WO2022065188A1 - Catalyseur d'oxydation de méthane, catalyseur multicouche d'oxydation de méthane, système de purification de gaz d'échappement utilisant ledit catalyseur d'oxydation de méthane ou ledit catalyseur multicouche d'oxydation de méthane, et procédé pour produire le catalyseur d'oxydation de méthane - Google Patents

Catalyseur d'oxydation de méthane, catalyseur multicouche d'oxydation de méthane, système de purification de gaz d'échappement utilisant ledit catalyseur d'oxydation de méthane ou ledit catalyseur multicouche d'oxydation de méthane, et procédé pour produire le catalyseur d'oxydation de méthane Download PDF

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WO2022065188A1
WO2022065188A1 PCT/JP2021/034080 JP2021034080W WO2022065188A1 WO 2022065188 A1 WO2022065188 A1 WO 2022065188A1 JP 2021034080 W JP2021034080 W JP 2021034080W WO 2022065188 A1 WO2022065188 A1 WO 2022065188A1
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methane oxidation
alumina
catalyst
methane
base material
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PCT/JP2021/034080
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English (en)
Japanese (ja)
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靖幸 伴野
大成 伊藤
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エヌ・イーケムキャット株式会社
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Publication of WO2022065188A1 publication Critical patent/WO2022065188A1/fr

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    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • 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
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • 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

Definitions

  • the present invention relates to a methane oxidation catalyst for oxidizing methane contained in gas, a methane oxidation laminated catalyst, an exhaust gas purification system using these, a method for producing a methane oxidation catalyst, and the like.
  • CNG compressed natural gas
  • LNG liquefied natural gas
  • city gas city gas
  • light oil kerosene, etc.
  • CO carbon monoxide
  • NO nitrogen monoxide
  • NOx nitrogen oxides
  • SOx sulfur oxides
  • HC unburned hydrocarbons
  • the exhaust gas emitted from a lean combustion gas engine such as a cogeneration system or a gas heat pump (GHP), and a bi-fuel engine (BF) or a dual fuel engine (BF) or a dual fuel engine in which CNG or LNG is used in combination with gasoline or light oil
  • a lean combustion gas engine such as a cogeneration system or a gas heat pump (GHP)
  • BF bi-fuel engine
  • BF dual fuel engine
  • a dual fuel engine in which CNG or LNG is used in combination with gasoline or light oil
  • the exhaust gas emitted from CNG-DFCI, LNG-DFCI, etc. may also contain a trace amount of methane.
  • platinum group elements such as platinum, palladium, and rhodium are supported on aluminum base material particles as catalytically active components, for example, Pd-supported alumina and Pt / Pd. Supported alumina and the like are known (see, for example, Patent Documents 1 to 3).
  • the catalysts described in Patent Documents 1 to 3 have a problem that they act in a high temperature region of, for example, 500 ° C. or higher and have low catalytic activity in a low temperature region of less than 500 ° C., and the oxidative activity of methane in such a low temperature region is high. Improvement is required.
  • the catalyst described in Patent Document 4 is found to have improved methane oxidation activity in the low temperature region as compared with the catalysts of Patent Documents 1 to 3, but the degree of improvement is not sufficient and there is still room for improvement. Further, since the catalyst described in Patent Document 5 uses tin, which can be a biological poison due to chemical action with organic compounds, ash, etc., from the viewpoint of safety during manufacturing and use, impact on the environment, etc. Therefore, the development of alternative products is required.
  • the present invention has been made in view of the above problems.
  • the purpose is to provide a novel methane oxidation catalyst, a methane oxidation laminated catalyst, an exhaust gas purification system using these, a method for producing a methane oxidation catalyst, etc., in which the methane catalyst activity is enhanced in a low temperature region of less than 500 ° C. To do.
  • the present inventors have diligently studied to solve the above problems. As a result, they have found that the above problems can be solved by using a composite catalyst in which Pd and Ni are supported on alumina-based base material particles, and have completed the present invention.
  • a methane oxidation catalyst for oxidizing methane contained in a gas which comprises alumina-based base material particles and composite particles containing Pd and Ni supported on the alumina-based base material particles.
  • Methane oxidation catalyst for oxidizing methane contained in a gas, which comprises alumina-based base material particles and composite particles containing Pd and Ni supported on the alumina-based base material particles.
  • alumina-based base metal particles include at least one selected from the group consisting of alkali metal elements, alkaline earth metal elements, transition elements, and rare earth elements.
  • a methane oxidation laminated catalyst for oxidizing methane contained in a gas comprising a catalyst carrier and a catalyst layer supported on the catalyst carrier, wherein the catalyst layer is an alumina-based base metal particle.
  • a methane oxidation laminated catalyst comprising a methane oxidation catalyst containing composite particles containing Pd and Ni supported on the alumina-based base metal particles.
  • the methane oxidation laminated catalyst further has the technical features described in any one of the above [1] to [10].
  • a methane oxidation catalyst containing alumina-based base material particles and composite particles containing Pd and Ni supported on the alumina-based base material particles is arranged in the exhaust gas flow path of the exhaust gas discharged from the internal combustion engine.
