively used for NOx purification. On the other hand, when the porosity of the honeycomb unit 11 exceeds 40%, the strength of the honeycomb unit 11 may be insufficient.
  • the porosity of the honeycomb unit 11 can be measured using a mercury intrusion method.
  • 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 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 .
  • the density of the through-holes 11a having a cross section perpendicular to the longitudinal direction is less than 31 / cm 2 , the exhaust gas and the zeolite are difficult to come into contact with each other, and the NOx purification rate may be lowered.
  • 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, if the thickness of the partition wall 11b exceeds 0.50 mm, the exhaust gas hardly penetrates into the partition wall 11b, and the 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 zeolite content 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.
  • the honeycomb structure 10 Next, an example of a method for manufacturing the honeycomb structure 10 will be described. First, it was extruded using a raw material paste containing zeolite and an inorganic binder, and further containing inorganic fibers and / or scaly substances, if necessary, and a plurality of through holes were arranged in parallel in the longitudinal direction with a partition wall therebetween. A raw cylindrical honeycomb formed body is produced. 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, the inorganic binder, the inorganic fiber, and the scaly substance.
  • 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 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 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 zeolite ion-exchanged with Cu and / or Fe.
  • a noble metal catalyst can be supported on the region A of the honeycomb unit 11 using an impregnation method or the like.
  • a carrier such as alumina carrying a noble metal catalyst may be carried in the region A of the honeycomb unit 11.
  • a noble metal catalyst may be supported. Further, the noble metal catalyst may be directly supported on the region A of the honeycomb unit 11.
  • 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 peripheral portion is a quadrangular prism shape, but is not particularly limited, and may be, for example, a hexagonal prism 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, 3100 g of SAPO 3g having an average particle diameter of 3 ⁇ m, 895 g of boehmite, 485 g of alumina fiber having an average fiber diameter of 6 ⁇ m and an average fiber length of 100 ⁇ m, 380 g of methylcellulose, 280 g of oleic acid and 2425 g of ion-exchanged water are mixed and kneaded to obtain a raw material paste 1 Was made.
  • the raw material paste 1 was extrusion-molded using an extrusion molding machine, and a raw regular quadrangular prism-shaped honeycomb molded body was manufactured. 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. In the honeycomb unit 11, the density of the through holes 11a was 93 / cm 2 , and the thickness of the partition walls 11b was 0.23 mm.
  • the zeolite was ion-exchanged with Cu ions by immersing the honeycomb unit 11 in an aqueous copper nitrate solution.
  • the ion exchange amount of the zeolite was determined by IPC emission analysis using ICPS-8100 (manufactured by Shimadzu Corporation) and found to be 2.7% by mass.
  • the platinum catalyst was supported by holding at 600 ° C. for 1 hour. At this time, the platinum catalyst content per apparent volume in the region A of the honeycomb unit 11 is 3 g / L.
  • 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 100 ′ (FIG. 2). reference).
  • the region A of the honeycomb unit 11 was arranged on the downstream side with respect to the flow direction of the exhaust gas.
  • Example 2 A honeycomb structure 10 ′ and an exhaust gas purification device 100 ′ were produced in the same manner as in Example 1 except that the length of the region A of the honeycomb unit 11 was changed to 5 mm.
  • Example 3 A honeycomb structure 10 ′ and an exhaust gas purification device 100 ′ were produced in the same manner as in Example 1 except that the length of the region A of the honeycomb unit 11 was changed to 25 mm.
  • the raw material paste is obtained by mixing and kneading 3000 g of ⁇ -type zeolite having an average particle diameter of 3 ⁇ m, 840 g of boehmite, 650 g of alumina fiber having an average fiber diameter of 6 ⁇ m and an average fiber length of 100 ⁇ m, 330 g of methylcellulose, 330 g of oleic acid and 1800 g of ion-exchanged water. 2 was produced.
