WO2016113631A1 - Catalyseur de matière particulaire de combustion (pct ou pccz) et catalyseur revêtu de matière particulaire de combustion (cpcc oucpccz) - Google Patents

Catalyseur de matière particulaire de combustion (pct ou pccz) et catalyseur revêtu de matière particulaire de combustion (cpcc oucpccz) Download PDF

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Publication number
WO2016113631A1
WO2016113631A1 PCT/IB2016/000027 IB2016000027W WO2016113631A1 WO 2016113631 A1 WO2016113631 A1 WO 2016113631A1 IB 2016000027 W IB2016000027 W IB 2016000027W WO 2016113631 A1 WO2016113631 A1 WO 2016113631A1
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Prior art keywords
corrugated
pmm
substrate
range
flat
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Ceased
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PCT/IB2016/000027
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English (en)
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WO2016113631A8 (fr
Inventor
Alok TRIGUNAYAT
Rajan Bosco
Ankit SHUKLA
Sumit KUKRETI
Arvind Kumar
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Ecocat India Private Ltd
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Ecocat India Private Ltd
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Priority to RU2017122627A priority Critical patent/RU2687389C2/ru
Publication of WO2016113631A1 publication Critical patent/WO2016113631A1/fr
Anticipated expiration legal-status Critical
Publication of WO2016113631A8 publication Critical patent/WO2016113631A8/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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • 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 [3D] 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
    • 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
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • 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
    • 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
    • F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • F01N3/2807—Metal other than sintered metal
    • F01N3/281—Metallic honeycomb monoliths made of stacked or rolled sheets, foils or plates
    • 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
    • F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • F01N3/2807—Metal other than sintered metal
    • F01N3/281—Metallic honeycomb monoliths made of stacked or rolled sheets, foils or plates
    • F01N3/2821—Metallic honeycomb monoliths made of stacked or rolled sheets, foils or plates the support being provided with means to enhance the mixing process inside the converter, e.g. sheets, plates or foils with protrusions or projections to create turbulence
    • 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
    • B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
    • 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
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • 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
    • F01N2330/00—Structure of catalyst support or particle filter
    • F01N2330/30—Honeycomb supports characterised by their structural details
    • F01N2330/48—Honeycomb supports characterised by their structural details characterised by the number of flow passages, e.g. cell density
    • 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
    • F01N2510/00—Surface coverings
    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Definitions

  • the present invention is towards elimination or reducing particulate matter of exhaust from combustion engines.
  • the invention relates to Particulate Combustion Catalyst (PCC), particulate filter, and exhaust gas clean-up system.
  • PCC Particulate Combustion Catalyst
  • the invention more particularly relates to a composition and device designed to remove particulate matter or soot from the exhaust gas of diesel engines, Gasoline Direct Injection (GDI) engines etc.
  • GDI Gasoline Direct Injection
  • the present invention also relates to methods for manufacturing the said device.
  • DPF wall-flow particulate filters
  • PM particulate matter
  • Filters require more maintenance than catalytic converters. Continuous built up of trapped particulate matter blocks the filter medium thereby leading to increase in the back pressure across such devices and adversely impacting engine performance and consequently emission compliance. The soot gets collected inside porous metallic medium and on the metallic screen due to principles of inertia! impact. There is a continuous need to develop efficient particulate removal and the present invention provides for the same.
  • the present invention provides for a device which produces less back pressure than a conventional DPF with more cross flows and utilization of the substrate.
  • the inventors have designed a PCC that overcomes risks of failure due to continuous built up of trapped particulate matter by allowing an alternate open flow path in case of soot saturation, thereby confining backpressure under permissible limits.
  • Simulation based approach and field testing was used to study, design and develop new cross flow structures by evaluating the pressure drop and collection efficiency.
  • the structure was optimized for efficient soot collection without blockage of the main flow paths.
  • the invention discloses a three dimensional device for the catalytic treatment of exhaust gases of automotive vehicles comprising of a substrate formed by connecting a plurality of honeycomb/substrate members, each having a structure in which a number of cells are arranged in parallel or in series or parallely arranged in series with respect to each another.
  • Another aspect of the present invention is a substrate formed by a unique combination of Porous Metallic Medium (PMM) and metallic screen with different shape of its openings, and different mesh numbers with or without or corrugated or micro corrugated material to form a three dimensional (3D) structure.
