WO2014034524A1 - Catalyseur d'épuration de gaz d'échappement - Google Patents

Catalyseur d'épuration de gaz d'échappement Download PDF

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WO2014034524A1
WO2014034524A1 PCT/JP2013/072437 JP2013072437W WO2014034524A1 WO 2014034524 A1 WO2014034524 A1 WO 2014034524A1 JP 2013072437 W JP2013072437 W JP 2013072437W WO 2014034524 A1 WO2014034524 A1 WO 2014034524A1
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mass
exhaust gas
catalyst
iron
gas purification
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PCT/JP2013/072437
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English (en)
Japanese (ja)
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中原　祐之輔
央記 法師人
誠治 森内
博昭 奥村
文和 木俣
豊史 津田
清藏 宮田
亀山　秀雄
ユ 郭
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三井金属鉱業株式会社
スズキ株式会社
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Priority to CN201380024605.8A priority Critical patent/CN104302392A/zh
Priority to DE112013004202.9T priority patent/DE112013004202B4/de
Publication of WO2014034524A1 publication Critical patent/WO2014034524A1/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
    • B01J37/08—Heat treatment
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • 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
    • F01N3/101—Three-way catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2065—Cerium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20738—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20746—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/70—Non-metallic catalysts, additives or dopants
    • B01D2255/702—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0248—Coatings comprising impregnated particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
    • 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 that can be used to purify exhaust gas discharged from an internal combustion engine.
  • the exhaust gas from gasoline fueled vehicles contains harmful components such as hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx).
  • the hydrocarbon (HC) is oxidized to be converted to water and carbon dioxide
  • the carbon monoxide (CO) is oxidized to be converted to carbon dioxide
  • the nitrogen oxide (NOx) is reduced to be converted to nitrogen It is necessary to purify each harmful component with a catalyst.
  • a catalyst for treating such exhaust gas hereinafter referred to as "exhaust gas purification catalyst”
  • a three-way catalyst capable of oxidizing and reducing CO, HC and NOx is used.
  • the three-way catalyst is generally mounted in the form of a converter between the engine and the muffler of the exhaust pipe.
  • a refractory oxide porous body having a high specific surface area for example, an alumina porous body having a high specific surface area, such as platinum (Pt), palladium (Pd), rhodium (Rh), etc. It is known to carry a noble metal and to carry it on a substrate, for example a monolithic substrate made of a refractory ceramic or metal honeycomb structure, or on refractory particles. There is.
  • the catalyst can not sufficiently exhibit the purification catalyst performance, so the function of controlling the air-fuel ratio (A / F) also in the catalyst layer itself is Desired. Then, the catalyst which added the co-catalyst to the precious metal which is a catalyst active component is used for the purpose of preventing the fall of the purification performance of the catalyst which arises due to change of an air fuel ratio with the chemical action of catalyst itself.
  • cocatalyst As such a cocatalyst, there is known a cocatalyst (referred to as “OSC material”) having an oxygen storage capacity (OSC: Oxygen Storage Capacity) which releases oxygen in a reducing atmosphere and absorbs oxygen in an oxidizing atmosphere.
  • OSC oxygen storage capacity
  • ceria cerium oxide, CeO 2
  • ceria-zirconia composite oxide etc. are known as OSC materials having an oxygen storage ability.
  • Patent Document 1 Japanese Unexamined Patent Publication No. 2005-296735 discloses a catalyst in which iron oxide is supported on a carrier containing a ceria-zirconia composite oxide.
  • Patent Document 2 Japanese Patent Laid-Open No. 2004-160433 includes a catalyst comprising a complex oxide of iron and at least one metal selected from the group consisting of ceria, zirconia, aluminum, titanium and manganese. It is disclosed.
  • Patent Document 3 Japanese Unexamined Patent Publication No. 2008-18322 discloses a catalyst having a structure in which iron oxide is dispersed in a ceria-zirconia composite oxide and at least partially in solid solution.