  • a honeycomb structure 10 ′ and an exhaust gas purification device 100 ′ were produced in the same manner as in Example 2 except that the raw material paste 2 was used instead of the raw material paste 1.
  • Example 5 A honeycomb structure 10 ′ and an exhaust gas purification device 100 ′ were manufactured in the same manner as in Example 4 except that the zeolite unit was ion-exchanged with Fe ions by immersing the honeycomb unit 11 in an aqueous iron nitrate solution.
  • the ion exchange amount of the zeolite was determined by IPC emission analysis using ICPS-8100 (manufactured by Shimadzu Corporation) and found to be 2.7% by mass.
  • Example 6 A honeycomb structure 10 ′ and an exhaust gas purification device 100 ′ were produced in the same manner as in Example 5 except that the length of the region A of the honeycomb unit 11 was changed to 25 mm.
  • Example 7 SAPO 3100 g having an average particle diameter of 3 ⁇ m, 895 g boehmite, 485 g alumina fiber having an average fiber length of 100 ⁇ m, 380 g methylcellulose, 280 g oleic acid, and ion-exchanged water ion-exchanged with Cu by 2.7% by mass 2425 g was mixed and kneaded to prepare a raw material paste 3.
  • a honeycomb structure 10 ′ and an exhaust gas purification device 100 ′ were produced in the same manner as in Example 2 except that the raw material paste 3 was used instead of the raw material paste 1 and the honeycomb unit 11 was not immersed in the copper nitrate aqueous solution. did.
  • Example 8 3000 g ⁇ -type zeolite having an average particle diameter of 3 ⁇ m ion-exchanged with 2.7 mass% of Fe, 840 g boehmite, 650 g alumina fiber having an average fiber diameter of 6 ⁇ m and an average fiber length of 100 ⁇ m, 330 g of methylcellulose, 330 g of oleic acid, and The raw material paste 4 was produced by mixing and kneading 1800 g of ion-exchanged water.
  • a honeycomb structure 10 ′ and an exhaust gas purification device 100 ′ were produced in the same manner as in Example 2 except that the raw material paste 4 was used instead of the raw material paste 1 and the honeycomb unit 11 was not immersed in the aqueous copper nitrate solution. did.
  • Example 1 A honeycomb structure 10 ′ and an exhaust gas purification device 100 ′ were produced in the same manner as in Example 1 except that the length of the region A of the honeycomb unit 11 was changed to 2 mm.
  • Example 2 A honeycomb structure 10 ′ and an exhaust gas purification device 100 ′ were produced in the same manner as in Example 1 except that the platinum catalyst was not supported on the honeycomb unit 11.
  • Example 3 A honeycomb structure 10 ′ and an exhaust gas purification device 100 ′ were produced in the same manner as in Example 5 except that the length of the region A of the honeycomb unit 11 was changed to 2 mm.
  • Example 4 A honeycomb structure 10 ′ and an exhaust gas purification device 100 ′ were manufactured in the same manner as in Example 5 except that the platinum catalyst was not supported on the honeycomb unit 11.
  • Example 5 A honeycomb structure 10 ′ and an exhaust gas purification device 100 ′ were produced in the same manner as in Example 7 except that the platinum catalyst was not supported on the honeycomb unit 11.
  • Example 6 A honeycomb structure 10 ′ and an exhaust gas purification device 100 ′ were produced in the same manner as in Example 8 except that the platinum catalyst was not supported on the honeycomb unit 11.
  • a diesel engine (1.6 L direct injection engine) 200, a diesel oxidation catalyst (DOC) 300, a diesel particulate filter (DPF) 400, and Examples 1 to 8 are connected via an exhaust pipe.
  • each exhaust gas purification device 100 ′ of Comparative Examples 1 to 6 was connected in series and operated in a NEDC (New European Driving Cycle) mode.
  • the exhaust gas purifying apparatus 100 ′ has an average temperature of 160 ° C., an average space velocity (SV) of 20000 / hr, and a volume ratio of nitrogen dioxide to NOx in the exhaust gas of 0.25 to 0.30.
