WO2014199740A1 - Structure en nid d'abeilles et filtre en nid d'abeilles - Google Patents

Structure en nid d'abeilles et filtre en nid d'abeilles Download PDF

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Publication number
WO2014199740A1
WO2014199740A1 PCT/JP2014/061883 JP2014061883W WO2014199740A1 WO 2014199740 A1 WO2014199740 A1 WO 2014199740A1 JP 2014061883 W JP2014061883 W JP 2014061883W WO 2014199740 A1 WO2014199740 A1 WO 2014199740A1
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Prior art keywords
honeycomb structure
oxide
coating layer
holes
structure according
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PCT/JP2014/061883
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English (en)
Japanese (ja)
Inventor
寛 岸田
沙織 大村
アンキット ディープチャンド ジャイン
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住友化学株式会社
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Publication of WO2014199740A1 publication Critical patent/WO2014199740A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7615—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
    • 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
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—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
    • F01N3/022—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 characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
    • F01N3/0222—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 characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous the structure being monolithic, e.g. honeycombs
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to a honeycomb structure and a honeycomb filter.
  • the honeycomb structure can be used to obtain a honeycomb filter that removes the collected substance from a fluid containing the collected substance.
  • the honeycomb filter include an exhaust gas filter for purifying exhaust gas exhausted from an internal combustion engine such as a diesel engine or a gasoline engine.
  • a honeycomb structure for obtaining such a honeycomb filter has, for example, a plurality of through holes partitioned by porous partition walls (see, for example, Patent Document 1 below).
  • the honeycomb structure it is required for the honeycomb structure to further improve the purification performance of a fluid (exhaust gas or the like) containing a trapped substance as compared with the conventional structure.
  • the present invention has been made in view of such circumstances, and an object of the present invention is to provide a honeycomb structure capable of improving purification performance and a honeycomb filter including the honeycomb structure.
  • the present inventor has conceived of forming a coating layer covering the surface of the partition wall in the through hole in order to reduce the pressure loss that increases as the collected object is collected.
  • the present inventors have found that when a honeycomb structure having a coating layer is exposed to a high temperature state, sufficient purification performance may not be obtained due to a decrease in the surface area of the coating layer. For example, when a honeycomb structure having a coating layer on which a catalyst is supported is exposed to a high temperature state, the active point of the catalyst decreases due to a decrease in the surface area of the coating layer, and the deterioration of the catalyst proceeds. May end up.
  • the present inventors have found that by adjusting the content of alkali metal in the particles constituting the coating layer, it is possible to suppress the surface area of the coating layer from decreasing, and to suppress the reduction in purification performance. It was.
  • the honeycomb structure according to the present invention has a plurality of through holes partitioned by porous partition walls, and a coating layer covering at least a part of the partition walls is formed inside at least one of the plurality of through holes.
  • the coating layer contains particles containing oxide, and the total amount of alkali metal oxides in the particles is 0.100% by mass or less.
  • the honeycomb structure according to the present invention it is possible to suppress a decrease in the surface area of the coating layer when the honeycomb structure is exposed to a high temperature state, and it is possible to suppress a decrease in purification performance.
  • a honeycomb structure having a coating layer on which a catalyst is supported is exposed to a high temperature state, a reduction in the surface area of the coating layer is suppressed.
  • the active point of a catalyst reduces, it can suppress that deterioration of a catalyst advances.
  • the honeycomb structure according to the present invention can also reduce the pressure loss without impairing the purification performance of the catalyst.
  • the present inventor presumes the following factors that can suppress the reduction in the surface area of the coating layer when the honeycomb structure is exposed to a high temperature state.
  • the factors are not limited to the following. That is, when the total amount of alkali metal oxides in the particles is 0.100% by mass or less, the active point of the catalyst may be covered even when the alkali metal easily moves in a high temperature state (for example, May cause ion exchange with active species such as copper ions and iron ions, may affect the local bonding state of the catalyst skeleton and cause structural changes in the catalyst, and may cause sintering of the catalyst and / or the particles It is conceivable that the possibility and the like can be effectively suppressed.
  • the total amount of the alkali metal may be 0.001% by mass or more. In this case, it is possible to further suppress the reduction in the surface area of the coating layer, and the purification performance can be further improved.
