WO2021240999A1 - 排ガス浄化触媒装置 - Google Patents
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- WO2021240999A1 WO2021240999A1 PCT/JP2021/014375 JP2021014375W WO2021240999A1 WO 2021240999 A1 WO2021240999 A1 WO 2021240999A1 JP 2021014375 W JP2021014375 W JP 2021014375W WO 2021240999 A1 WO2021240999 A1 WO 2021240999A1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0246—Coatings comprising a zeolite
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- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J23/745—Iron
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- 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
- B01J29/723—CHA-type, e.g. Chabazite, LZ-218
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- 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
- B01J29/763—CHA-type, e.g. Chabazite, LZ-218
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
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- 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
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- 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
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- 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
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- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
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- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20738—Iron
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- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20761—Copper
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- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/209—Other metals
- B01D2255/2092—Aluminium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2255/00—Catalysts
- B01D2255/50—Zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/402—Dinitrogen oxide
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
- B01D2258/012—Diesel engines and lean burn gasoline engines
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- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
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- 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 an exhaust gas purification catalyst device.
- a selective catalytic reduction (SCR) system is known as a technique for reducing and purifying NOx in exhaust gas discharged from an internal combustion engine such as a diesel engine before it is released to the atmosphere.
- the SCR system is a technique using an SCR catalyst that reduces NO x in exhaust gas to N 2 by using a reducing agent such as ammonia.
- N 2 O dinitrogen monoxide
- N 2 O contributes greatly as a greenhouse gas, it is desired that the amount of N 2 O emitted from the internal combustion engine is as small as possible.
- Patent Document 1 describes a first catalyst composition layer containing a mixed oxide (eg, vanasia / titania) and a second catalyst composition layer containing a metal exchanged zeolite (eg, Cu-zeolite). but on a substrate, which is disposed from the upstream side of the exhaust gas flows in this order, describes a SCR catalyst system, emissions of N 2 O is described as be reduced by this configuration.
- a mixed oxide eg, vanasia / titania
- a metal exchanged zeolite eg, Cu-zeolite
- An object of the present invention emissions of N 2 O (N 2 O slip amount) is extremely suppressed, it is to provide an exhaust gas purifying catalyst device.
- the present invention is as follows.
- ⁇ Aspect 1 An exhaust gas purification catalyst device including a base material and one or a plurality of catalyst layers on the base material. At least one catalyst layer among the one or a plurality of catalyst layers is It contains both Cu-CHA-type zeolite particles and iron-supported metal oxide particles in which iron is supported on the metal oxide particles.
- ⁇ Aspect 2 The metal oxide particles are one type of metal oxide particles selected from the group consisting of alumina, silica, titania, zirconia, and ceria, or two or more types of metal composite oxide particles.
- ⁇ Aspect 3 The exhaust gas purification catalyst device according to Aspect 2, wherein the metal oxide particles are alumina particles.
- ⁇ Aspect 4 The amount of iron in the exhaust gas purification catalyst device is 0.3 g / L or more and 1.3 g / L or less as the mass of iron in terms of ferric oxide (Fe 2 O 3) per 1 L of the base material.
- ⁇ Aspect 5 The amount of iron in the exhaust gas purification catalyst device is 0.6 g / L or more and 1.3 g / L or less as the mass of iron in terms of ferric oxide (Fe 2 O 3) per 1 L of the base material.
- ⁇ Aspect 6 The ratio of the Cu-CHA type zeolite particles and the iron-supported metal oxide particles in the catalyst layer is 5% by mass or more as the mass percentage of the iron-supporting metal oxide particles to the total of both.
- ⁇ Aspect 7 The exhaust gas purification catalyst device according to any one of aspects 1 to 6, which is for selective contact reduction.
- ⁇ Aspect 8 The method for manufacturing an exhaust gas purification catalyst device according to any one of aspects 1 to 7. (1) The Cu-CHA type zeolite particles and the iron-supported metal oxide particles are mixed and wet-ground to obtain a slurry for forming a catalyst layer, and (2) the catalyst is placed on the substrate.
- a layer-forming slurry is applied and fired to form the catalyst layer on the substrate.
- Manufacturing method of exhaust gas purification catalyst device ⁇ Aspect 9 >> An exhaust gas purification method for purifying exhaust gas using the exhaust gas purification catalyst device according to Aspect 7.
- the exhaust gas purification catalyst device is supplied with an exhaust gas and a reducing agent to reduce NO x in the exhaust gas to N 2 .
- Exhaust gas purification method is supplied with an exhaust gas and a reducing agent to reduce NO x in the exhaust gas to N 2 .
- the exhaust gas purification catalyst device of the present invention An exhaust gas purification catalyst device including a base material and one or more catalyst layers on the base material. At least one of the above one or a plurality of catalyst layers is It is characterized by containing both Cu-CHA type zeolite particles and iron-supported metal oxide particles in which iron is supported on the metal oxide particles.
- Patent Document 1 focuses on the difference in N 2 producing ability and N 2 O producing ability between the mixed oxide and the metal exchange zeolite, and focuses on the function of the mixed oxide and the metal exchange zeolite. It is intended to be used separately from the functions. Then, the first catalyst composition layer containing the mixed oxide, which has an excellent N 2 forming ability and a low N 2 O forming ability, is first brought into contact with the NOx-rich exhaust gas to suppress the formation of N 2 O. It is based on the idea that.
- N 2 O for example, derived from the degradation reaction of ammonium nitrate which is an intermediate of the SCR reaction (NH 4 ⁇ NO 3).
- Generation of N 2 O by the decomposition of ammonium nitrate is believed to be facilitated by metal-exchanged zeolite (e.g. Cu- zeolites).
- mixed oxides e.g. iron-based material is believed to promote the decomposition of the generated N 2 O.