  • Patent Document 4 Japanese Unexamined Patent Publication No. 2012-50980 discloses an exhaust gas purification catalyst consisting of carbon (C) -iron (Fe) -cerium (Ce).
  • catalysts for automobiles are required to have performance capable of exhibiting stable purification performance even when the flow velocity of exhaust gas changes.
  • the exhaust gas catalyst tends to reduce the surface area and the catalyst activity by sintering.
  • C-Fe-Ce catalyst which has high catalytic activity, has a problem that sintering tendency is strong.
  • an object of the present invention is to provide a new exhaust gas purification catalyst containing C-Fe-Ce, which has not only durability against severe temperature change, but also new performance capable of exhibiting stable purification performance even when the flow velocity of exhaust gas changes. To provide an exhaust gas catalyst.
  • the present invention is characterized in that a mixture containing carbon (C), iron (Fe) and cerium (Ce) is supported on an inorganic porous powdery carrier. Proposes an exhaust gas purification catalyst.
  • the exhaust gas purification catalyst proposed by the present invention has a mixture containing carbon (C), iron (Fe) and cerium (Ce) supported on an inorganic porous powdery support, and has a temperature of 900 to 1,000.degree. Even when exposed to high temperatures, sintering is suppressed, and as a result, it is possible to exhibit stable purification performance at a high level even if the durability is high and the flow velocity of the exhaust gas changes.
  • Exhaust gas purification catalyst In an exhaust gas purification catalyst (referred to as "the present catalyst") as an example of an embodiment of the present invention, a mixture containing carbon (C), iron (Fe) and cerium (Ce) is supported on an inorganic porous powdery carrier An exhaust gas purification catalyst having a configuration as described above.
  • iron carbide (Fe 3 C), iron oxide and cerium oxide each act as active sites showing an oxidation / reduction action.
  • Fe 3 C exhibits high activity as an active site exhibiting an oxidation / reduction action.
  • when Fe 3 C is used alone for example, when it is subjected to durability treatment at 900 ° C. to 1,000 ° C., most of it is oxidized to form oxides such as Fe 2 O 3 because of its low heat resistance. It is usual that the activity will be greatly reduced.
  • it has high catalytic activity even after such durability treatment Can be demonstrated.
  • the content of the mixture relative to the inorganic porous powdery carrier (100% by mass) is preferably 10.0 to 300% by mass, and more preferably at least 20.0% by mass or at most 180% by mass Are particularly preferable, and among them, it is particularly preferable that the content is 30% by mass or more or 120% by mass or less.
  • the content of the mixture with respect to the inorganic porous powdery support is 300% by mass or less, the composite carbonated particles can be prevented from being in intimate contact with each other, and when exposed to high temperatures. Since the sintering can be prevented, it is possible to suppress the decrease of the purification rate due to the reduction of the effective area.
  • it is 10.0 mass% or more the number of catalyst particles can be maintained, and the purification rate can be maintained by the presence of effective active sites.
  • the mass ratio of C, Fe, and Ce atoms (C: Fe: Ce) contained in the mixture is 0.01 to 1.4 with respect to the total amount (100 mass%) of C, Fe, and Ce. It is preferable that the content is 0.1% to 98.9% by mass: 0.1% to 98.9% by mass.
  • the content of carbon (C) is preferably 0.01 to 1.4% by mass, particularly 0.3% by mass, with respect to the total amount (100% by mass) of C, Fe and Ce. It is more preferable that the content is above or 1.3 mass% or less.
  • the content of iron (Fe) is preferably 0.1 to 98.9% by mass with respect to the total amount (100% by mass) of C, Fe and Ce, and in particular, 7.8% by mass or more or 98.
  • the content is particularly preferably 7% by mass or less, and more preferably 26.7% by mass or more or 90.8% by mass or less.
  • the content of cerium (Ce) is preferably 0.1 to 98.9% by mass with respect to the total amount (100% by mass) of C, Fe and Ce, and more preferably 0.1% by mass or more or 92.