  • an exhaust gas purification system is arranged in the exhaust gas flow path of the exhaust gas discharged from the internal combustion engine.
  • this exhaust gas purification system it is preferable that this exhaust gas purification system further has the technical features described in any one of the above [1] to [14].
  • Alumina-based base material particles are immersed in a solution containing Pd salt and Ni salt, Pd and Ni are co-supported on the alumina-based base material particles, and Pd and Ni are placed on the alumina-based base material particles.
  • a method for producing a methane oxidation catalyst which forms composite particles on which the particles are supported.
  • the method for producing the methane oxidation catalyst further has the technical features described in any one of the above [1] to [10].
  • a novel methane oxidation catalyst having enhanced methane catalytic activity in a low temperature region of less than 500 ° C., a methane oxidation laminated catalyst, an exhaust gas purification system using these, a method for producing a methane oxidation catalyst, etc. can be realized.
  • Example 6 is a graph showing the particle diameters of Pd particles on the aluminum-based base material particles of Examples 2, 6 and 7, and Comparative Example 1. It is a graph which shows the methane oxidation removal performance of Examples 10-11. It is a graph which shows the methane oxidation removal performance of Examples 7, 12 to 16.
  • the methane oxidation catalyst 100 of the present embodiment is an oxidation catalyst for oxidizing methane contained in the gas, and is a Pd supported on the alumina-based base material particles 11 and the surface 11a of the alumina-based base material particles 11. It is characterized by containing composite particles 21 containing Ni and Ni.
  • the alumina-based base material particles 11 are particles containing alumina as a constituent component, and are carrier particles that support Pd and Ni on the surface 11a thereof.
  • alumina means aluminum oxide such as ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, and ⁇ -alumina, as well as boehmite [ ⁇ -AlO (OH)] and diaspoa [ ⁇ -AlO ( ⁇ -AlO). OH)] and the like are aluminum oxide hydroxides or alumina hydrates Al 2 O 3 ⁇ n (H 2 O)) and the like.
  • alumina one type can be used alone, or two or more types can be used in any combination and ratio.
  • alumina ⁇ -alumina, ⁇ -alumina, and boehmite are preferable.
  • alkali metal elements such as potassium and sodium, alkaline earth metal elements such as barium and magnesium, transition elements such as iron, cobalt and titanium, cerium, lanthanum, neodymium and zirconium, It may contain other components such as rare earth elements such as praseodymium. However, these contents are preferably 30% by mass or less from the viewpoint of maintaining a high BET specific surface area of the alumina-based base material particles 11.
  • one kind may be used alone, or two or more kinds may be used in any combination and ratio.
  • the particle shape of the alumina-based base material particles 11 is not particularly limited, and may be, for example, spherical, ellipsoidal, crushed, flat, indefinite, or the like.
  • the average particle diameter (D50) of the alumina-based base material particles 11 can be appropriately set according to the desired performance, and is not particularly limited, but maintains a large specific surface area and enhances heat resistance to increase the number of its own catalytically active sites. From the viewpoint of allowing the particles to grow, the thickness is preferably 5 to 200 ⁇ m, more preferably 10 to 150 ⁇ m, and even more preferably 15 to 100 ⁇ m.
  • the average particle size D50 means a median diameter measured by a laser diffraction type particle size distribution measuring device (for example, a laser diffraction type particle size distribution measuring device SALD-7100 manufactured by Shimadzu Corporation).
  • the pore diameter of the alumina-based base material particles 11 used here can be appropriately set according to the desired performance and is not particularly limited, but is 5 nm or more and 30 nm or less from the viewpoint of improving the catalytic activity of methane in a low temperature region of less than 500 ° C. Is more preferable, and more preferably 7 nm or more and 29 nm or less, and further preferably 10 nm or more and 28 nm or less.
  • the pore diameter of the alumina-based base material particles 11 means a value calculated by the mercury intrusion method.
  • the pore volume is measured under the conditions described in Examples described later, and the value of the peak top position in the pore distribution curve of the pore diameter-differential pore volume obtained at this time is set as the alumina-based base material particles.
  • the pore diameter is 11.
  • the pore volume of the alumina-based base material particles 11 can be appropriately set according to the desired performance and is not particularly limited, but is preferably 1.0 cc / g or more and 3.0 cc / g or less, and more preferably 1.2 cc / g. It is g or more and 2.8 cc / g or less, more preferably 1.5 cc / g or more and 2.5 cc / g or less.
  • the pore volume of the alumina-based base material particles 11 means a value calculated by the mercury intrusion method. Here, the pore volume is measured under the conditions described in Examples described later.
  • Pd and Ni are supported as catalytically active components on the surface 11a of the above-mentioned alumina-based base material particles 11.
  • the Pd and Ni on the surface 11a of the alumina-based base material particles 11 can change to a simple substance of a metal, an oxide, or the like depending on the external environment. Therefore, the oxidation state of Pd and Ni is not particularly limited, but it is preferably particles in a reducing atmosphere.
  • the molar ratio (Pd / Ni) of Pd and Ni contained in the composite particle 21 can be appropriately set according to the desired performance and is not particularly limited, but is preferably 0.25/1 to 1/5, more preferably 0. .5 / 1 to 1/4, more preferably 1/1 to 1/3.