  • PMM Porous Metallic Medium
  • Another aspect of the present invention is to combine a corrugated or micro corrugated PMM with the 5 corrugated or micro corrugated metallic screen with different shape of its openings, and different mesh , numbers with or without or corrugated or micro corrugated material to form a three dimensional (3D) structure.
  • 3D three dimensional
  • Another aspect of the present invention is to combine a corrugated or micro corrugated PMM with the non- corrugated metallic screen with different shape of its openings, and different mesh numbers with or without l o or corrugated or micro corrugated material to form a three dimensional (3D) structure.
  • Yet another aspect of the present invention is a non-corrugated PMM can be uniquely combined with the corrugated or micro corrugated metallic screen with different shape of its openings and different mesh numbers with or without or corrugated or micro corrugated material to form a three dimensional (3D) structure.
  • every cell inside the substrate is composed of metallic screen with different shape of its openings and different mesh numbers and/or corrugated or micro corrugated notched metallic material and / or inorganic material and PMM as its walls.
  • CPCC Z is coated with a unique washcoat material that is capable of continuously producing in-situ nitrogen dioxide, which is essential for continuous oxidation of trapped
  • Figure 1.3 Straight channel corrugated substrate structure.
  • Figure 1.4 Straight channel corrugated porous metallic media with micro corrugated / notched metallic foil.
  • Figure 1.5 Straight channel corrugated foil with micro corrugation 0
  • Figure 1.6 Angle corrugated foil with higher cpsi & with micro corrugation
  • Figure 1.7 Angle corrugated foil with lower cpsi and with micro corrugation
  • Figure 1.15 Structure of rectangular screen
  • Figure 1.16 Structure of square screen
  • Figure 2 Examples of the different shapes of Particulate Combustion Catalyst and Coated Particulate Combustion Catalyst
  • Figure 3.1 - 3.13 ⁇ variations of selected samples having different combinations and with corrugation.
  • FIG 4 Mass emission data of selected samples having different combinations and with corrugation.
  • Figure 5 Outline of Scheme 1 Process flow for Particulate Combustion Catalyst (PCC) and Coated Paniculate Combustion Catalyst (CPCC);
  • Figures 9 - 22 Comparative Laboratory Simulation Plots of oxidation reactions of Carbon monoxide oxidation, Propylene oxidation & Nitrogen dioxide formation with temperature for different combinations of PCC Z and CPCC Z (henceforth called as catalytic activity), tested under different operating conditions.
  • Figures 9a & 9b compare the CO, HC conversion-% and O2 formation % as a function of temperature with Space Velocity 30.000 fr 1 for one and two layer VF-structures with flat porous metallic medium (PMM) and angle corrugated metallic screen with rectangular mesh with PGM-loadiiigs 1 , 2, 5, 10 and 20 g/ft 3 .
  • PMM flat porous metallic medium
  • Figure 10 compares the CO, HC conversion-% and O2 formation % as a function of temperature with Space Velocity 30.000 tv 1 for one layer VF-structure with flat porous metallic medium (PMM) and angle corrugated metallic screen with rectangular mesh with PGM-loading 1 g/ft3 and for one layer Prior art VX-structure with PGM-loading 20 g/ft 3 .
  • Figures 11a & 11b compare the CO, HC conversion-% and NO2 formation % as a function of temperature with Space Velocity 30.000 and 60.000 IT 1 for one layer VF-structures with flat porous metallic medium (PMM) and angle corrugated metallic screen with rectangular mesh with PGM-loadings 1 and 5 g/ft 3 .
  • Figures 12a & 12b compare the CO, HC conversion-% and NO2 formation % as a function of temperature with Space Velocity 60.000 IT 1 for one and two layer VF- with flat porous metallic medium (PMM) and angle corrugated metallic screen with rectangular mesh with PGM-loadings 1 , 5, 10 and 20 g/ft 3 .
  • PMM flat porous metallic medium
  • Figures 13a & 13b compare the CO, HC conversion-% and NO2 formation % as a function of temperature with Space Velocity 30.000 IT 1 for uncoated structures with three different type of corrugations for porous metallic medium (PMM) with flat / uncorrugated foil (UF) or with micro corrugated / notched foil (MF).