  • the content is particularly preferably 1% by mass or less, and more preferably 7.9% by mass or more or 73.0% by mass or less.
  • the mixture may further contain Co.
  • Heat resistance can be improved by containing Co.
  • the content of Co is preferably more than 0.1% by mass and less than 15% by mass, and more preferably 5% by mass or more or 10% by mass or less based on the total amount (100% by mass) of C, Fe and Ce Is preferred.
  • inorganic porous powdery carrier examples include a compound selected from the group consisting of silica, alumina and a titania compound, or an inorganic porous powdery carrier consisting of an OSC material such as ceria-zirconia complex oxide.
  • OSC material such as ceria-zirconia complex oxide.
  • porous powder comprising a compound selected from alumina, silica, silica-alumina, alumino-silicates, alumina-zirconia, alumina-chromia and alumina-ceria.
  • alumina having a specific surface area of more than 50 m 2 / g, such as ⁇ , ⁇ , ⁇ , ⁇ alumina can be used. Among them, it is preferable to use ⁇ or ⁇ alumina.
  • a trace amount of lanthanum (La) can also be included.
  • a cerium compound, a zirconium compound, ceria-zirconia complex oxide etc. can be mentioned, for example.
  • the present catalyst may have a constitution in which a noble metal is supported on an inorganic porous powdery carrier in addition to the above mixture.
  • the amount of the noble metal supported is preferably 0.01% by mass or more, and more preferably 0.41% by mass or more, based on the mass (100% by mass) of the catalyst powder to be supported.
  • palladium (Pd), platinum (Pt), rhodium (Rh) can be mentioned as a precious metal.
  • palladium (Pd) and platinum (Pt) are remarkably preferable.
  • an inorganic porous powdery carrier is added to a solution of an iron compound and a cerium compound, and after the iron compound and the cerium compound are attached to the inorganic porous powdery carrier, the inorganic porous powdery carrier is heated and calcined in the air to obtain the inorganic compound.
  • the present catalyst can be produced by supporting iron oxide and cerium oxide on a porous powdery carrier and then heating in a reactive carbon-containing gas atmosphere such as carbon monoxide (CO) gas.
  • an iron compound and a cerium compound adhere to an inorganic porous powdery carrier for example, after adding an inorganic porous powdery carrier to the solution of an iron compound and a cerium compound, ammonia water and carbonic acid are stirred, A complex hydroxide of Fe and Ce or a complex carbonate is precipitated by adding an alkaline substance such as sodium dropwise to adjust the pH to 10-11.
  • the method of washing the precipitate with water and drying can be mentioned. However, it is not limited to such a method.
  • the Fe compound and the Ce compound are deposited in the solution state on the inorganic porous powdery carrier, the Fe and Ce can enter into the fine pores, and the catalyst is very well dispersed. You can get In addition, heating is performed in a reactive carbon-containing gas atmosphere such as CO gas, in other words, when CO treatment is performed by a vapor phase method, a mixture of iron oxide and cerium oxide is uniformly dispersed in the inorganic porous powdery carrier Not only can it be supported in a state, but it is also possible to disperse carbon (C) as iron carbide uniformly.
  • a reactive carbon-containing gas atmosphere such as CO gas
  • An exhaust gas purification catalyst structure (referred to as “the present catalyst structure") can be produced by forming a catalyst layer containing the present catalyst on a base material.
  • a catalyst layer can be formed by wash-coating a catalyst composition containing the present catalyst on the surface of a substrate exhibiting a honeycomb (monolith) structure, to form a catalyst structure.
  • examples of the material of the base include refractory materials such as ceramics and metal materials.
  • the material of the ceramic base material is refractory ceramic material such as cordierite, cordierite-alpha alumina, silicon nitride, zircon mullite, spodumene, alumina-silica magnesia, zirconium silicate, sillimanite, magnesium silicate, Zircon, petalite, alpha alumina and aluminosilicates can be mentioned.