- Cu-CHA-type zeolite particles and iron-supported metal oxide particles are arranged in the same catalyst layer to increase the degree of proximity between the two, thereby N 2
- N 2 We have reached an exhaust gas purification catalyst device in which the amount of O-slip is sufficiently suppressed.
- the present invention is not bound by any particular theory.
- Base material As the base material in the exhaust gas purification catalyst device of the present invention, those generally used as the base material of the exhaust gas purification catalyst device can be used.
- it may be, for example, a straight flow type monolith honeycomb base material composed of materials such as cordierite, SiC, stainless steel, and inorganic oxide particles.
- the exhaust gas purification catalyst device of the present invention has one or a plurality of catalyst layers, one of which contains both Cu-CHA-type zeolite particles and iron-supported metal oxide particles. That is, in the exhaust gas purification catalyst device of the present invention, the Cu-CHA type zeolite particles and the iron-supported metal oxide particles are contained in the same catalyst layer.
- a catalyst layer containing both Cu-CHA type zeolite particles and iron-supported metal oxide particles is referred to as a "specific catalyst layer”.
- Cu-CHA type zeolite particles in the present invention mean particles composed of CHA (Chabazite) -type zeolite ion-exchanged with copper.
- CHA Chozite
- SCR catalysts those known as SCR catalysts may be appropriately selected and used.
- Cu-CHA-type zeolite particles from the viewpoint of ensuring high SCR catalytic ability, SAR (Silica Alumina Ratio, SiO 2 / Al 2 O 3 molar ratio), 20 or less, 18 or less, 15 or less, 12 or less, 10 or less , 9 or less, or 8 or less.
- SAR Silica Alumina Ratio, SiO 2 / Al 2 O 3 molar ratio
- the SAR of the Cu-CHA type zeolite is excessively low, the specific surface area of the zeolite may become small and the NO x purification ability may be impaired. From the viewpoint of avoiding this, the SAR of the Cu-CHA type zeolite particles may be 3 or more, 4 or more, 5 or more, 6 or more, or 7 or more.
- Cu in the Cu-CHA-type zeolite particles is supported on the surface Al site of the CHA-type zeolite and constitutes a catalytic activity point for NO x purification in the SCR catalyst.
- the amount of Cu in the Cu-CHA type zeolite is 0.05 or more, 0.10 or more, 0.15 or more, from the viewpoint of expressing high NO x purification ability as the molar ratio (Cu / Al) of Cu and Al. It may be 0.20 or more or 0.25 or more, and from the viewpoint of stably maintaining the NO x purification ability, 1.00 or less, 0.80 or less, 0.60 or less, 0.50 or less, 0. It may be 45 or less, 0.40 or less, 0.35 or less, 0.30 or less, or 0.25 or less.
- the Cu-CHA type zeolite particles in the present invention may contain an alkali metal.
- Cu-CHA-type zeolite containing an appropriate amount of alkali metal further improves its hydrothermal durability while maintaining high initial NOx purification ability.
- the amount of alkali metal contained in the Cu-CHA type zeolite particles is excessively large, the initial NO x purification ability may be impaired.
- the amount of alkali metal in the Cu-CHA type zeolite particles is 0.2 mass as the ratio of the M 2 O (M indicates an alkali metal) equivalent mass to the total mass of the Cu-CHA type zeolite. % Or more, 0.3% by mass or more, 0.4% by mass or more, 0.5% by mass or more, 0.6% by mass or more, 0.7% by mass or more, or 0.8% by mass or more. 2.0% by mass or less, 1.8% by mass or less, 1.6% by mass or less, 1.4% by mass or less, 1.2% by mass or less, 1.0% by mass or less, 0.9% by mass or less, or It may be 0.8% by mass or less.
- the alkali metal contained in the Cu-CHA type zeolite particles may be lithium (Li), sodium (Na), potassium (K), cesium (Cs) or the like, and may be typically potassium.
- the primary particle size of the Cu-CHA type zeolite particles may be 0.1 ⁇ m or more, 0.2 ⁇ m or more, 0.3 ⁇ m or more, or 0.4 ⁇ m or more, and may be 1.0 ⁇ m or less, 0.8 ⁇ m or less, 0.6 ⁇ m. Hereinafter, it may be 0.5 ⁇ m or less, or 0.4 ⁇ m or less.
- the amount of Cu-CHA-type zeolite particles in the exhaust gas purification catalyst device of the present invention is 70 g / L or more, 80 g, from the viewpoint of ensuring a sufficiently high SCR catalytic ability as the mass of Cu-CHA-type zeolite per 1 L of the base material. It may be / L or more, 100 g / L or more, 120 g / L or more, 130 g / L or more, or 140 g / L or more, and from the viewpoint of suppressing pressure loss of the exhaust gas purification catalyst device, 200 g / L or less, 180 g / L or less. , 160 g / L or less, 150 g / L or less, or 140 g / L or less.
- the iron-supported metal oxide particles in the present invention are particles in which iron is supported on the metal oxide particles.
- the metal oxide particles may be oxide particles of one kind of metal selected from alumina, silica, titania, zirconia, ceria and the like, or composite oxide particles of two or more kinds of metals.
- the metal oxide particles are typically alumina particles.
- the iron-supported amount of the iron-supported metal oxide particles is converted to ferric oxide (Fe 2 O 3 ) with respect to the total mass of the iron-supported metal oxide particles from the viewpoint of sufficiently suppressing the N 2 O slip amount.
- the proportion of iron in the mass may be 0.5% by mass or more, 1% by mass or more, 3% by mass or more, 5% by mass or more, 6% by mass or more, or 7% by mass or more.
- the supported amount of iron 20 wt% or less, 15 wt% or less, 12 wt% or less, or even 10 wt% or less, sufficiently high N 2 O slip suppression effect is obtained.