  • the content of Pd and Ni supported on the alumina-based base material particles 11 can be appropriately determined according to the desired performance and is not particularly limited, but is not particularly limited, but is a composite particle from the viewpoint of improving the low temperature catalytic activity below 500 ° C.
  • the metal equivalent amount with respect to the total amount of 21 is preferably 3 to 20% by mass, more preferably 4 to 17% by mass, and further preferably 5 to 15% by mass, respectively.
  • the average particle diameter (D50) of Pd on the surface 11a of the alumina-based base material particles 11 is preferably 0.5 nm or more and 3.0 nm or less, more preferably 0.7 nm or more and 2.5 nm or less, and further preferably 0.9 nm. It is 2.0 nm or less.
  • the composite particles 21 do not substantially contain mercury, lead, tin, zinc, and oxides thereof. These can be biotoxic due to chemical action with organic compounds, ash and the like. Therefore, the content ratio of mercury, lead, tin, zinc, and their oxides is preferably less than 10% by mass, more preferably less than 3% by mass, still more preferably 1 in terms of metal equivalent to the total amount of the composite particles 21. It is less than mass%, particularly preferably less than 0.5% by mass, and most preferably less than 0.1% by mass.
  • the methane oxidation catalyst 100 of the present embodiment may contain other components as long as it contains the above-mentioned composite particles 21.
  • the other components include catalytically active components other than Pd and Ni (hereinafter, may be simply referred to as “other catalytically active components”), and base material particles other than the above-mentioned alumina-based base material particles 11. In the above, it may be simply referred to as "other base material particles”) and the like.
  • Examples of other catalytically active components include platinum group elements other than Pd, specifically platinum (Pt), rhodium (Rh), iridium (Ir), ruthenium (Ru), and osmium (Os).
  • platinum group elements one type may be used alone, or two or more types may be used in any combination and ratio.
  • Other base material particles include alumina-based particles in which Pd and / or Ni are not supported, metal oxides such as ceria and zirconia; zirconia and ceria-zirconia doped with rare earth elements and / or transition elements, and the like.
  • the proportion of these other catalytically active components and other base metal particles used is not particularly limited, but is preferably 0.01 to 30% by mass in total, and more preferably in total, with respect to the total amount of the methane oxidation catalyst 100. It is 0.01 to 15% by mass, more preferably 0.01 to 5% by mass in total.
  • the methane oxidation catalyst 100 of the present embodiment may contain additives known in the art in addition to the above-mentioned composite particles 21 and other components.
  • the additive include, but are not limited to, various binders, dispersion stabilizers such as nonionic surfactants and anionic surfactants, pH adjusters, viscosity adjusters and the like.
  • the proportion of these additives used is not particularly limited, but is preferably 0.01 to 10% by mass in total, more preferably 0.05 to 8% by mass in total, and total to the total amount of the methane oxidation catalyst 100. It is more preferably 0.1 to 5% by mass.
  • the above-mentioned composite particles 21 can be produced according to a conventional method, and the production method thereof is not particularly limited. From the viewpoint of reproducibility, simplicity, and low cost, the evaporation-drying method (impregnation method, spray-drying method, etc.) is preferable.
  • the alumina-based base material particles 11 (hereinafter, may be referred to as “raw material alumina powder”) is immersed in a solution containing a Pd salt, and Pd is supported on the surface 11a of the alumina-based base material particles 11. Then, the composite particles 21 can be obtained by further immersing the particles in a solution containing a Ni salt and supporting Ni on the surface 11a of the alumina-based base material particles 11.
  • Pd ions and / or Ni ions are adsorbed (adhered) to the surface 11a of the alumina-based base material particles 11 in a highly dispersed state.
  • the order in which Pd and Ni are supported can be reversed.
  • the alumina-based base material particles 11 are immersed in a solution containing a Pd salt and a Ni salt, and alumina is used. A method of co-supporting Pd and Ni on the surface 11a of the system base material particles 11 can be mentioned.
  • the BET specific surface area of the raw material alumina powder is not particularly limited, but can be appropriately set depending on the high dispersion support of Pd and Ni, gas diffusivity, etc., and is not particularly limited, but is preferably 10 to 400 m 2 / g, more preferably. Is 20 to 350 m 2 / g, more preferably 50 to 300 m 2 / g.
  • As the alumina powder many grades are commercially available from domestic and overseas manufacturers, and the commercially available products of various grades can be used as the alumina-based base material particles 11 (raw material alumina powder) of the present embodiment. can. Further, the above-mentioned alumina-based base material particles 11 (raw material alumina powder) can also be produced by a method known in the art.
  • the solution containing the Pd salt and / or the Ni salt is not particularly limited, but the Pd salt and / or the Ni salt and other components and additives to be blended as necessary are mixed with water, and the Pd salt and / or A Ni salt-containing aqueous solution is preferably used.
  • the form of the salt used here may be selected according to a conventional method and is not particularly limited, but is generally limited to hydrochloride, oxyhydrochloride, nitrate, oxynitrate, carbonate, phosphate, acetate and shu. Acidates, citrates, ammine complex salts and the like are preferred.