  • the alkali metal may be sodium and potassium. In this case, the purification performance can be further improved.
  • the average major axis of the particles may be 5 to 500 ⁇ m, and the average minor axis of the particles may be 0.10 to 50 ⁇ m.
  • the purification performance can be further improved.
  • it can further suppress that a pressure loss increases excessively as a thing to be collected is collected by the honeycomb structure.
  • the oxide may be at least one selected from the group consisting of alumina, titania, zirconia, silica, magnesia, calcia, strontium oxide, aluminosilicate, mullite, cordierite, and aluminum titanate.
  • the heat resistance of the coating layer can be improved, and the function or shape of the coating layer can be easily maintained even when exposed to high temperatures.
  • the partition wall may contain at least one selected from the group consisting of aluminum titanate, cordierite, silicon carbide, silicon nitride, and mullite.
  • the coating layer may further contain a catalyst.
  • the purification performance can be further improved.
  • the honeycomb filter according to the present invention includes the honeycomb structure, and a sealing portion that seals one end of a part of the plurality of through holes and the other end of the remaining part of the plurality of through holes.
  • the honeycomb filter according to the present invention includes the honeycomb structure so that the purification performance can be improved and the pressure loss is prevented from excessively increasing as the collected material is collected. it can.
  • the present invention it is possible to suppress a decrease in the surface area of the coating layer when the honeycomb structure is exposed to a high temperature state, and it is possible to suppress a decrease in purification performance.
  • the honeycomb structure having the coating layer on which the catalyst is supported is exposed to a high temperature state, it is possible to suppress the deterioration of the catalyst.
  • pressure loss can also be reduced.
  • FIG. 1 is a perspective view showing a honeycomb filter according to an embodiment of the present invention.
  • FIG. 2 is a view taken along the line II-II in FIG.
  • FIG. 3 is a cross-sectional view showing a honeycomb filter according to another embodiment of the present invention.
  • FIG. 1 is a perspective view showing a honeycomb filter according to the present embodiment
  • FIG. 2 is a view taken in the direction of arrows II-II in FIG.
  • the honeycomb filter 1 includes a honeycomb structure 100 and a sealing portion 130.
  • the honeycomb structure 100 is a cylindrical body having a plurality of through holes 110 arranged in parallel to each other, as shown in FIGS. Each of the plurality of through holes 110 is partitioned by a partition wall 120 extending in parallel with the central axis of the honeycomb structure 100.
  • the through hole 110 includes a through hole (first through hole) 110 a constituting a part of the through hole 110 and a through hole (second through hole) 110 b constituting the remaining part of the through hole 110. Have.
  • the end portion on one end side of the honeycomb structure 100 in the through hole 110a is opened as a gas inlet on the one end face 100a of the honeycomb structure 100, and the end portion on the other end side of the honeycomb structure 100 in the through hole 110a is The other end surface 100 b of the honeycomb structure 100 is sealed by the sealing portion 130.
  • the end of one end side of the honeycomb structure 100 in the through hole 110b is sealed by the sealing portion 130 on the one end face 100a, and the end of the other end side of the honeycomb structure 100 in the through hole 110b is the other end face. In 100b, it opens as a gas outlet.
  • the through hole 110b is adjacent to the through hole 110a.
  • the through holes 110a and the through holes 110b are alternately arranged to form a lattice structure.
  • the through holes 110a and 110b are perpendicular to both end faces of the honeycomb structure 100, and are arranged in a square shape when viewed from the end face, that is, the central axes of the through holes 110a and 110b are respectively located at the apexes of the square. Yes.
  • the cross section perpendicular to the axial direction (longitudinal direction) of the through holes in the through holes 110a and 110b is, for example, a square shape.
  • the length of the honeycomb structure 100 in the longitudinal direction of the through holes 110a and 110b is, for example, 30 to 300 mm.
  • the outer diameter (diameter) of the honeycomb structure 100 is, for example, 10 to 300 mm.
  • the inner diameter of the cross section perpendicular to the axial direction of the through hole in each of the through holes 110a and 110b is, for example, 0. 5 to 1.5 mm.
  • the average thickness (cell wall thickness) of the partition wall 120 is, for example, 0.1 to 0.5 mm.