  • Urea water was injected only when the temperature was 180 ° C. or higher, and 6.0 g of ammonia was adsorbed in advance on the honeycomb structure 10 ′ of the exhaust gas purification apparatus 100 ′.
  • a gas detection pipe was installed on the downstream side of the exhaust gas purification apparatus 100 'to evaluate the presence or absence of ammonia slip.
  • a honeycomb structure (commercial product) having a diameter of 143.8 mm and a length of 100 mm and a honeycomb structure (commercial product) having a diameter of 143.8 mm and a length of 152.4 mm were used as the DOC 300 and the DPF 400, respectively.
  • Table 1 shows the NOx purification rate measurement results and ammonia slip evaluation results.
  • the exhaust gas purification apparatuses 100 ′ of Examples 1 to 8 can suppress ammonia slip while maintaining the NOx purification rate.
  • the exhaust gas purification apparatus 100 ′ of Comparative Examples 2 and 4 is further provided with a DOC on the downstream side via the exhaust pipe, ammonia slip can be suppressed.
  • the exhaust gas purifying apparatus 100 ′ of Comparative Examples 2 and 4 cannot suppress ammonia slip when the DOC is not installed on the downstream side via the exhaust pipe.
  • the exhaust gas purifying apparatus 100 ′ of Examples 1 to 8 does not need to install a DOC on the downstream side via the exhaust pipe, it can be understood that an increase in the arrangement space of the SCR system can be suppressed. .
  • the honeycomb unit 11 has the honeycomb structure 10 ′ by supporting the noble metal catalyst only in the region A which is 1.5 to 20% of the entire length from one end portion in the longitudinal direction. Further, it is understood that the exhaust gas purifying apparatus 100 ′ can suppress ammonia slip while maintaining NOx purification performance, and can suppress an increase in the arrangement space of the SCR system.
  • 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、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、前記長手方向に対して、一方の端部から全長の１．５％以上２０％以下である領域のみに貴金属触媒が担持されている。

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、ＳＣＲシステムを具備する定置燃焼源により発生される排気ガスを処理する方法として、ＳＣＲシステムの下流側で、アンモニア放出物を貴金属触媒にさらすことにより、貴金属触媒において、未反応気体アンモニアを酸素と反応させ、窒素の酸化状態がより高い反応生成物を生成する方法が開示されている。
　また、特許文献２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。
特開２００６－５１４９９号公報 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の方法は、ＳＣＲシステムの下流側で、別体として、貴金属触媒が設けられているため、ＳＣＲシステムの配置スペースが大きくなるという問題がある。