- the iron (for example, ferric oxide) in the iron-supported metal oxide particles may be in the form of particles and may have a particle size of about 1 nm or more and 50 nm or less.
- Such iron-supported metal oxide particles may be prepared by, for example, an appropriate method such as a spray-drying method or an impregnation method using desired metal oxide particles.
- the production of iron-supported metal oxide particles by the spray-drying method may be carried out, for example, by a method including the following steps: The sol of the desired metal oxide particles and the iron compound are mixed in a suitable solvent (eg, water) to prepare a mixed solution; The resulting mixture is spray-dried to give a dry powdered precursor particle gel; and the resulting precursor particle gel is calcined.
- a suitable solvent eg, water
- the production of iron-supported metal oxide particles by the impregnation method may be carried out, for example, by a method including the following steps: Immersing the desired metal oxide particles in a solution of the iron compound in a suitable solvent (eg, water); and firing the soaked metal oxide particles.
- a suitable solvent eg, water
- the iron compound used in the spray-drying method and the impregnation method may be a solvent-soluble iron compound or a water-soluble iron compound, and specifically, for example, iron sulfate, iron nitrate, iron chloride, etc. It may be potassium hexacyanoferrate or the like.
- the primary particle size of the iron-supported metal oxide particles may be 0.01 ⁇ m or more, 0.03 ⁇ m or more, or 0.05 ⁇ m or more, and may be 1 ⁇ m or less, 0.5 ⁇ m or less, or 0.2 ⁇ m or less.
- the iron supported on the metal oxide particles is dispersed as high as possible.
- the crystal peaks attributed to ferric oxide Fe 2 O 3
- the amount of the iron supported metal oxide particles in the exhaust gas purifying catalyst device of the present invention as the mass of the iron-supported metal oxide per substrate 1L, from the viewpoint of sufficiently high effect of suppressing N 2 O slip amount, 1 g / It may be L or more, 3 g / L or more, 5 g / L or more, 10 g / L or more, or 12 g / L or more, and from the viewpoint of suppressing pressure loss of the exhaust gas purification catalyst device, 30 g / L or less, 25 g / L or less, It may be 20 g / L or less, 18 g / L or less, or 15 g / L or less.
- the amount of iron in the exhaust gas purification catalyst device is 0.3 g / L or more and 0.5 g / L as the mass of iron in terms of ferric oxide (Fe 2 O 3) per 1 L of the base material. It may be 1.7 g / L or more, or 1.0 g / L or more, and 1.3 g / L or less, 1.2 g / L or less, 1.1 g / L or less, or 1.0 g / L or less. It may be there.
- the mass ratio (mass percentage) of the iron-supported metal oxide to the total mass of the Cu-CHA type zeolite and the iron-supported metal oxide is 5% by mass or more, 7% by mass or more, 10% by mass or more, and 12% by mass. It may be more than or equal to 15% by mass, and may be 20% by mass or less, 18% by mass or less, 15% by mass or less, or 12% by mass or less.
- the specific catalyst layer in the exhaust gas purification catalyst device of the present invention contains both Cu-CHA type zeolite particles and iron-supported metal oxide particles. In addition to these, the specific catalyst layer may contain other optional components.
- the other component contained in the specific catalyst layer may be, for example, metal oxide particles other than Cu-CHA type zeolite particles and iron-supported metal oxide particles, a binder and the like.
- the other metal oxide particles may be, for example, oxide particles of one kind of metal selected from alumina, silica, titania, zirconia, ceria and the like, or composite oxide particles of two or more kinds of metals.
- the binder may be, for example, a calcined product of a metal oxide sol such as an alumina sol, a silica sol, a titania sol, or a zirconia sol.
- the amount (coating amount) of the specific catalyst layer in the exhaust gas purification catalyst device of the present invention is 80 g / L or more and 100 g / L from the viewpoint of exhibiting a sufficiently high SCR catalytic ability as the mass of the specific catalyst layer per 1 L of the base material. It may be L or more, 120 g / L or more, 130 g / L or more, or 140 g / L or more, and from the viewpoint of suppressing pressure loss of the exhaust gas purification catalyst device, 250 g / L or less, 200 g / L or less, 180 g / L or less, It may be 160 g / L or less, 150 g / L or less, or 140 g / L or less.
- the exhaust gas purification catalyst device of the present invention has a specific catalyst layer.
- the exhaust gas purification catalyst device of the present invention may have other catalyst layers in addition to the specific catalyst layer, if necessary.
- the other catalyst layer in the exhaust gas purification catalyst device of the present invention may be, for example, a catalyst layer exhibiting NOx oxidizing ability, a catalyst layer exhibiting ASC (Ammonia Slip Catalyst, ammonia slip catalyst) ability, or the like. These may have the same structure as the known catalyst layer. Further, in the exhaust gas purification catalyst device of the present invention, the specific catalyst layer and the other catalyst layers may be laminated on the base material in any order, or the exhaust gas may be present on the base material in any order. It may exist as a catalyst layer on the upstream side and the downstream side in the flow direction.
- ASC Ammonia Slip Catalyst, ammonia slip catalyst
- the exhaust gas purification catalyst device of the present invention may be manufactured by any method as long as it has the above configuration.
- a case where a characteristic catalyst layer is provided as a single layer on a base material is taken as an example, and the following method is exemplified as a manufacturing method thereof: (1) Cu-CHA type zeolite particles and iron-supported metal oxide particles are mixed and wet-ground to obtain a catalyst layer forming slurry (catalyst layer forming slurry preparation step), and (2) group.
- a catalyst layer forming slurry is applied on a material and fired to form a catalyst layer on a substrate (catalyst layer forming step).
- a method for manufacturing an exhaust gas purification catalyst device including.