  • the partition wall 120 is porous and includes, for example, a porous ceramic sintered body.
  • the partition wall 120 has a structure that allows fluid (for example, exhaust gas containing fine particles such as soot) to pass therethrough. Specifically, a large number of communication holes through which fluid can pass are formed in the partition wall 120.
  • the porosity of the partition wall 120 is, for example, 30 to 70% by volume.
  • the pore diameter (pore diameter) of the partition wall 120 is, for example, 5 to 30 ⁇ m.
  • the porosity and pore diameter of the partition wall 120 can be adjusted by the particle diameter of the raw material, the amount of the pore-forming agent added, the kind of the pore-forming agent, and the firing conditions, and can be measured by a mercury intrusion method.
  • the partition wall 120 includes ceramics such as aluminum titanate, cordierite, silicon carbide, silicon nitride, mullite, and includes at least one selected from the group consisting of aluminum titanate, cordierite, silicon carbide, silicon nitride, and mullite. And at least one selected from the group consisting of aluminum titanate, cordierite and silicon carbide may be included.
  • the partition 120 may further include magnesium and / or silicon.
  • the partition 120 is made of, for example, porous ceramics mainly made of an aluminum titanate crystal. “Mainly composed of an aluminum titanate-based crystal” means that the main crystal phase constituting the aluminum titanate-based ceramic fired body is an aluminum titanate-based crystal phase. An aluminum titanate crystal phase, an aluminum magnesium titanate crystal phase, or the like may be used.
  • a coating layer 140 that covers the surface of the partition wall 120 (the inner wall surface of the through hole 110a) is formed inside the through hole 110a.
  • the coating layer 140 is formed on the surface of the partition wall 120 inside the through hole 110a. Is formed.
  • the covering layer 140 is formed, for example, inside all the through holes 110a, and is not formed inside the through holes 110b.
  • Each of the covering layers 140 is formed along the longitudinal direction of the through hole 110a, and covers the entire surface of the partition wall 120 in each of the through holes 110a.
  • the covering layer 140 in each of the through holes 110a is continuously formed on the partition wall 120 along the partition wall 120 surrounding the through hole 110a in a cross section perpendicular to the axial direction of the through hole 110a. It has an annular cross section along the inner wall.
  • the thickness of the covering layer 140 is, for example, 5 to 500 ⁇ m.
  • the coating layer 140 contains a coating material (particles) containing an oxide.
  • the coating material is, for example, fibrous or flat.
  • the coating material may contain at least one selected from the group consisting of alumina, titania, zirconia, silica, magnesia, calcia, strontium oxide, aluminosilicate, mullite, cordierite, and aluminum titanate as the oxide. .
  • the coating material may contain silicon carbide or the like.
  • the coating material may have biological solubility, for example, biologically soluble particles containing silica, magnesia, calcia, strontium oxide, and the like. As the coating material, only a single type of particle may be used, or a plurality of types of particles may be used in combination.
  • the coating material can contain, for example, at least one selected from the group consisting of alumina and silica.
  • the heat resistance of the coating layer can be improved, and the function or shape of the coating layer can be easily maintained even when exposed to high temperatures.
  • the total amount of oxide of alkali metal in the coating material is converted from oxide to the content of the coating material from the viewpoint of suppressing a decrease in the surface area of the coating layer when the honeycomb structure is exposed to a high temperature state. In some cases, it is 0.100% by mass or less.
  • the total amount in terms of oxide of alkali metal in the coating material is preferably 0.090% by mass or less, more preferably 0.080% by mass or less, from the viewpoint of easily suppressing the decrease in the surface area of the coating layer. 0.070 mass% or less is still more preferable, and 0.050 mass% or less is especially preferable.
  • 0.001 mass% or more may be sufficient as the total amount of the oxide of the alkali metal in a coating material, 0.002 mass% or more may be sufficient, and 0.003 mass% or more may be sufficient.
  • the alkali metal examples include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and francium (Fr).
  • the alkali metal may be both sodium and potassium.
  • the alkali metal oxide is, for example, Li 2 O, Na 2 O, K 2 O, Rb 2 O, Cs 2 O, Fr 2 O.
  • the total amount of alkali metal in terms of oxide can be measured, for example, by inductively coupled plasma emission spectroscopy.