  • the content ratio of Pd ion and / or Ni ion in the aqueous solution can be appropriately adjusted so that the content ratio of Pd and Ni in the obtained methane oxidation catalyst 100 is a desired content ratio, and is not particularly limited.
  • the above-mentioned alumina-based base material particles 11 (raw material alumina powder) are impregnated or immersed in such a solution to remove the solvent (for example, water), and if necessary, a drying treatment and / or about 200 to 600 ° C.
  • the heat treatment (firing treatment) of the above the composite particles 21 containing Pd and Ni supported on the surface 11a of the alumina-based base material particles 11 can be obtained with good productivity.
  • the firing conditions may be in accordance with a conventional method and are not particularly limited.
  • the firing atmosphere may be any of an oxidizing atmosphere, a reducing atmosphere, and a neutral atmosphere. From the viewpoint of productivity and the like, generally, it is preferably 0.1 to 12 hours at 150 ° C to 1300 ° C, and more preferably 0.1 to 4 hours at 350 ° C to 600 ° C.
  • vacuum drying may be performed using a vacuum dryer or the like, and drying treatment may be performed at about 50 ° C. to 200 ° C. for about 1 to 48 hours.
  • the obtained composite particle 21 has a composite structure in which Pd and Ni are co-supported on the surface 11a of the alumina-based base particle 11, and these Pd and Ni function as main catalytically active sites.
  • the particle size of the composite particles 21 may be adjusted according to the required performance.
  • the particle size of the composite particle 21 can be adjusted according to a conventional method, and is not particularly limited.
  • the composite particles 21 are preferably wet-milled to have an average particle diameter (D90) of 3 to 50 ⁇ m, more preferably 5 to 40 ⁇ m, and even more preferably 10 to 30 ⁇ m. ..
  • the methane oxidation catalyst 100 of the present embodiment exhibits a catalytic ability to oxidize (oxidize and remove) methane by exposing the composite particles 21 to a gas containing methane.
  • the form of use of the methane oxidation catalyst 100 is not particularly limited. For example, it can be used as it is in the form of the catalyst powder which is an aggregate of the composite particles 21 described above. Further, for example, the composite particles 21 can be molded into an arbitrary shape to obtain a granular or pellet-shaped molding catalyst.
  • various known dispersion devices, kneading devices, and molding devices can be used.
  • the methane oxidation catalyst 100 of the present embodiment can also be used in a form of being supported on a catalyst carrier such as a monolith carrier.
  • This form can be defined as a laminated catalyst comprising a catalyst carrier and a catalyst layer containing a methane oxidation catalyst 100 (composite particles 21) supported on the catalyst carrier.
  • the catalyst area of the laminated catalyst may be a single layer having only one catalyst layer or a laminated body composed of two or more catalyst layers, and is known in the art as one or more catalyst layers. It may be any of the laminated bodies in which one or more other layers are combined.
  • a catalyst carrier known in the art can be appropriately selected.
  • Typical examples thereof include ceramic monolith carriers made of cordierite, silicon carbide, silicon nitride and the like, metal honeycomb carriers made of stainless steel and the like, wire mesh carriers made of stainless steel and the like, but are not particularly limited thereto. It should be noted that these can be used alone or in any combination and ratio of two or more.
  • the method for forming the catalyst layer may be performed according to a conventional method, and is not particularly limited. Various known coating methods, wash coat methods, and zone coat methods can be applied.
  • the methane oxidation catalyst 100 of the present embodiment of the present embodiment an aqueous medium, and optionally a binder known in the art, other catalysts, co-catalyst particles, OSC material, base material particles, addition.
  • a slurry-like mixture can be prepared by mixing the agent and the like in a desired blending ratio, and the obtained slurry-like mixture can be applied to the surface of the catalyst carrier, dried and fired.
  • an acid or a base can be blended for pH adjustment, or a surfactant, a dispersion resin, or the like for adjusting the viscosity or improving the slurry dispersibility can be blended.
  • a surfactant, a dispersion resin, or the like for adjusting the viscosity or improving the slurry dispersibility can be blended.
  • pulverization and mixing using a ball mill or the like can be applied, but other pulverization or mixing methods can also be applied.
  • the catalyst layer containing the methane oxidation catalyst 100 of the present embodiment is provided on the catalyst carrier by drying and firing according to a conventional method (methane oxidation laminated catalyst). ) Can be obtained.
  • the coating amount of the methane oxidation catalyst 100 can be appropriately set according to the desired performance and is not particularly limited, but is 100 g / L or more with respect to 1 L of the catalyst carrier as a base material from the viewpoint of the coating amount and pressure loss. It is preferably 200 g / L or less, more preferably 100 g / L or more and 180 g / L or less, and further preferably 110 g / L or more and 150 g / L or less.
  • the coating amount of Pd can be appropriately set according to the desired performance and is not particularly limited, but is preferably 4.5 g / L or more and 16.0 g / L or less with respect to 1 L of the catalyst carrier as a base material. It is more preferably 5.0 g / L or more and 14.0 g / L or less, and further preferably 6.0 g / L or more and 12.0 g / L or less.