- the Cu-CHA type zeolite particles specified in the present invention and the iron-supported metal oxide particles specified in the present invention are mixed at a predetermined ratio and wet-ground, and the catalyst layer forming slurry is pulverized. (Slurry for forming a specific catalyst layer) is obtained.
- the pulverization in this slurry preparation step for forming a catalyst layer is suitable from the viewpoint of making the particle size of each particle uniform and stabilizing the catalytic activity, and particularly from the viewpoint of suppressing the generation of crystal defects of Cu-CHA type zeolite particles. It is carried out by wet grinding performed in a liquid medium (for example, water).
- Wet pulverization may be performed using an appropriate pulverizer such as a ball mill, a bead mill, a jet mill, or an air jet mill, using an appropriate liquid medium, for example.
- an appropriate pulverizer such as a ball mill, a bead mill, a jet mill, or an air jet mill, using an appropriate liquid medium, for example.
- the catalyst layer forming slurry is applied onto the base material and fired to form the catalyst layer on the base material.
- the base material may be appropriately selected depending on the base material in the desired exhaust gas purification catalyst device, and may be, for example, a straight flow type monolith honeycomb base material manufactured by Cordellite.
- the slurry for forming a catalyst layer on the substrate may be applied and fired by a known method, respectively, or by a method obtained by appropriately modifying a known method by a person skilled in the art.
- the firing temperature may be, for example, 300 ° C. or higher, 350 ° C. or higher, 400 ° C. or higher, 450 ° C. or higher, or 500 ° C. or higher, and may be, for example, 1,000 ° C. or lower, 800 ° C. or lower, 700 ° C. or lower, 600 ° C. or higher. It may be °C or less, 550 °C or less, or 500 °C or less.
- the exhaust gas purification catalyst device of the present invention may be used as a catalyst device for selective catalytic reduction (SCR) for purifying exhaust gas discharged from, for example, a diesel internal combustion engine, a gasoline internal combustion engine, or the like.
- SCR selective catalytic reduction
- the exhaust gas purification catalyst device of the present invention also includes a DPF (Diesel Particulat Filter) device, a GPF (Gasoline Particulat Filter) device, and an ASC (Ammonia Slip Catalyst) device. May be used as part of an exhaust gas purification catalyst system in combination with one or more selected from the above.
- DPF Diesel Particulat Filter
- GPF Gasoline Particulat Filter
- ASC Ammonia Slip Catalyst
- the present invention further provides an exhaust gas purification method for purifying exhaust gas using the exhaust gas purification catalyst device of the present invention.
- the exhaust gas purification method of the present invention is a method including supplying an exhaust gas and a reducing agent to the exhaust gas purification catalyst device of the present invention to reduce NO x in the exhaust gas to N 2.
- the reducing agent in the exhaust gas purification method of the present invention may be, for example, ammonia, aqueous ammonia, urea, hydrocarbons, atomized fuel or the like.
- the exhaust gas purifying catalyst device of the present invention derived from ammonia (NH 3) used as a reducing agent in the SCR reaction, since N 2 O generated is what is extremely suppressed, as the reducing agent, in particular, ammonia, ammonia
- ammonia ammonia
- ammonia ammonia
- ammonia ammonia
- One or more selected from water and urea may be used.
- honeycomb base material made of cordierite having a cell density of 400 cpsi (cell per square inch, wall thickness of 6 mil (0.15 mm), and a capacity of 35 mL) was used as the base material.
- Cu-CHA type zeolite particles particles having a silica / alumina molar ratio (SAR) of 7.5 and a molar ratio of Cu to Al (Cu / Al) of 0.25 were used.
- SAR silica / alumina molar ratio
- Example 1 (1) Preparation of slurry for forming a catalyst layer In 200 parts by mass of pure water, 100 parts by mass of silica binder sol dispersion (15 parts by mass of dry mass), 85 parts by mass of Cu-CHA type zeolite particles, and iron-supported metal oxide. as particles, iron-alumina particles (spray drying iron alumina particles, Fe 2 O 3 supported amount 9.0 wt%) 2 parts by weight, were mixed in this order, by milling by a wet grinding method, a catalyst layer formed Slurry was obtained.
- silica binder sol dispersion 15 parts by mass of dry mass
- Cu-CHA type zeolite particles 85 parts by mass of Cu-CHA type zeolite particles
- iron-supported metal oxide as particles
- iron-alumina particles spray drying iron alumina particles, Fe 2 O 3 supported amount 9.0 wt% 2 parts by weight
- the exhaust gas purification catalyst device is heated to raise the temperature from room temperature to 600 ° C. at a heating rate of 25 ° C./min, and the gas having the composition of gas condition 1 shown in Table 1 below is inserted into the exhaust gas purification catalyst device.
- the heating was stopped and the device was allowed to cool.
- the gas having the composition of gas condition 2 shown in Table 2 below is circulated at a space velocity (SV) of 60,000 h -1 to exhaust gas.
- the composition of NO x was examined, and the purification rate of NO x and the amount of N 2 O slip were calculated. The results are shown in Table 3.
- Examples 2 to 4 and Comparative Examples 1 and 2 Spray-drying method Slurries for forming a catalyst layer were prepared in the same manner as in Example 1 except that the amount of Fe 2 O 3 supported on the iron alumina particles was changed as shown in Table 3. Using this, the slurry for forming a catalyst layer was applied onto the substrate in the same manner as in Example 1 except that the coating amount was changed so that the coating amount after firing was the value shown in Table 3. , Drying and firing were performed to manufacture an exhaust gas purification catalyst device.
- Comparative Example 2 the amount of pure water used when preparing the slurry for forming the catalyst layer was set to 250 parts by mass.