  • the coating material preferably has a specific average major axis and / or a specific average minor axis.
  • the length in the longitudinal direction of the coating material can be a major axis
  • the length in the circumferential direction in a cross section perpendicular to the longitudinal direction of the coating material can be a minor axis.
  • the coating material is plate-shaped, the length of the long side of the rectangle with the smallest area circumscribing the main surface of the coating material can be the major axis, and the length of the short side of the rectangle can be the minor axis.
  • the average major axis and average minor axis of the coating material can be measured, for example, by the following procedure. First, the coating layer is observed with an electron microscope at a desired magnification (for example, 200 to 5000 times) to obtain an image in which a plurality of coating materials are observed. Next, for example, arbitrary 10 coating materials are selected in the obtained image. The major axis and the minor axis are measured for each of the ten selected coating materials. By calculating the average value based on the measured values of the ten coating materials, the average major axis and the average minor axis can be obtained.
  • a desired magnification for example, 200 to 5000 times
  • the average major axis of the coating material (for example, the average major axis of the ten coating materials) is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and more preferably 20 ⁇ m or more from the viewpoint of improving the initial collection efficiency of the collected material. Further preferred.
  • the average major axis of the coating material is preferably 500 ⁇ m or less, more preferably 300 ⁇ m or less, and even more preferably 200 ⁇ m or less, from the viewpoint that pressure loss is easily reduced.
  • the average minor axis of the coating material (for example, the average minor axis of the above ten coating materials) is preferably 0.10 ⁇ m or more, more preferably 0.50 ⁇ m or more from the viewpoint of improving the initial collection efficiency of the collected material. More preferred is 1.00 ⁇ m or more.
  • the average minor axis of the coating material is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, and even more preferably 10 ⁇ m or less, from the viewpoint that pressure loss is easily reduced.
  • the covering layer 140 may further contain a catalyst (for example, an exhaust gas purifying catalyst).
  • a catalyst for example, an exhaust gas purifying catalyst.
  • the catalyst include zeolite, metal-substituted (eg, copper, iron) zeolite, alumina, titania, silica, rare earth oxide, ceria-based complex oxide, zirconia-based complex oxide, perovskite-type complex oxide, and these The mixture of 2 or more types of them is mentioned.
  • the oxide catalyst may carry a transition metal species such as copper, iron, manganese, vanadium, tungsten and silver; a noble metal species such as platinum, palladium and rhodium; and a mixture of two or more of these.
  • the ratio of the coating material content to the catalyst content is preferably 0.05 or more from the viewpoint of effectively reducing the pressure loss of the honeycomb structure. 0.2 or more is more preferable, and 0.5 or more is still more preferable.
  • the ratio of the coating material content to the catalyst content is preferably 20 or less, more preferably 10 or less, from the viewpoint of obtaining further excellent purification performance. 5 or less is more preferable.
  • the coating layer 140 may be a single layer containing a coating material or a single layer containing a coating material and a catalyst.
  • the covering layer 140 may have a first layer containing a coating material and a second layer containing a substance (for example, a catalyst) different from the coating material. In this case, for example, the second layer is disposed on the first layer.
  • the honeycomb filter 1 is suitable as a particulate filter that collects a collection object such as soot contained in exhaust gas from an internal combustion engine such as a diesel engine or a gasoline engine.
  • a collection object such as soot contained in exhaust gas from an internal combustion engine such as a diesel engine or a gasoline engine.
  • the gas G supplied from the one end face 100a to the through hole 110a passes through the inside of the coating layer 140 and the communication hole in the partition wall 120 to the adjacent through hole 110b. It reaches and is discharged from the other end surface 100b.
  • the trapped substance in the gas G is collected in the surface and / or inside of the coating layer 140 and in the surface and / or communication hole of the partition wall 120 and removed from the gas G, whereby the honeycomb is collected.
  • the filter 1 functions as a filter.
  • the honeycomb structure 100 is not only used for obtaining the particulate filter described above, but also a filter used for filtering food and drink such as beer; gas components generated during petroleum refining (for example, carbon monoxide, carbon dioxide, nitrogen) , Oxygen) permselective filter for selectively permeating; used for catalyst carrier and the like.
  • the shape of the honeycomb structure is not necessarily limited to the shape described above.