  • the material of the metallic substrate can include refractory metals, such as stainless steel or other suitable corrosion resistant alloys based on iron.
  • the shape of the substrate may be honeycomb, pellet, or spherical.
  • honeycomb material in general, cordierite materials such as ceramics are often used.
  • a honeycomb made of a metal material such as ferritic stainless steel can also be used.
  • a honeycomb-shaped substrate for example, a monolithic substrate having a large number of fine gas flow passages parallel to the inside of the substrate, ie, channels, can be used so that the fluid can flow inside the substrate.
  • the catalyst composition can be coated on the inner wall surface of each channel of the monolithic substrate by wash coating or the like to form a catalyst layer.
  • Catalyst composition As a catalyst composition for forming the catalyst layer of the present catalyst structure, in addition to the above-mentioned present catalyst, if necessary, a stabilizer and other components may be contained.
  • a stabilizer can be blended for the purpose of suppressing the reduction of palladium oxide (PdOx) to metal under a fuel-rich atmosphere.
  • PdOx palladium oxide
  • examples of this type of stabilizer include alkaline earth metals and alkali metals. Among them, it is possible to select one or more of metals selected from the group consisting of magnesium, barium, calcium and strontium, preferably strontium and barium. Among them, barium is preferable from the viewpoint that the temperature at which PdO x is reduced is the highest, that is, it is difficult to be reduced.
  • a binder component such as a binder component.
  • an inorganic binder for example, a water-soluble solution such as alumina sol, silica sol, or zirconia sol can be used. These can take the form of inorganic oxides when fired.
  • the present catalyst is added to water, mixed, stirred by a ball mill or the like to form a slurry, and a substrate such as a ceramic honeycomb body is immersed in the slurry,
  • a substrate such as a ceramic honeycomb body
  • the method of pulling up, baking, and forming a catalyst layer in the base-material surface etc. can be mentioned.
  • any known method can be adopted, and the present invention is not limited to the above example.
  • the mass of iron nitrate (II) (9 hydrate), cerium nitrate (III) (hexahydrate), alumina powder and OSC material used is iron nitrate (II) (9 hydrate)
  • the mass of iron atoms contained, the mass of cerium atoms contained in cerium (III) nitrate (hexahydrate), the mass of alumina, and the OSC material were adjusted to have the compositions shown in Table 1.
  • iron carbide Fe 3 C
  • iron oxide Fe 3 C
  • cerium oxide A C-Fe-Ce / alumina catalyst or a C-Fe-Ce / OSC material catalyst was obtained, having a configuration in which the mixture containing the catalyst is supported on alumina or OSC material.
  • FIG. 1 is a schematic view of an apparatus for measuring the concentration of a model gas containing NOx, CO, H 2 , and C 3 H 3 as HC.
  • the schematic of the reaction tube which is a part of said measuring apparatus is shown in FIG.
  • the measuring apparatus comprising a standard gas cylinder 1, a mass flow controller 2, a water tank 3, a water pump 4, an evaporator 5, a reaction tube 6, a cooler 8, a gas analyzer 9, etc.
  • Each model gas is generated from the gas cylinder 1, mixed by the mass flow controller 2, the water introduced from the water pump 4 is vaporized by the evaporator 5, and the gases are combined by the evaporator 5 to the reaction pipe 6 Introduce.
  • the reaction tube 6 containing the model gas is heated by the electric heating furnace 7.
  • Each model gas is oxidized or reduced by the catalyst 10 in the reaction tube 6.
  • the gas after reaction is analyzed for composition by the gas analyzer 9 after water vapor is removed in the cooler 8.
  • the gas analyzer 9 can perform quantitative analysis of O 2 , CO, N 2 O, CO 2 , HC (C 3 H 6 ), H 2 and the like by gas chromatography, and NOx, NO, NO 2 , CO and the like can be quantitatively analyzed by the NOx analyzer.