- Example 5 Exhaust gas purification is carried out in the same manner as in Example 3 except that the impregnated iron alumina particles having the same amount of Fe 2 O 3 supported on the alumina by the impregnation method are used instead of the spray dry iron alumina particles.
- the catalyst device was manufactured and evaluated. The results are shown in Table 3.
- Comparative Example 3 Spray-dry method An exhaust gas purification catalyst device was manufactured and evaluated in the same manner as in Example 3 except that a mixture of 9.1 parts by mass of alumina and 0.9 parts by mass of iron oxide was used instead of the iron alumina particles. bottom. The results are shown in Table 3.
- the value of the NOx purification rate has good larger, the value of N 2 O slip amount is smaller is better.
- Examples 1 to 4 containing iron supported metal oxide particles are N 2 O slip amount is suppressed, further, according proportion of iron supported metal oxide particles coated layer is increased, N 2 O slip amount tended to decreases.
- the proportion of iron supported metal oxide particles coated layer is more than 2.0 mass%, in the above about 4.8 wt%, decreasing the N 2 O slip amount becomes moderate.
- the proportion of iron supported metal oxide particles coated layer is from the viewpoint of suppressing N 2 O slip amount, 2.0 mass% or more, 3.0 wt% or more, 4.0 wt%
- the above or 4.5% by mass or more may be used, and from the viewpoint of the effectiveness of the formulation, it may be 20% by mass or less, 18% by mass or less, or 16% by mass or less.
- the amount of iron in the exhaust gas purification catalyst device (the mass of iron in terms of ferric oxide (Fe 2 O 3 ) per 1 L of the base material) is in the range of 0.3 g / L or more and 2.5 g / L or less. if, in comparison with Comparative example, which is N 2 O slip amount is suppressed and good results were obtained. Further, when the amount of iron in the exhaust gas purification catalyst device was in the range of 0.6 g / L or more and 2.5 g / L or less, the NOx purification ability was also excellent as compared with the comparative example.
- the amount of N 2 O slip is suppressed in Examples 3, 6 and 7 containing iron-supported metal oxide particles as compared with Comparative Example 1 containing no iron-supported metal oxide particles. Furthermore, as the Fe 2 O 3 carrying ratio in the iron-supported metal oxide particles increased, the N 2 O slip amount tended to decrease. From this, if the Fe 2 O 3 supporting ratio in the iron-supported metal oxide particles in the coat layer is 2.0% by mass or more, the effect of suppressing the amount of N 2 O slip can be exhibited. 2.0 mass% or more, 4.0 wt% or more, or if 5.0 mass% or more, the effect of suppressing the N 2 O slip amount is preferably expressed was confirmed.
- Example 8 to 11 The catalyst layer was formed in the same manner as in Example 3 except that the iron-supported metal oxide particles (Fe 2 O 3 supported amount 9.0% by mass) shown in Table 5 were used instead of the iron alumina particles.
- a slurry for exhaust gas was prepared and used to manufacture an exhaust gas purification catalyst device.
- Comparative Example 5 Using the catalyst layer forming slurry 1 and the catalyst layer forming slurry 2 prepared in the same manner as in Comparative Example 4, Cu was placed on the substrate in the same manner as in Comparative Example 3 except that the order of application was reversed.
- An exhaust gas purification catalyst device was manufactured by forming a catalyst layer composed of a lower layer containing CHA-type zeolite particles (coating amount 140 g / L) and an upper layer containing iron-supported metal oxide particles (coating amount 14 g / L). The SCR performance of the obtained exhaust gas purification catalyst device was evaluated in the same manner as in Example 1. The results are shown in Table 6.
- Comparative Example 6 An exhaust gas purification catalyst device obtained in the same manner as in Comparative Example 1 is placed on the upstream side of the exhaust gas flow. An exhaust gas purification catalyst device obtained in the same manner as in Comparative Example 2 is placed on the downstream side of the exhaust gas flow. They were arranged and connected in series to form a tandem type exhaust gas purification catalyst system. The SCR performance of the obtained exhaust gas purification catalyst system was evaluated in the same manner as in Example 1. The results are shown in Table 6.
- Comparative Example 7 An exhaust gas purification catalyst device obtained in the same manner as in Comparative Example 2 is placed on the upstream side of the exhaust gas flow. An exhaust gas purification catalyst device obtained in the same manner as in Comparative Example 1 is placed on the downstream side of the exhaust gas flow. They were arranged and connected in series to form a tandem type exhaust gas purification catalyst system. The SCR performance of the obtained exhaust gas purification catalyst system was evaluated in the same manner as in Example 1. The results are shown in Table 6.
- Example 3 relates to an example of the catalyst device of the present invention having a single catalyst coat layer in which Cu-CHA type zeolite particles and iron-supported metal oxide particles are mixed.
- Cu-CHA type zeolite particles and iron-supported metal oxide particles are mixed in the same catalyst coat layer, and it is considered that the contact frequency between the two is high. ..
- N 2 O slip amount is very small.
- Comparative Examples 4 and 5 relate to a catalyst apparatus having a two-layered catalyst coat layer in which a layer containing Cu-CHA type zeolite particles and a layer containing iron-supported metal oxide particles are laminated, respectively.
- the Cu-CHA type zeolite particles and the iron-supported metal oxide particles are in contact with each other only at the contact interface of both layers.
- N 2 O slip amount of suppression is insufficient.
- Comparative Examples 6 and 7 are tandem type in which a catalyst device having a catalyst coat layer containing Cu-CHA type zeolite particles and a catalyst device having a catalyst coat layer containing iron-supported metal oxide particles are connected in series. Regarding the catalytic system of. In the catalyst coat layer of these comparative examples, the Cu-CHA type zeolite particles and the iron-supported metal oxide particles are not in contact with each other. In Comparative Examples 6 and 7, as compared with Comparative Examples 4 and 5, N 2 O slip amount was more often.