  • the cross section of the through hole perpendicular to the axial direction of the through hole is not limited to a rectangular shape such as a square shape, and may be a triangular shape, a hexagonal shape, an octagonal shape, a circular shape, an elliptical shape, or the like. The same effect as in the case of the rectangular shape can be obtained.
  • those having different diameters may be mixed, and those having different cross-sectional shapes may be mixed.
  • the arrangement of the through holes is not particularly limited, and the arrangement of the central axes of the through holes may be an equilateral triangle arrangement, a staggered arrangement, or the like arranged at the apex of the equilateral triangle.
  • the honeycomb structure is not limited to a cylindrical body, and may be an elliptical column, a triangular column, a quadrangular column, a hexagonal column, an octagonal column, or the like.
  • the coating layer 140 covers the entire surface of the partition wall 120 in each of the through holes 110a, but it is only necessary to cover at least a part of the surface of the partition wall 120. Further, in the honeycomb structure 100, the coating layer 140 is formed inside all the through holes 110a, but may be formed inside at least one of the plurality of through holes 110. The covering layer 140 may be formed inside the through hole 110a and may be formed inside the through hole 110b (see FIG. 3). In this case, purification performance can be improved not only in the through hole 110a but also in the through hole 110b.
  • the honeycomb filter manufacturing method includes, for example, (a) a raw material preparation step of preparing a raw material mixture containing inorganic compound powder and additives, and (b) forming the raw material mixture to obtain a formed body having through holes.
  • a molding step and (c) a firing step for firing the molded body are provided in this order, and further include a sealing step and a coating layer forming step.
  • an inorganic compound powder and additives are mixed and then kneaded to prepare a raw material mixture.
  • the inorganic compound powder includes an aluminum source powder such as ⁇ -alumina powder and a titanium source powder (titanium source powder) such as anatase type or rutile type titania powder.
  • a magnesium source powder such as magnesia powder and / or a silicon source powder such as silicon oxide powder or glass frit can be further included.
  • the additive include a pore forming agent, a binder, a plasticizer, a dispersant, and a solvent.
  • a formed body having a honeycomb shape is obtained.
  • a so-called extrusion molding method in which the raw material mixture is extruded from a die while being kneaded by a single screw extruder can be employed.
  • the molded body is fired at a firing temperature of 1300 to 1650 ° C., for example.
  • degreasing for removing the pore-forming agent and the like contained in the molded body (in the raw material mixture) may be performed.
  • the sealing step is performed between the molding step and the firing step or after the firing step.
  • a sealing step is performed between the molding step and the firing step, after sealing one end of each through hole of the unfired molded body obtained in the molding step with a sealing material, the sealing material is sealed together with the molded body in the firing step.
  • the sealing part which seals one edge part of a through-hole is obtained by baking.
  • the sealing step is performed after the firing step, one end of each through hole of the fired body obtained in the firing step is sealed with a sealing material, and then the sealing material is fired together with the fired body, whereby one of the through holes.
  • the sealing part which seals the edge part of is obtained.
  • the mixture similar to the raw material mixture for obtaining the said molded object can be used.
  • the coating layer forming process is performed after the molding process.
  • a method for forming the coating layer a method of drying and baking the treatment solution after attaching the treatment solution to the surface of the partition wall in the through hole by an immersion method or the like can be used.
  • the treatment object the fired body obtained in the firing process or the molded body obtained in the molding process
  • the treatment solution is adhered to the surface of the partition wall, and then the treatment object is removed. Dry and fire.
  • the processing target object may be sealed and may not be sealed.
  • the temperature is in the range of 400 to 1000 ° C. as necessary.
  • the coating layer can be formed by firing.
  • the treatment solution used for forming the coating layer contains, for example, the coating material and water.
  • the treatment solution further contains a catalyst.
  • a treatment solution containing a coating material and water and a treatment solution containing a catalyst and water can be used. .
  • a honeycomb filter can be obtained through the above steps.
  • the formed body is fired and the coating layer is formed without sealing the through holes of the formed body obtained in the forming step.