  • the amount of Ni coated can be appropriately set according to the desired performance and is not particularly limited, but is preferably 1.0 g / L or more and 11.0 g / L or less with respect to 1 L of the catalyst carrier as a base material. It is more preferably 2.0 g / L or more and 9.5 g / L or less, and further preferably 5.0 g / L or more and 8.0 / L or less.
  • the methane oxidation catalyst 100 of the present embodiment is useful as an oxidation catalyst for oxidizing methane contained in the gas.
  • oxidation catalyst for oxidizing methane contained in the gas.
  • the oxidation catalyst of methane contained in the gas discharged from the gas such as, the methane oxidation catalyst 100 of the present embodiment can be used.
  • the methane oxidation catalyst 100 of the present embodiment is exhaust gas discharged from a compressed ignition internal combustion engine such as a diesel engine, a bi-fuel engine (BF) or a dual fuel engine (CNG-DFCI, LNG-DFCI, etc.) using the compressed ignition internal combustion engine. It is particularly useful as an oxidation catalyst for methane contained in.
  • a compressed ignition internal combustion engine such as a diesel engine, a bi-fuel engine (BF) or a dual fuel engine (CNG-DFCI, LNG-DFCI, etc.
  • DOC diesel oxidation catalyst
  • DOC particulate substance such as soot contained in the exhaust gas
  • Diesel Particulate Filler for collecting PM: Particulate matter, Catalyzed Particulate Filler (CPF) or Catalyzed Soot Filter (CSF); Lean condition A lean NOx particulate filter (LNT, Lean NOx Trap) that absorbs NOx underneath and releases NOx under rich conditions to oxidize CO and HC to CO 2 and H 2 O and reduce NOx to N 2 . It can be carried out by appropriately providing a catalytic reduction (SCR: Selective Catalytic Reduction catalyst); an ammonia oxidation catalyst (AMOX: Ammonia Oxidation catalyst) or the like. The arrangement order and the number of these arrangements can be appropriately changed according to the required performance, and are not limited to the above example.
  • SCR Selective Catalytic Reduction catalyst
  • AMOX ammonia oxidation catalyst
  • the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. That is, the materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention.
  • the values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the preferable value of the upper limit or the lower limit described above.
  • the preferred range may be a range defined by a combination of the above-mentioned upper limit or lower limit value and the value of the following examples or the values of the examples.
  • the pore distribution of the alumina-based base material particles 11 is determined by the mercury intrusion method.
  • 110.2 g of alumina-based base material particles are used as a sample, and a mercury porosimeter (manufactured by Thermo Fisher Scientific, trade names: PASCAL140 and PASCAL440) is used under the conditions of a mercury contact angle of 130 ° and a surface tension of 484 dyn / cm.
  • the pore volume is measured below, and the value (mode diameter) of the peak top position in the pore distribution curve of the pore diameter-differential pore volume obtained at this time is taken as the pore diameter of the alumina-based base material particles 11.
  • Average particle diameter D50 of alumina-based base material particles 11 The particle size distribution is measured using a laser diffraction type particle size distribution measuring device (for example, a laser diffraction type particle size distribution measuring device SALD-7100 manufactured by Shimadzu Corporation), and the median diameter thereof is the average particle size of the alumina-based base material particles 11. Let it be D50.
  • a laser diffraction type particle size distribution measuring device for example, a laser diffraction type particle size distribution measuring device SALD-7100 manufactured by Shimadzu Corporation
  • BET specific surface area For the BET specific surface area, use a specific surface area / pore distribution measuring device (trade name: BELSORP-mini II, manufactured by Microtrac Bell Co., Ltd.) and analysis software (trade name: BEL_Master, manufactured by Microtrac Bell Co., Ltd.). Then, the BET specific surface area is obtained by the BET one-point method.
  • BELSORP-mini II manufactured by Microtrac Bell Co., Ltd.
  • analysis software trade name: BEL_Master, manufactured by Microtrac Bell Co., Ltd.
  • Example 1 Alumina-based base particle (manufactured by Sasol, trade name: TH100 / 150, BET specific surface area: 150 m 2 / g, average particle diameter D50: 32 ⁇ m, pore diameter (peak value): 17.2 nm, pore volume: 1.82 cc / G) was used.
  • An aqueous solution of Pd nitrate and an aqueous solution of nickel (II) nitrate hexahydrate were mixed to prepare an aqueous solution containing a Pd salt and a Ni salt (containing 3.6% by mass in terms of Pd and 1.6% by mass in terms of Ni). ..
  • the aqueous solution containing the Pd salt and the Ni salt is impregnated with the above alumina-based base material particles to co-support Pd and Ni on the alumina-based base material particles, and then fired at 500 ° C. for 1 hour.
  • the particles are kneaded by a wet milling method until the average particle diameter D90 is within the range of 14 to 18 ⁇ m, and the methane oxidation of Example 1 is carried out.
  • a catalyst (containing 3.0% by mass in terms of Pd and 1.6% by mass in terms of Ni) was obtained.
  • Comparative Example 1 The same procedure as in Example 1 was carried out except that the use of the Nitric acid Nitric acid aqueous solution was omitted, to obtain the methane oxidation catalyst of Comparative Example 1 (containing 3.0% by mass in terms of Pd).