- the XRD measurement conditions were as follows.
- FIGS. 1 to 3 The XRD charts obtained in Analysis Example 1 are shown in FIGS. 1 to 3, and the XRD charts obtained in Analysis Example 2 are shown in FIGS. 4 to 6, respectively.
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Abstract
Description
前記1又は複数の触媒層のうちの少なくとも1つの触媒層が、
Cu-CHA型ゼオライト粒子、及び
金属酸化物粒子上に鉄が担持された、鉄担持金属酸化物粒子
の双方を含む、
排ガス浄化触媒装置。
《態様2》前記金属酸化物粒子が、アルミナ、シリカ、チタニア、ジルコニア、及びセリアより成る群から選択される、1種の金属の酸化物粒子、又は2種以上の金属の複合酸化物粒子である、態様1に記載の排ガス浄化触媒装置。
《態様3》前記金属酸化物粒子が、アルミナ粒子である、態様2に記載の排ガス浄化触媒装置。
《態様4》前記排ガス浄化触媒装置における鉄の量が、前記基材1L当たりの酸化第二鉄(Fe2O3)換算の鉄の質量として、0.3g/L以上1.3g/L以下である、態様1~3のいずれか一項に記載の排ガス浄化触媒装置。
《態様5》前記排ガス浄化触媒装置における鉄の量が、前記基材1L当たりの酸化第二鉄(Fe2O3)換算の鉄の質量として、0.6g/L以上1.3g/L以下である、態様1~3のいずれか一項に記載の排ガス浄化触媒装置。
《態様6》前記触媒層における、前記Cu-CHA型ゼオライト粒子と、前記鉄担持金属酸化物粒子との割合が、両者の合計に対する鉄担持金属酸化物粒子の質量百分率として、5質量%以上20質量%以下である、態様1~5のいずれか一項に記載の排ガス浄化触媒装置。
《態様7》選択的接触還元用である、態様1~6のいずれか一項に記載の排ガス浄化触媒装置。
《態様8》態様1~7のいずれか一項に記載の排ガス浄化触媒装置の製造方法であって、
(1)前記Cu-CHA型ゼオライト粒子と、前記鉄担持金属酸化物粒子とを、混合して湿式粉砕し、触媒層形成用スラリーを得ること、及び
(2)前記基材上に、前記触媒層形成用スラリーを塗布して焼成し、前記基材上に前記触媒層を形成すること
を含む、
排ガス浄化触媒装置の製造方法。
《態様9》態様7に記載の排ガス浄化触媒装置を用いて排ガスを浄化する、排ガス浄化方法であって、
前記排ガス浄化触媒装置に、排ガス及び還元剤を供給して、前記排ガス中のNOxをN2に還元することを含む、
排ガス浄化方法。
基材と、基材上の1又は複数の触媒層とを含む排ガス浄化触媒装置であって、
上記1又は複数の触媒層のうちの少なくとも1つの触媒層が、
Cu-CHA型ゼオライト粒子、及び
金属酸化物粒子上に鉄が担持された、鉄担持金属酸化物粒子
の双方を含むことを特徴とする。
本発明の排ガス浄化触媒装置における基材としては、排ガス浄化触媒装置の基材として一般に使用されているものを使用することができる。例えば、コージェライト、SiC、ステンレス鋼、無機酸化物粒子等の材料から構成されている、例えばストレートフロー型のモノリスハニカム基材であってよい。
本発明の排ガス浄化触媒装置は、1又は複数の触媒層を有し、そのうちの1つの触媒層は、Cu-CHA型ゼオライト粒子、及び鉄担持金属酸化物粒子の双方を含む。すなわち、本発明の排ガス浄化触媒装置において、Cu-CHA型ゼオライト粒子と、鉄担持金属酸化物粒子とは、同一の触媒層内に含まれる。
本発明におけるCu-CHA型ゼオライト粒子は、銅でイオン交換されたCHA(Chabazite、チャバサイト)型のゼオライトから成る粒子を意味する。このCu-CHA型ゼオライト粒子としては、SCR触媒として公知のものから適宜選択して用いてよい。
本発明における鉄担持金属酸化物粒子は、金属酸化物粒子上に鉄が担持されて成る粒子である。
所望の金属酸化物粒子のゾルと、鉄化合物とを、適当な溶媒(例えば水)中で混合して、混合液を調製すること;
得られた混合液を、スプレードライして、乾燥粉末状態の前駆体粒子ゲルを得ること;及び
得られた前駆体粒子ゲルを焼成すること。
所望の金属酸化物粒子を、鉄化合物を適当な溶媒(例えば水)中に溶解した溶液中に浸漬すること;及び
浸漬後の金属酸化物粒子を焼成すること。
本発明の排ガス浄化触媒装置では、特定触媒層における、Cu-CHA型ゼオライト粒子と、鉄担持金属酸化物粒子との割合は、SCR触媒能と、N2Oスリップ量の抑制効果とのバランスの観点から、Cu-CHA型ゼオライト及び鉄担持金属酸化物の合計質量に対する鉄担持金属酸化物の質量割合(質量百分率)として、5質量%以上、7質量%以上、10質量%以上、12質量%以上、又は15質量%以上であってよく、20質量%以下、18質量%以下、15質量%以下、又は12質量%以下であってよい。
本発明の排ガス浄化触媒装置における特定触媒層は、Cu-CHA型ゼオライト粒子、及び鉄担持金属酸化物粒子の双方を含む。この特定触媒層は、これら以外に、他の任意成分を含んでいてよい。
本発明の排ガス浄化触媒装置における特定触媒層の量(コート量)は、基材1L当たりの特定触媒層の質量として、十分に高いSCR触媒能を発現する観点から、80g/L以上、100g/L以上、120g/L以上、130g/L以上、又は140g/L以上であってよく、排ガス浄化触媒装置の圧損を抑制する観点から、250g/L以下、200g/L以下、180g/L以下、160g/L以下、150g/L以下、又は140g/L以下であってよい。