  • Example 1 After weighing 0.5 g each of oxide particles having the physical properties shown in Table 1 below (total amount of alkali metal is 0.069% by mass in terms of oxide) and ⁇ -zeolite, ion-exchanged water was added. A slurry having a solid content of 10% by mass was prepared. The slurry was subjected to dispersion treatment by ultrasonic treatment for 10 minutes and then sufficiently dried in an oven at 80 ° C. After lightly mixing in an agate mortar, the powder A was obtained by baking at 500 ° C. for 50 minutes in the air. A numerical value A was obtained by measuring the BET specific surface area of the powder A.
  • Powder A was calcined in the atmosphere at 800 ° C. for 5 hours to obtain Powder B.
  • the BET specific surface area of the powder B was measured to obtain a numerical value B.
  • powder A was obtained again by the same procedure as described above, and then powder A was calcined in water vapor containing 10% water at 800 ° C. for 5 hours to obtain powder C.
  • a numerical value C was obtained by measuring the BET specific surface area of the powder C.
  • the change rate 1 ((numerical value A-numerical value B) / numerical value A ⁇ 100 [%]) of the BET specific surface area before and after firing was calculated.
  • the change rate 2 ((numerical value A-numerical value C) / numerical value A ⁇ 100 [%]) of the BET specific surface area before and after firing was calculated.
  • Example 2 The change rate 1 of the BET specific surface area was calculated in the same manner as in Example 1 except that the oxide particles having the physical properties of Examples 2 to 4 shown in Table 1 below were used and that the powder C was not prepared. did.
  • Example 5 The use of oxide particles having the physical properties of Example 5 shown in Table 1 below, the use of zeolite supporting copper (Cu-zeolite) instead of ⁇ -zeolite, and the preparation of powder C were not performed. Except that, the change rate 1 of the BET specific surface area was calculated in the same manner as in Example 1.
  • composition analysis of oxide particles Qualitative and quantitative analysis of the composition of each oxide particle was performed using an inductively coupled plasma emission spectrometer.
  • the physical properties (composition, average major axis, average minor axis) of each oxide particle are shown in Table 1 below.
  • the change rate 1 of the numerical value A, the numerical value B, and the BET specific surface area is shown in Table 2 below.
  • Table 3 below shows the change rate 2 of the numerical value A, the numerical value C, and the BET specific surface area.
  • Example 6 Oxide particles similar to Example 3 (total amount of alkali metal is 0.033 mass% in terms of oxide, average major axis is 100 ⁇ m) 0.005 g, copper supported zeolite (Cu-zeolite) 0.05 g, After measuring each, ion-exchange water was added and the slurry whose solid content is 10 mass% was produced. The slurry was subjected to dispersion treatment by ultrasonic treatment for 10 minutes and then sufficiently dried in an oven at 80 ° C. After lightly mixing in an agate mortar, powder D was obtained by firing in the atmosphere at 500 ° C. for 50 minutes. The powder D was measured for nitrogen oxide purification performance, and a numerical value D was obtained.
  • the powder D was obtained again by the same procedure as described above, and then the powder D was calcined in water vapor containing 10% water at 800 ° C. for 5 hours to obtain a powder E.
  • the powder E was measured for nitrogen oxide purification performance, and a numerical value E was obtained.
  • the change rate 3 ((numerical value D ⁇ numerical value E) / numerical value D ⁇ 100 [%]) of the purification performance of nitrogen oxides before and after firing was calculated.
  • Example 7 Purification of nitrogen oxides as in Example 6 except that the same oxide particles as in Example 5 (the total amount of alkali metals is less than 0.004% by mass in terms of oxides and the average major axis is 100 ⁇ m) are used. A performance change rate of 3 was calculated.
  • Example 8 Oxide particles similar to Example 5 (total amount of alkali metals is less than 0.004% by mass in terms of oxides, average major axis is 100 ⁇ m) 0.05 g and copper supported zeolite (Cu-zeolite) 0.05 g Then, the change rate 3 of the nitrogen oxide purification performance was calculated in the same manner as in Example 6 except that ion-exchanged water was added to prepare a slurry having a solid content of 10% by mass.
  • Example 9 The same oxide particles as in Example 1 (total amount of alkali metal is 0.069% by mass in terms of oxides, average major axis is 100 ⁇ m) 0.05 g, copper supported zeolite (Cu-zeolite) 0.05 g, After measuring each, the change rate 3 of the nitrogen oxide purification performance was calculated in the same manner as in Example 6, except that ion-exchanged water was added to prepare a slurry having a solid content of 10% by mass.