  • Example 2 The same procedure as in Example 1 was carried out except that an aqueous solution of tetraammine platinum (II) nitrate was used instead of the aqueous solution of Ni nitric acid. (Containing 0% by mass) was obtained.
  • II tetraammine platinum
  • Example 3 The same procedure as in Example 1 was carried out except that an aqueous solution of cerium (IV) nitrate hexahydrate was used instead of the aqueous solution of Ni nitrate, and the methane oxidation catalyst of Comparative Example 3 (containing 3.0% by weight in Pd conversion, converted to Ce). (Containing 10.0% by mass) was obtained.
  • Example 4 The same procedure as in Example 1 was carried out except that an aqueous solution of magnesium (II) nitrate hexahydrate was used instead of the aqueous solution of Ni nitrate, and the methane oxidation catalyst of Comparative Example 4 (containing 3.0% by mass in terms of Pd, converted to Mg). (Containing 0.7% by mass) was obtained.
  • an aqueous solution of magnesium (II) nitrate hexahydrate was used instead of the aqueous solution of Ni nitrate, and the methane oxidation catalyst of Comparative Example 4 (containing 3.0% by mass in terms of Pd, converted to Mg). (Containing 0.7% by mass) was obtained.
  • Example 5 The same procedure as in Example 1 was carried out except that an aqueous solution of cobalt (II) nitrate hexahydrate was used instead of the aqueous solution of Ni nitrate, and the methane oxidation catalyst of Comparative Example 5 (containing 3.0% by mass in terms of Pd, converted to Co). (Containing 1.7% by mass) was obtained.
  • an aqueous solution of cobalt (II) nitrate hexahydrate was used instead of the aqueous solution of Ni nitrate, and the methane oxidation catalyst of Comparative Example 5 (containing 3.0% by mass in terms of Pd, converted to Co). (Containing 1.7% by mass) was obtained.
  • Example 6 The same procedure as in Example 1 was carried out except that an aqueous solution of barium (II) acetate was used instead of the aqueous solution of Ni nitrate, and the methane oxidation catalyst of Comparative Example 6 (containing 3.0% by mass in terms of Pd and 3.9 in terms of Ba). (Containing% by mass) was obtained.
  • Example 7 The same procedure as in Example 1 was carried out except that an aqueous solution of copper (II) nitrate trihydrate was used instead of the aqueous solution of Ni nitrate, and the methane oxidation catalyst of Comparative Example 7 (containing 3.0% by mass in terms of Pd, converted to Cu). (Containing 1.8% by mass) was obtained.
  • Example 8 The same procedure as in Example 1 was carried out except that an aqueous solution of iron (III) nitrate hydrate was used instead of the aqueous solution of Ni nitrate, and the methane oxidation catalyst of Comparative Example 8 (containing 3.0% by mass in terms of Pd, converted to Fe). (Containing 1.6% by mass) was obtained.
  • Example 9 The same procedure as in Example 1 was carried out except that an aqueous solution of yttrium (III) nitrate hexahydrate was used instead of the aqueous solution of Ni nitric acid, and the methane oxidation catalyst of Comparative Example 9 (containing 3.0% by mass in Pd conversion, converted to Y). (Containing 2.5% by mass) was obtained. Used as.
  • Example 10 The same procedure as in Example 1 was carried out except that an aqueous solution of cerium (IV) nitrate hexahydrate was used instead of the aqueous solution of Ni nitrate, and the methane oxidation catalyst of Comparative Example 10 (containing 3.0% by mass in terms of Pd, converted to Ce). (Containing 3.9% by mass) was obtained.
  • Comparative Example 11 The same procedure as in Example 1 was carried out except that a praseodymium nitrate (III) hexahydrate aqueous solution was used instead of the Nitric acid Nitric acid aqueous solution, and the methane oxidation catalyst of Comparative Example 11 (containing 3.0% by mass in Pd conversion, Pr conversion). (Containing 4.0% by mass) was obtained.
  • a praseodymium nitrate (III) hexahydrate aqueous solution was used instead of the Nitric acid Nitric acid aqueous solution, and the methane oxidation catalyst of Comparative Example 11 (containing 3.0% by mass in Pd conversion, Pr conversion). (Containing 4.0% by mass) was obtained.
  • Comparative Example 12 The same procedure as in Example 1 was carried out except that an aqueous solution of neodymium (III) nitrate hexahydrate was used instead of the aqueous solution of Ni nitric acid, and the methane oxidation catalyst of Comparative Example 12 (containing 3.0% by mass in Pd conversion, converted to Nd). (Containing 4.1% by mass) was obtained.
  • Example 2 An aqueous solution containing a Pd salt and a Ni salt obtained by mixing an aqueous solution of Pd nitrate and an aqueous solution of nickel (II) nitrate hexahydrate (containing 3.6% by mass in terms of Pd and 2.0% by mass in terms of Ni).
  • Alumina-based base particle (manufactured by Sasol, trade name: TH100 / 150, BET specific surface area: 150 m 2 / g, average particle diameter D50: 32 ⁇ m, pore diameter (peak value): 17.2 nm, pore volume: 1 .82cc / g) was impregnated to co-support Pd and Ni on the alumina-based base material particles, and then fired at 450 ° C. for 0.5 hours to cause Pd and Ni on the alumina-based base material particles.