本発明の排ガス浄化触媒装置は、特定触媒層を有する。本発明の排ガス浄化触媒装置は、必要に応じて、特定触媒層以外に、その他の触媒層を有していてもよい。
本発明の排ガス浄化触媒装置は、上記の構成を有している限り、任意の方法によって製造されてよい。本発明の排ガス浄化触媒装置の一例として、基材上に特性触媒層を単層で有する場合を例にとり、その製造方法として、以下の方法を例示する:
(1)Cu-CHA型ゼオライト粒子と、鉄担持金属酸化物粒子とを、混合して湿式粉砕し、触媒層形成用スラリーを得ること(触媒層形成用スラリー調製工程)、及び
(2)基材上に、触媒層形成用スラリーを塗布して焼成し、基材上に触媒層を形成すること(触媒層形成工程)
を含む、排ガス浄化触媒装置の製造方法。
本発明の排ガス浄化触媒装置は、例えば、ディーゼル内燃機関、ガソリン内燃機関等から排出される排ガスを浄化するための、選択的接触還元(SCR)用の触媒装置として使用されてよい。
本発明は、更に、本発明の排ガス浄化触媒装置を用いて排ガスを浄化する、排ガス浄化方法を提供する。
(1)触媒層形成用スラリーの調製
純水200質量部中に、シリカバインダーゾル分散液100質量部(乾燥質量15質量部)、Cu-CHA型ゼオライト粒子85質量部、及び鉄担持金属酸化物粒子としての、鉄アルミナ粒子(スプレードライ法鉄アルミナ粒子、Fe2O3担持量9.0質量%)2質量部を、この順に混合し、湿式粉砕法にて粉砕することにより、触媒層形成用スラリーを得た。
基材上に、上記で得られた触媒層形成用スラリーを、焼成後のコート量が142.8g/Lとなるように塗布し、250℃において乾燥後、500℃にて1時間焼成することにより、基材上に触媒層を形成して、排ガス浄化触媒装置を製造した。この外ガス浄化触媒装置の触媒層における、添加剤(鉄アルミナ粒子)のコート量は、2.8g/Lであった。次いで、この排ガス浄化触媒装置を、水熱耐久炉中、630℃にて50時間耐久した後に、SCR性能の評価に供した。
上記で得られた排ガス浄化触媒装置のSCR性能の評価は、モデルガスを用いて行った。
スプレードライ法鉄アルミナ粒子におけるFe2O3担持量を、表3に示したように変更した他は、実施例1と同様にして、それぞれ触媒層形成用スラリーを調製した。これを用いて、焼成後のコート量が表3に記載の値となるように、塗布量を変更した他は、実施例1と同様にして、基材上に触媒層形成用スラリーを塗布し、乾燥及び焼成を行って、排ガス浄化触媒装置を製造した。
スプレードライ法鉄アルミナ粒子の代わりに、含侵法によりアルミナ上に同量のFe2O3を担持した、含侵法鉄アルミナ粒子を用いた他は、実施例3と同様にして、排ガス浄化触媒装置を製造し、評価した。結果は表3に示す。
スプレードライ法鉄アルミナ粒子の代わりに、アルミナ9.1質量部及び酸化鉄0.9質量部との混合物を用いた他は、実施例3と同様にして、排ガス浄化触媒装置を製造し、評価した。結果は表3に示す。
鉄アルミナ粒子におけるFe2O3担持量を、表4に示したように変更した他は、実施例3と同様にして、それぞれ触媒層形成用スラリーを調製し、これを用いて、排ガス浄化触媒装置を製造した。
鉄アルミナ粒子の代わりに、表5に示した鉄担持金属酸化物粒子(Fe2O3担持量9.0質量%)をそれぞれ用いた他は、実施例3と同様にして、それぞれ触媒層形成用スラリーを調製し、これを用いて、排ガス浄化触媒装置を製造した。
スプレードライ法鉄アルミナ:γ-アルミナ上に酸化鉄(Fe2O3)が担持された粒子、スプレードライ法により製造
スプレードライ法鉄シリカアルミナ:シリカアルミナ(SiO2:Al2O3=5:95(質量比))上に酸化鉄(Fe2O3)が担持された粒子、スプレードライ法により製造
スプレードライ法鉄チアニア:チタニア上に酸化鉄(Fe2O3)が担持された粒子、スプレードライ法により製造
スプレードライ法鉄セリア:セリア上に酸化鉄(Fe2O3)が担持された粒子、スプレードライ法により製造
(1)触媒層形成用スラリー1の調製
純水250質量部中に、アルミナバインダーゾル5質量部、及び鉄担持金属酸化物粒子としての、鉄アルミナ(Fe2O3含量9.0質量%)粒子95質量部を、この順に混合し、湿式粉砕法にて粉砕することにより、触媒層形成用スラリー1を得た。
純水200質量部中に、シリカバインダーゾル分散液100質量部(乾燥質量15質量部)、及びCu-CHA型ゼオライト粒子85質量部を、この順に混合し、湿式粉砕法にて粉砕することにより、触媒層形成用スラリー2を得た。
基材上に、触媒層形成用スラリー1を、焼成後のコート量が14g/Lとなるように塗布し、250℃において乾燥した。次いで、触媒層形成用スラリー1を塗布及び乾燥後の基材上に、触媒層形成用スラリー2を、焼成後のコート量が140g/Lとなるように塗布し、250℃において乾燥した後、500℃にて1時間焼成することにより、基材上に、鉄担持金属酸化物粒子を含む下層、及びCu-CHA型ゼオライト粒子を含む上層から成る触媒層を形成して、排ガス浄化触媒装置を製造した。
上記で得られた排ガス浄化触媒装置について、実施例1と同様にして、SCR性能の評価を行った。結果は表6に示す。