  • total amount of alkali metal is 0.069% by mass in terms of oxides, average major axis is 100 ⁇ m
  • Cu-zeolite copper supported zeolite
  • Comparative Example 3 Oxide particles similar to Comparative Example 2 (total amount of alkali metal is 0.102 mass% in terms of oxide, average major axis is 70 to 150 ⁇ m) 0.005 g, and copper-supported zeolite (Cu-zeolite) 0. After measuring each of 05 g, a change rate 3 of the nitrogen oxide purification performance was calculated in the same manner as in Example 6 except that a slurry having a solid content of 10% by mass was prepared by adding ion exchange water. .
  • Tables 4 and 5 below show the numerical value D, the numerical value E, and the change rate 3 of the nitrogen oxide purification performance.
  • Table 4 shows the results at a reaction temperature of 300 ° C.
  • Table 5 shows the results at a reaction temperature of 350 ° C.

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Abstract

　L'invention concerne une structure en nid d'abeilles (100) comportant une pluralité de trous traversants (110) divisés par une cloison poreuse (120), une couche de revêtement (140) est formée à l'intérieur d'un trou traversant (110a) de la pluralité de trous traversants (110), la couche de revêtement (140) couvre au moins une partie de la cloison (120) et contient des particules incluant un oxyde, et la quantité totale d'un métal alcalin en termes d'un oxyde dans les particules est de 0,100 % en masse ou moins.
PCT/JP2014/061883 2013-06-14 2014-04-28 Structure en nid d'abeilles et filtre en nid d'abeilles WO2014199740A1 (fr)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60106514A (ja) * 1983-11-14 1985-06-12 Toyota Motor Corp 微粒子捕集用セラミツクフイルタ
JPH07171403A (ja) * 1993-12-21 1995-07-11 Nikki Universal Co Ltd 耐被毒脱臭光触媒
JPH0957099A (ja) * 1995-08-28 1997-03-04 Toyota Motor Corp ディーゼルエンジン用排ガス浄化触媒
JP2004243189A (ja) * 2003-02-13 2004-09-02 Hitachi Ltd 内燃機関の排ガス浄化装置
JP2008239401A (ja) * 2007-03-27 2008-10-09 Kyocera Corp 耐熱性セラミック部材
JP2008272664A (ja) * 2007-04-27 2008-11-13 Ngk Insulators Ltd ハニカムフィルタシステム
JP2008302282A (ja) * 2007-06-06 2008-12-18 Toyota Motor Corp 排ガス浄化用触媒とその製造方法
JP2013511462A (ja) * 2009-11-24 2013-04-04 ビーエーエスエフ ソシエタス・ヨーロピア Ｃｈａ構造を有するゼオライトの製造方法
JP2013240763A (ja) * 2012-05-22 2013-12-05 Honda Motor Co Ltd 排気浄化触媒及び排気浄化装置

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60106514A (ja) * 1983-11-14 1985-06-12 Toyota Motor Corp 微粒子捕集用セラミツクフイルタ
JPH07171403A (ja) * 1993-12-21 1995-07-11 Nikki Universal Co Ltd 耐被毒脱臭光触媒
JPH0957099A (ja) * 1995-08-28 1997-03-04 Toyota Motor Corp ディーゼルエンジン用排ガス浄化触媒
JP2004243189A (ja) * 2003-02-13 2004-09-02 Hitachi Ltd 内燃機関の排ガス浄化装置
JP2008239401A (ja) * 2007-03-27 2008-10-09 Kyocera Corp 耐熱性セラミック部材
JP2008272664A (ja) * 2007-04-27 2008-11-13 Ngk Insulators Ltd ハニカムフィルタシステム
JP2008302282A (ja) * 2007-06-06 2008-12-18 Toyota Motor Corp 排ガス浄化用触媒とその製造方法
JP2013511462A (ja) * 2009-11-24 2013-04-04 ビーエーエスエフ ソシエタス・ヨーロピア Ｃｈａ構造を有するゼオライトの製造方法
JP2013240763A (ja) * 2012-05-22 2013-12-05 Honda Motor Co Ltd 排気浄化触媒及び排気浄化装置

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