  • NOx conversion rate ⁇ (inlet NO molar flow rate 10 NO 2 molar flow rate)-(outlet NO molar flow rate 10 NO 2 molar flow rate) / (inlet NO molar flow rate 10 NO 2 molar flow rate) x 100%
  • the present catalyst is produced by heat treatment in a CO gas atmosphere as a compounding ratio, amorphous C adheres to the surface, so a C amount larger than the stoichiometric carbon ratio of Fe 3 C is measured. There is a thing. Therefore, in order to compare stable catalyst performance, it is desirable to evaluate the catalyst subjected to the durability treatment. Therefore, after performing an endurance treatment at 1,000 ° C. for 5 hours as necessary, the temperature (T50) at which the conversion rate of NOx and the conversion rate of NOx become 50% was measured.
  • the catalyst dispersed on alumina powder was found to have a low T50 even after durability treatment. It is considered that this is because sintering was suppressed by dispersing on alumina.
  • the results of changing the SV value are also shown in Table 4.
  • the catalyst dispersed on alumina was found to have low T50 and high activity even under high SV.
  • Table 5 shows the results of measurement of the temperature (T50) at which the conversion of NOx of the catalyst in which C-Fe-Ce is dispersed on the OSC material becomes 50%.
  • OriginPro 7.5 graph creation software of Lightstone Co., Ltd. is used to create a triangle composition isoactivity diagram with carbon + iron, cerium, alumina as the apex, T50 725 ° C, 750
  • the compositions which become ° C, 775 ° C, 800 ° C, 850 ° C, 900 ° C and 950 ° C were connected by a line (isoactivity temperature line).
  • the triangular diagram is shown in FIG.
  • the ratio of the catalyst component (C + Fe + Ce) to alumina (100% by mass) is preferably 12.3 to 268% by mass, more preferably 21.4 to 177% by mass, and particularly preferably 34.4 to 116% by mass Is preferred.
  • the optimum compositions for minimizing T50 were (carbon + iron), cerium and alumina 18.50 mass%, 18.55 mass%, and 62.94 mass%, respectively. From these results, the content of the mixture relative to the inorganic porous powdery carrier (100% by mass) is preferably 10.0 to 300% by mass, and more preferably at least 20.0% by mass or at most 180% by mass. It is considered particularly preferable that there be 30% by mass or more or 120% by mass or less.
  • the content of carbon (C) is 0.01 to 1.4 mass% with respect to the total amount (100 mass%) of C, Fe and Ce It can be considered that is preferably 0.3 to 1.3 among them.
  • the content of iron (Fe) is preferably 0.1 to 98.9% by mass, more preferably 7.8 to 98.7% by mass, with respect to the total amount (100% by mass) of C, Fe and Ce. It is particularly preferable that the ratio is 26.7 to 90.8% by mass.
  • the content of cerium (Ce) is preferably 0.1 to 98.9% by mass, more preferably 0.1 to 92.1% by mass, based on the total amount (100% by mass) of C, Fe and Ce. It is particularly preferable that it is particularly preferable that 7.9 to 73.0% by mass is more preferable.
  • Example 29 to 31 Examination of precious metal addition effect> A catalyst was produced in the same manner as in Examples 1 to 28 except that the mass of iron atom, the mass of cerium atom, and the mass of alumina were changed to the ratios shown in Table 7. Then, the obtained catalyst powder was added to a Pd nitrate solution measured to have the amount of the supported noble metal shown in Table 7, stirred at a rotational speed of 600 rpm for 3 hours, and then dried in a dryer at 120 ° C. Next, the noble metal-supported powder catalyst has a configuration in which the mixture containing iron carbide (Fe 3 C), iron oxide and cerium oxide is supported on alumina by calcining at 600 ° C. for 3 hours in the air atmosphere (Example 29) I got ⁇ 31).