　また、特許文献２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の浄化性能を維持しながら、アンモニアスリップを抑制すると共に、ＳＣＲシステムの配置スペースが大きくなることを抑制することが可能な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、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、前記長手方向に対して、一方の端部から全長の１．５％以上２０％以下である領域のみに貴金属触媒が担持されている。
前記ゼオライトは、β型ゼオライト、ＺＳＭ－５型ゼオライト又はリン酸塩系ゼオライトであることが望ましい。　
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し、前記貴金属触媒が担持されている領域が、排ガスの流れる方向に対して、下流側に配置されている。　
本発明の排ガス浄化装置は、ディーゼルエンジンのＳＣＲシステムに使用されることが望ましい。
　本発明によれば、ＮＯｘの浄化性能を維持しながら、アンモニアスリップを抑制すると共に、ＳＣＲシステムの配置スペースが大きくなることを抑制することが可能な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。 実施例及び比較例の評価方法を示す図である。
　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。
　このとき、ハニカムユニット１１は、長手方向に対して、一方の端部から全長の１．５～２０％である領域Ａのみに貴金属触媒が担持されている。以下、ハニカムユニット１１の貴金属触媒が担持されている領域Ａを、ハニカムユニット１１の領域Ａという。
　このようなハニカムユニット１１の領域Ａを、排ガス浄化装置１００（図２参照）の排ガスの流れる方向に対して、下流側に配置すると、ハニカムユニット１１の領域Ａに担持されている貴金属触媒により、アンモニアが酸化されるため、アンモニアスリップを抑制することができる。
　なお、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。
　ハニカムユニット１１の領域Ａがハニカムユニット１１の長手方向に対して、一方の端部から全長の１．５％未満であると、アンモニアスリップを抑制する効果が不十分となる。一方、ハニカムユニット１１の領域Ａがハニカムユニット１１の長手方向に対して、一方の端部から全長の２０％を超えると、ＮＯｘの浄化率が低下する。
　ハニカムユニット１１に担持されている貴金属触媒としては、アンモニアを酸化することが可能であれば、特に限定されないが、白金、パラジウム、ロジウム等が挙げられ、二種以上併用してもよい。
　ハニカムユニット１１に含まれるゼオライトとしては、特に限定されないが、β型ゼオライト、ＺＳＭ－５型ゼオライト、リン酸塩系ゼオライト等が挙げられ、二種以上併用してもよい。中でも、ＮＯｘの浄化能が高いため、リン酸塩系ゼオライトが好ましい。
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。
　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ゼオライトを含むことが好ましい。なお、ゼオライトは、イオン交換されていないゼオライト、上記以外の金属でイオン交換された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。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り、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。
　さらに、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。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、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、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、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、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は、無機バインダの含有量が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り、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、気孔率が２５～４０％であることが好ましい。ハニカムユニット１１の気孔率が２５％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、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、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の強度が不十分となることがある。
　なお、ハニカムユニット１１の気孔率は、水銀圧入法を用いて測定することができる。