比較例4と同様にして調製した、触媒層形成用スラリー1及び触媒層形成用スラリー2を用い、塗布する順番を逆にした他は、比較例3と同様にして、基材上に、Cu-CHA型ゼオライト粒子を含む下層(コート量140g/L)、及び鉄担持金属酸化物粒子を含む上層(コート量14g/L)から成る触媒層を形成して、排ガス浄化触媒装置を製造した。得られた排ガス浄化触媒装置について、実施例1と同様にして、SCR性能の評価を行った。結果は表6に示す。
比較例1と同様にして得られた排ガス浄化触媒装置を、排ガス流れの上流側に、
比較例2と同様にして得られた排ガス浄化触媒装置を、排ガス流れの下流側に、
配置して、これらを直列に接続して、タンデム型の排ガス浄化触媒システムとした。得られた排ガス浄化触媒システムについて、実施例1と同様にして、SCR性能の評価を行った。結果は表6に示す。
比較例2と同様にして得られた排ガス浄化触媒装置を、排ガス流れの上流側に、
比較例1と同様にして得られた排ガス浄化触媒装置を、排ガス流れの下流側に、
配置して、これらを直列に接続して、タンデム型の排ガス浄化触媒システムとした。得られた排ガス浄化触媒システムについて、実施例1と同様にして、SCR性能の評価を行った。結果は表6に示す。
上記の実施例3で使用したスプレードライ法鉄アルミナ粒子を粉砕して、XRDを測定した。その結果、2θ=31°付近及び51°付近に、Fe2O3結晶に由来するピークは観測されず、アルミナ上にFe2O3が極めて高分散にて担持されていることが確認された。
XRD測定装置:(株)リガク製、粉末・薄膜X線回折装置、型式名「RINT TTR III」
測定方法:ステップスキャニング法
送り速度:4°/分
回折角範囲:2θ=5~85°
ステップ幅:0.02°
加速電圧:40kV
加速電流:250mA
上記の実施例5で使用した含侵法鉄アルミナを粉砕して、分析例1と同様にして、XRDを測定した。その結果、2θ=31°付近及び51°付近に、それぞれ、Fe2O3結晶に帰属されるピークが観測され、アルミナ上でFe2O3が凝集して結晶相を形成していることが分かった。2θ=31°付近のピークは、ショルダーピークである。
Claims (9)
- 基材と、前記基材上の1又は複数の触媒層とを含む排ガス浄化触媒装置であって、
前記1又は複数の触媒層のうちの少なくとも1つの触媒層が、
Cu-CHA型ゼオライト粒子、及び
金属酸化物粒子上に鉄が担持された、鉄担持金属酸化物粒子
の双方を含む、
排ガス浄化触媒装置。 - 前記金属酸化物粒子が、アルミナ、シリカ、チタニア、ジルコニア、及びセリアより成る群から選択される、1種の金属の酸化物粒子、又は2種以上の金属の複合酸化物粒子である、請求項1に記載の排ガス浄化触媒装置。
- 前記金属酸化物粒子が、アルミナ粒子である、請求項2に記載の排ガス浄化触媒装置。
- 前記排ガス浄化触媒装置における鉄の量が、前記基材1L当たりの酸化第二鉄(Fe2O3)換算の鉄の質量として、0.3g/L以上1.3g/L以下である、請求項1~3のいずれか一項に記載の排ガス浄化触媒装置。
- 前記排ガス浄化触媒装置における鉄の量が、前記基材1L当たりの酸化第二鉄(Fe2O3)換算の鉄の質量として、0.6g/L以上1.3g/L以下である、請求項1~3のいずれか一項に記載の排ガス浄化触媒装置。
- 前記触媒層における、前記Cu-CHA型ゼオライト粒子と、前記鉄担持金属酸化物粒子との割合が、両者の合計に対する鉄担持金属酸化物粒子の質量百分率として、5質量%以上20質量%以下である、請求項1~5のいずれか一項に記載の排ガス浄化触媒装置。
- 選択的接触還元用である、請求項1~6のいずれか一項に記載の排ガス浄化触媒装置。
- 請求項1~7のいずれか一項に記載の排ガス浄化触媒装置の製造方法であって、
(1)前記Cu-CHA型ゼオライト粒子と、前記鉄担持金属酸化物粒子とを、混合して湿式粉砕し、触媒層形成用スラリーを得ること、及び
(2)前記基材上に、前記触媒層形成用スラリーを塗布して焼成し、前記基材上に前記触媒層を形成すること
を含む、
排ガス浄化触媒装置の製造方法。 - 請求項7に記載の排ガス浄化触媒装置を用いて排ガスを浄化する、排ガス浄化方法であって、
前記排ガス浄化触媒装置に、排ガス及び還元剤を供給して、前記排ガス中のNOxをN2に還元することを含む、
排ガス浄化方法。
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JP2013013894A (ja) * | 2009-11-30 | 2013-01-24 | Johnson Matthey Plc | 過渡NOx排気ガスを処理するための触媒 |
JP2014530097A (ja) * | 2011-10-05 | 2014-11-17 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | ガス流中のNOxを処理するためのCu−CHA/Fe−BEA混合ゼオライト触媒および方法 |
WO2015087816A1 (ja) * | 2013-12-11 | 2015-06-18 | 株式会社キャタラー | 排ガス浄化材 |
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JP2014530097A (ja) * | 2011-10-05 | 2014-11-17 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | ガス流中のNOxを処理するためのCu−CHA/Fe−BEA混合ゼオライト触媒および方法 |
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