  • Fe 3 C iron carbide
  • cerium oxide cerium oxide
  • the results of measuring the temperature (T50) at which the conversion of NOx of the catalyst supporting Pd on the composition of Example 1 is 50% are shown in Table 7. It was found that T50 of NOx decreased as the loading amount of Pd increased, and Pd greatly contributed to the improvement of the performance of the exhaust gas catalyst. Further, the amount of Pd supported is about a fraction of the amount usually supported on the exhaust gas purification catalyst, which can also contribute to the reduction of the amount of expensive Pd used. In consideration of such a viewpoint, the supported amount of the noble metal is preferably 0.01% by mass or more with respect to the supported catalyst powder (100% by mass), and more preferably 0.41% by mass or more. It is considered preferable.
  • Examples 32 to 34 Examination of Co Addition Effect After dissolving iron nitrate (II) (9 hydrate), cerium nitrate (III) (hexahydrate) and cobalt nitrate in pure water, add alumina powder (m 001) while stirring to prepare a mixed solution did.
  • the mass of iron (II) nitrate (9 hydrate), cerium (III) nitrate (6 hydrate), cobalt nitrate and alumina powder to be used is contained in iron (II) nitrate (9 hydrate)
  • the ratio of mass of iron atom, mass of cerium atom contained in cerium (III) nitrate (hexahydrate), mass of cobalt atom contained in cobalt nitrate, and mass of alumina are shown in Table 8 Adjusted to
  • the T50 of NOx decreases as the addition amount of Co increases, and increases above a certain amount. From this result, it is found that Co contributes to the improvement of the performance of the exhaust gas catalyst.
  • the content of Co is preferably more than 0.1% by mass and less than 15% by mass with respect to the catalyst material (100% by mass), and particularly preferably 5 to 10% by mass. Is considered to be more preferable.
  • Example 35 Effects of Co and Pt Addition After dissolving iron nitrate (II) (9 hydrate), cerium nitrate (III) (hexahydrate) and cobalt nitrate in pure water, add alumina powder (m 001) while stirring to prepare a mixed solution did.
  • the mass of iron (II) nitrate (9 hydrate), cerium (III) nitrate (6 hydrate) and cobalt nitrate and alumina powder to be used is contained in iron (II) nitrate (9 hydrate)
  • the mass of iron atom, the mass of cerium atom contained in cerium (III) nitrate (hexahydrate), the mass of cobalt atom contained in cobalt nitrate, and the mass of alumina become the ratios shown in Table 9 Adjusted to
  • Example 36 Effects of Co and Pd Addition
  • Pd / C-Fe is used in the same manner as Example 35 except that an acetone solution of palladium acetate is used instead of an aqueous solution of chloroplatinic acid and palladium (Pd) is supported by vacuum drying.
  • a Ce-Co / alumina catalyst is obtained.
  • the amount of supported Pd is shown in Table 9.
  • the T50 of NOx shows a low value even when the SV value is as high as 3,000 mL / min ⁇ g, and in C-Fe-Ce-Co / alumina catalysts supporting Pt or Pd, Pt or Pd is usually an exhaust gas purification It has been found that even when only a fraction of the amount supported by the catalyst is supported, good performance is exhibited.

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  • Exhaust Gas After Treatment (AREA)

Abstract

La présente invention concerne un catalyseur d'épuration de gaz d'échappement, qui contient du C-Fe-Ce, et constitue un nouveau catalyseur de gaz d'échappement possédant une efficacité d'épuration stable, même si le débit des gaz d'échappement change, et qui présente une durabilité en présence de grands changements de température. L'invention concerne un catalyseur d'épuration de gaz d'échappement, conçu de manière à présenter un mélange contenant du carbone (C), du fer (Fe) et du cérium (Ce), supporté par un support pulvérulent poreux inorganique, et est caractérisé en ce que la proportion du mélange par rapport au support pulvérulent poreux inorganique est de 10-300% en masse.
PCT/JP2013/072437 2012-08-27 2013-08-22 Catalyseur d'épuration de gaz d'échappement WO2014034524A1 (fr)

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CN104302392A (zh) 2015-01-21

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