　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、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、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、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、ゼオライト、無機バインダ、無機繊維及び鱗片状物質の総質量に対して、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、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、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ゼオライトを含む原料ペーストを用いてもよい。
　一方、含浸法等を用いて、ハニカムユニット１１の領域Ａに貴金属触媒を担持させることができる。このとき、ハニカムユニット１１の領域Ａに、貴金属触媒が担持されているアルミナ等の担持体を担持させてもよい。また、ハニカムユニット１１の領域Ａに、アルミナ等の担持体を担持させた後、貴金属触媒を担持させてもよい。さらに、ハニカムユニット１１の領域Ａに、貴金属触媒を直接担持させてもよい。
　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、周縁部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、平均粒径が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であった。
　次に、ハニカムユニット１１を硝酸銅水溶液中に浸漬することにより、ゼオライトをＣｕイオンでイオン交換した。ゼオライトのイオン交換量を、ＩＣＰＳ－８１００（島津製作所社製）を用いて、ＩＰＣ発光分析することにより求めたところ、２．７質量％であった。
　また、ハニカムユニット１１の領域Ａ（長さ１０ｍｍ）を硝酸白金溶液に浸漬した後、６００℃で１時間保持することにより、白金触媒を担持させた。このとき、ハニカムユニット１１の領域Ａの見掛けの体積当たりの白金触媒の含有量は３ｇ／Ｌである。
　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１００’を作製した（図２参照）。このとき、ハニカムユニット１１の領域Ａを、排ガスの流れる方向に対して、下流側に配置した。
　［実施例２］
　ハニカムユニット１１の領域Ａの長さを５ｍｍに変更した以外は、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１００’を作製した。
　［実施例３］
　ハニカムユニット１１の領域Ａの長さを２５ｍｍに変更した以外は、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１００’を作製した。
　［実施例４］
　平均粒径が３μｍであるβ型ゼオライト３０００ｇ、ベーマイト８４０ｇ、平均繊維径が６μｍ、平均繊維長が１００μｍのアルミナ繊維６５０ｇ、メチルセルロース３３０ｇ、オレイン酸３３０ｇ及びイオン交換水１８００ｇ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２と同様にして、ハニカム構造体１０’及び排ガス浄化装置１００’を作製した。
　［実施例５］
　ハニカムユニット１１を硝酸鉄水溶液中に浸漬することにより、ゼオライトをＦｅイオンでイオン交換した以外は、実施例４と同様にして、ハニカム構造体１０’及び排ガス浄化装置１００’を作製した。
　なお、ゼオライトのイオン交換量を、ＩＣＰＳ－８１００（島津製作所社製）を用いて、ＩＰＣ発光分析することにより求めたところ、２．７質量％であった。
　［実施例６］
　ハニカムユニット１１の領域Ａの長さを２５ｍｍに変更した以外は、実施例５と同様にして、ハニカム構造体１０’及び排ガス浄化装置１００’を作製した。
　［実施例７］
　Ｃｕで２．７質量％イオン交換された、平均粒径が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、ハニカムユニット１１を硝酸銅水溶液中に浸漬しなかった以外は、実施例２と同様にして、ハニカム構造体１０’及び排ガス浄化装置１００’を作製した。
　［実施例８］
　Ｆｅで２．７質量％イオン交換された、平均粒径が３μｍであるβ型ゼオライト３０００ｇ、ベーマイト８４０ｇ、平均繊維径が６μｍ、平均繊維長が１００μｍのアルミナ繊維６５０ｇ、メチルセルロース３３０ｇ、オレイン酸３３０ｇ及びイオン交換水１８００ｇ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、ハニカムユニット１１を硝酸銅水溶液中に浸漬しなかった以外は、実施例２と同様にして、ハニカム構造体１０’及び排ガス浄化装置１００’を作製した。
　［比較例１］
　ハニカムユニット１１の領域Ａの長さを２ｍｍに変更した以外は、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１００’を作製した。
　［比較例２］
　ハニカムユニット１１に白金触媒を担持しなかった以外は、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１００’を作製した。
　［比較例３］
　ハニカムユニット１１の領域Ａの長さを２ｍｍに変更した以外は、実施例５と同様にして、ハニカム構造体１０’及び排ガス浄化装置１００’を作製した。
　［比較例４］
　ハニカムユニット１１に白金触媒を担持しなかった以外は、実施例５と同様にして、ハニカム構造体１０’及び排ガス浄化装置１００’を作製した。
　［比較例５］
　ハニカムユニット１１に白金触媒を担持しなかった以外は、実施例７と同様にして、ハニカム構造体１０’及び排ガス浄化装置１００’を作製した。
　［比較例６］