  • the particles were kneaded by a wet milling method until the average particle diameter D90 was within the range of 14 to 18 ⁇ m, and the methane oxidation catalyst of Example 2 (containing 3.6% by mass in terms of Pd) was kneaded. , 2.0% by mass in terms of Ni) was obtained.
  • the obtained methane oxidation catalyst of Example 2 was wet-coated on a cordierite carrier (manufactured by NGK, ⁇ 25.4 x 50 mm) (coating amount: 125 g / L, Pd equivalent coating amount: 4.5 g / L,
  • the methane oxidation laminated catalyst of Example 2 was obtained by firing treatment at 450 ° C. for 30 minutes at a Ni equivalent coating amount: 2.5 g / L).
  • the alumina-based base particle to be used is an alumina-based base particle (manufactured by Sasol, trade name: Silarox 1.5 / 100, BET specific surface area: 100 m 2 / g, average particle diameter D50: 37 ⁇ m, pore diameter (peak value) :.
  • the same procedure as in Example 2 was carried out except that the particle volume was changed to 11.6 nm and the pore volume: 0.46 cc / g) to obtain the methane oxide laminated catalyst of Example 3.
  • the alumina-based base particle to be used is an alumina-based base particle (manufactured by Solvay, trade name: MI386, BET specific surface area: 200 m 2 / g, average particle diameter D50: 22 ⁇ m, pore diameter (peak value): 10.4 nm, The same procedure as in Example 2 was carried out except that the pore volume was changed to 1.00 cc / g) to obtain the methane oxide lamination catalyst of Example 4.
  • the alumina-based base particle to be used is an alumina-based base particle (manufactured by Sasol, trade name: TH130 / 130, BET specific surface area: 130 m 2 / g, average particle diameter D50: 22 ⁇ m, pore diameter (peak value): 26.
  • the same procedure as in Example 2 was carried out except that the particle volume was changed to 2 nm and the pore volume: 2.29 cc / g) to obtain the methane oxide lamination catalyst of Example 5.
  • Example 6 The same procedure as in Example 2 was carried out except that the amount of supported Ni was changed to 3 times the amount of supported Pd, and the methane oxidation catalyst of Example 6 (containing 3.6% by mass in Pd conversion, 6.0 in Ni conversion) was carried out. (Containing% by mass) was obtained.
  • the obtained methane oxidation catalyst of Example 6 was wet-coated on a cordierite carrier ( ⁇ 25.4 x 50 mm) (coating amount: 125 g / L, Pd equivalent coating amount: 4.5 g / L, Ni equivalent coating). Amount: 7.4 g / L) and firing treatment at 450 ° C. for 30 minutes to obtain the methane oxidation laminated catalyst of Example 6.
  • the alumina-based base particle to be used is an alumina-based base particle (manufactured by Sasol, trade name: TH130 / 130, BET specific surface area: 130 m 2 / g, average particle diameter D50: 22 ⁇ m, pore diameter (peak value): 26.
  • the same procedure as in Example 6 was carried out except that the particle volume was changed to 2 nm and the pore volume: 2.29 cc / g) to obtain the methane oxide lamination catalyst of Example 7.
  • the alumina-based base particle to be used is an alumina-based base particle (manufactured by Sasol, trade name: TH100 / 100, BET specific surface area: 100 m 2 / g, average particle diameter D50: 29 ⁇ m, pore diameter (peak value): 26.
  • the same procedure as in Example 6 was carried out except that the particle volume was changed to 7 nm and the pore volume: 1.78 cc / g) to obtain the methane oxide lamination catalyst of Example 8.
  • the alumina-based base particle to be used is an alumina-based base particle (manufactured by Sasol, trade name: TM100 / 150, BET specific surface area: 150 m 2 / g, average particle diameter D50: 27 ⁇ m, pore diameter (peak value): 24.
  • the same procedure as in Example 6 was carried out except that the particle volume was changed to 8 nm and the pore volume: 1.60 cc / g) to obtain the methane oxide lamination catalyst of Example 9.
  • Example 10 Alumina-based base material particles (manufactured by Sasol, trade name) in an aqueous solution containing a Pd salt and a Ni salt obtained by mixing an aqueous solution of tetraammine palladium (II) chloride hydrate and an aqueous solution of nickel (II) nitrate hexahydrate. : TH100 / 150, BET specific surface area: 150 m 2 / g, average particle diameter D50: 32 ⁇ m, pore diameter (peak value): 17.2 nm, pore volume: 1.82 cc / g) to impregnate the alumina-based mother.
  • Pd and Ni are co-supported on the material particles and then fired at 450 ° C. for 0.5 hours to form composite particles in which Pd and Ni are supported on the alumina-based base material particles, and then wet milling.
  • the particles are kneaded until the average particle size D90 is within the range of 14 to 18 ⁇ m to obtain the methane oxidation catalyst of Example 10 (containing 3.6% by mass in terms of Pd and 6.0% by mass in terms of Ni). rice field.