　ハニカムユニット１１に白金触媒を担持しなかった以外は、実施例８と同様にして、ハニカム構造体１０’及び排ガス浄化装置１００’を作製した。
　［ＮＯｘの浄化率の測定及びアンモニアスリップの評価］
　図５に示すように、排気管を介して、ディーゼルエンジン（１．６Ｌ直噴エンジン）２００と、ディーゼル酸化触媒（ＤＯＣ）３００と、ディーゼルパーティキュレートフィルタ（ＤＰＦ）４００と、実施例１～８及び比較例１～６の各排ガス浄化装置１００’とを直列に接続した状態で、ＮＥＤＣ（Ｎｅｗ　Ｅｕｒｏｐｅａｎ　Ｄｒｉｖｉｎｇ　Ｃｙｃｌｅ）モードで運転させた。このとき、ＭＥＸＡ－７５００ＤＥＧＲ（ＨＯＲＩＢＡ社製）を用いて、排ガス浄化装置１００’へのＮＯｘの流入量及び排ガス浄化装置１００’からのＮＯｘの流出量を測定し、式
　（ＮＯｘの流入量－ＮＯｘの流出量）／（ＮＯｘの流入量）×１００
で表されるＮＯｘの浄化率［％］を測定した（検出限界０．１ｐｐｍ）。このとき、排ガス浄化装置１００’の直前の排気管で、ディーゼルエンジン２００から排出されるＮＯｘを検知しながら、ＮＯｘに対する尿素のモル比が１．２となるように、尿素水を噴射した。なお、排ガス浄化装置１００’の平均温度を１６０℃、平均空間速度（ＳＶ）２００００／ｈｒ、排ガス中のＮＯｘに対する二酸化窒素の体積比を０．２５～０．３０とし、排ガス浄化装置１００’の温度が１８０℃以上であるときのみ尿素水を噴射し、排ガス浄化装置１００’のハニカム構造体１０’に予め６．０ｇのアンモニアを吸着させた。
　また、排ガス浄化装置１００’の下流側にガス検知管を設置して、アンモニアスリップの有無を評価した。
　このとき、ＤＯＣ３００及びＤＰＦ４００としては、それぞれ直径１４３．８ｍｍ、長さ１００ｍｍのハニカム構造体（市販品）及び直径１４３．８ｍｍ、長さ１５２．４ｍｍのハニカム構造体（市販品）を用いた。
　なお、比較例２、４の排ガス浄化装置１００’を用いる場合は、図５において、排ガス浄化装置１００’の下流側に、ＤＯＣとして、直径１４３．８ｍｍ、長さ５０ｍｍのハニカム構造体（市販品）を、排気管を介して、さらに設置した。
　表１に、ＮＯｘの浄化率の測定結果及びアンモニアスリップの評価結果を示す。
Figure JPOXMLDOC01-appb-T000001
  
表１より、実施例１～８の排ガス浄化装置１００’は、ＮＯｘの浄化率を維持しながら、アンモニアスリップを抑制できることがわかる。このとき、比較例２、４の排ガス浄化装置１００’は、その下流側に、排気管を介して、ＤＯＣをさらに設置すると、アンモニアスリップを抑制できる。しかしながら、比較例２、４の排ガス浄化装置１００’は、その下流側に、排気管を介して、ＤＯＣを設置しない場合、アンモニアスリップを抑制することができない。一方、実施例１～８の排ガス浄化装置１００’は、その下流側に、排気管を介して、ＤＯＣを設置しなくてもよいため、ＳＣＲシステムの配置スペースが大きくなることを抑制できることがわかる。
　以上のことから、ハニカムユニット１１は、長手方向に対して、一方の端部から全長の１．５～２０％である領域Ａのみに貴金属触媒が担持されていることにより、ハニカム構造体１０’及び排ガス浄化装置１００’は、ＮＯｘの浄化性能を維持しながら、アンモニアスリップを抑制でき、ＳＣＲシステムの配置スペースが大きくなることを抑制できることがわかる。
　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
　Ａ　　第一の領域
　Ｂ　　第二の領域
　１２　　外周コート層
　１３　　接着層
　２０　　保持シール材
　３０　　金属管
　１００、１００’　　排ガス浄化装置

Claims (11)

  1. 　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、前記長手方向に対して、一方の端部から全長の１．５％以上２０％以下である領域のみに貴金属触媒が担持されていることを特徴とするハニカム構造体。
  2. 前記ゼオライトは、β型ゼオライト、ＺＳＭ－５型ゼオライト又はリン酸塩系ゼオライト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２に記載のハニカム構造体。
  4. 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３に記載のハニカム構造体。
  5. 前記ゼオライトは、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４のいずれか一項に記載のハニカム構造体。
  6. 　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５のいずれか一項に記載のハニカム構造体。
  7. 　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６のいずれか一項に記載のハニカム構造体。
  8. 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７に記載のハニカム構造体。
  9. 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８のいずれか一項に記載のハニカム構造体。
  10. 請求項１乃至９のいずれか一項に記載のハニカム構造体を有する排ガス浄化装置であって、　前記貴金属触媒が担持されている領域が、排ガスの流れる方向に対して、下流側に配置されていることを特徴とする排ガス浄化装置。
  11. ディーゼルエンジンのＳＣＲシステムに使用されることを特徴とする請求項１０に記載の排ガス浄化装置。
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