  • the obtained methane oxidation catalyst of Example 10 was wet-coated on a cordierite carrier (manufactured by NGK, ⁇ 25.4 x 50 mm) (coating amount: 125 g / L, Pd equivalent coating amount: 4.5 g / L, Ni-equivalent coating amount: 7.4 g / L))) was fired at 450 ° C. for 30 minutes to obtain the methane oxidation lamination catalyst of Example 10.
  • the alumina-based base particle to be used is an alumina-based base particle (manufactured by Sasol, trade name: TH130 / 130, BET specific surface area: 130 m 2 / g, average particle diameter D50: 22 ⁇ m, pore diameter (peak value): 26.
  • the same procedure as in Example 10 was carried out except that the particle volume was changed to 2 nm and the pore volume: 2.29 cc / g) to obtain the methane oxide lamination catalyst of Example 11.
  • Example 12 to 16 The same procedure as in Example 7 was carried out except that the amount of coating applied during wet coating was changed as shown in Table 2, to obtain methane oxidation laminated catalysts of Examples 12 to 16.
  • the methane oxidation catalyst, the methane oxidation laminated catalyst, and the like of the present invention have enhanced catalytic activity of methane contained in the gas in a low temperature region of less than 500 ° C., compressed natural gas (CNG), liquefied natural gas, etc.
  • CNG compressed natural gas
  • oxidation catalyst for methane contained in gas discharged from (LNG) city gas, light oil, kerosene and other boilers, heating furnaces, gas engines, gas turbines, dilute combustion gas engines, and other internal combustion engines.
  • oxidation catalyst for methane contained in exhaust gas discharged from compression ignition internal combustion engines such as diesel engines, bifuel engines (BF) and dual fuel engines (CNG-DFCI, LNG-DFCI, etc.) using the same. It can be effectively used.
  • compression ignition internal combustion engines such as diesel engines, bifuel engines (BF) and dual fuel engines (CNG-DFCI, LNG-DFCI, etc.) using the same. It can be effectively used.

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Abstract

La présente invention concerne : un nouveau catalyseur d'oxydation du méthane qui a une activité catalytique de méthane améliorée dans une plage de basses températures inférieure à 500 °C ; un catalyseur multicouche d'oxydation du méthane ; un système de purification de gaz d'échappement qui utilise ce catalyseur d'oxydation du méthane ou ce catalyseur multicouche d'oxydation du méthane ; un procédé de production d'un catalyseur d'oxydation du méthane ; et similaire. Un catalyseur d'oxydation du méthane est utilisé dans le but d'oxyder le méthane contenu dans un gaz, et qui contient des particules de matériau de base à base d'alumine et des particules composites qui sont supportées par les particules de matériau de base à base d'alumine, tout en contenant du Pd et du Ni.
PCT/JP2021/034080 2020-09-25 2021-09-16 Catalyseur d'oxydation de méthane, catalyseur multicouche d'oxydation de méthane, système de purification de gaz d'échappement utilisant ledit catalyseur d'oxydation de méthane ou ledit catalyseur multicouche d'oxydation de méthane, et procédé pour produire le catalyseur d'oxydation de méthane WO2022065188A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06106059A (ja) * 1991-03-27 1994-04-19 Mitsubishi Heavy Ind Ltd 酸化触媒
JP2002113367A (ja) * 2000-10-10 2002-04-16 Toyota Central Res & Dev Lab Inc 飽和炭化水素酸化用触媒
JP2003071288A (ja) * 2001-08-30 2003-03-11 Toyota Central Res & Dev Lab Inc 飽和炭化水素酸化触媒
WO2014141903A1 (fr) * 2013-03-15 2014-09-18 エヌ・イーケムキャット株式会社 Catalyseur d'oxydation et dispositif de purification de gaz d'échappement l'utilisant
JP2016504182A (ja) * 2012-11-29 2016-02-12 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ パラジウム、金およびセリアを含むディーゼル酸化触媒
JP2016215091A (ja) * 2015-05-15 2016-12-22 株式会社 Ａｃｒ 二元燃料酸化触媒、二元燃料ｓｃｒ排ガス処理機構、二元燃料ディーゼル内燃機関、および、その制御方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06106059A (ja) * 1991-03-27 1994-04-19 Mitsubishi Heavy Ind Ltd 酸化触媒
JP2002113367A (ja) * 2000-10-10 2002-04-16 Toyota Central Res & Dev Lab Inc 飽和炭化水素酸化用触媒
JP2003071288A (ja) * 2001-08-30 2003-03-11 Toyota Central Res & Dev Lab Inc 飽和炭化水素酸化触媒
JP2016504182A (ja) * 2012-11-29 2016-02-12 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ パラジウム、金およびセリアを含むディーゼル酸化触媒
WO2014141903A1 (fr) * 2013-03-15 2014-09-18 エヌ・イーケムキャット株式会社 Catalyseur d'oxydation et dispositif de purification de gaz d'échappement l'utilisant
JP2016215091A (ja) * 2015-05-15 2016-12-22 株式会社 Ａｃｒ 二元燃料酸化触媒、二元燃料ｓｃｒ排ガス処理機構、二元燃料ディーゼル内燃機関、および、その制御方法

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