  • PMM porous metallic medium
  • UF uncorrugated foil
  • MF micro corrugated / notched foil
  • Figures 14a & 14b compare the CO, HC conversion-% and NO2 formation % as a function of temperature with Space Velocity 30.000 Ir 1 for one layer structures with three different type of corrugations for porous metallic medium (PMM) with flat / uncorrugated foil (UF) or with micro corrugated./ notched foil (MF). PGM-loading is the same 1 g/ft 3 in all cases.
  • PMM porous metallic medium
  • UF uncorrugated foil
  • MF micro corrugated./ notched foil
  • Figures 15a & 15b compare the CO, HC conversion-% and NO2 formation % as a function of temperature with Space Velocity 30,000 Ir 1 for one layer structures with different type of corrugations for porous metallic medium (PMM) with flat / uncorrugated foil (UF) or with Micro corrugated / notched foil (MF). PGM-loading is the same 5 g/ft 3 in all cases.
  • PMM porous metallic medium
  • UF uncorrugated foil
  • MF Micro corrugated / notched foil
  • Figures 16a & 16b compare the CO, HC conversion-% and N0 2 formation % as a function of temperature with Space Velocity 30,000 and 60.000 IT 1 for one layer structures with angle type of corrugation of porous metallic medium (PMM) with flat / uncorrugated foil (UF) or with Micro corrugated / notched foil (MF).
  • PGM-loading is 10 g/ft 3 .
  • Figures 17a & 17b compare the CO, HC conversion-% and N0 2 formation % as a function of temperature with Space Velocity 60.000 tv 1 for one layer structures with with three different type of corrugations of porous metallic medium (PMM) with flat / uncorrugated foil (UF) or with Micro corrugated / notched foil (MF). PGM-loading is 10 g/ft 3 .
  • Figures 18a & 18b compare the CO, HC conversion-% and N0 2 formation % as a function of temperature with Space Velocity 30.000 rr 1 for one layer Prior art VX-structure with 330 cpsi, corrugated metallic screen having a PGM-loading of 1 , 5, and 10 g/ft 3 .
  • Figure 19 compares the GO, HC conversion-% and NO2 formation % as a function of temperature with Space Velocity 30.000 and 60.000 tv for one layer structures with the three different type of corrugations for foil (CF) with flat porous metallic medium (PMM). PGM-loading is the same 1 g/ft 3 in all cases.
  • Figure 20 compares the CO, HC conversion-% and NO2 formation % as a function of temperature with Space Velocity 30.000 and 60.000 fr 1 for one layer structures with the three different type of corrugations for foil (CF) with flat porous metallic medium (PMM). PGM-loading is the same 5 g/ft 3 in all cases.
  • Figure 21 compares CO, HC conversion-% and NO2 formation % as a function of temperature with Space Velocity 30.000 and 60.000 lr 1 for one layer structures with the three different type of corrugations for foil (CF) with flat porous metallic medium (PMM). PGM-loading is the same 10 g/ft 3 in all cases.
  • Figures 22a & 22b compare the CO, HC conversion-% and NO2 formation % as a function of temperature with Space Velocity 30.000 and 60.000 IT 1 for one layer structures with two different type of corrugations for porous metallic medium (PMM) with flat / uncorrugated foil (UF) or with micro corrugated / notched foil (MF). PGM- loading is the same 1 g/ft 3 in all cases.
  • Figures 23.1 & 23.2 describe Soot loading behavior as a function of distance covered CPCC Z samples having a different structural combination and different corrugations.
  • the device disclosed in the present invention is for catalytic treatment of exhaust gases which is comprised of a substrate formed by connecting a plurality of individual members wherein said individual member comprises of a plurality of cells.
  • the individual member can have a honeycomb body.
  • the plurality of cells are arranged in parallel or in series or in parallel series with respect to each another.
  • the invention discloses a substrate formed by a unique combination of Porous Metallic Medium (PMM) and metallic screen with different shape of its openings, and different mesh numbers with or without or corrugated or micro corrugated material to form a three dimensional (3D) structure.
  • PMM Porous Metallic Medium
  • the invention allows for substantial trapping of particulate matter emancipating from an engine.
  • a corrugated or micro corrugated PMM is combined with the corrugated or micro corrugated metallic screen with different shape of its openings and different mesh numbers and/or corrugated or micro corrugated notched metallic foil and/or inorganic fibrous woven matrix material to arrive at the three dimensional (3D) structure.
  • Alternative embodiment of the invention is to combine a corrugated or micro corrugated PMM with the non-corrugated metallic screen with different shape of its openings, preferably rectangular and different mesh numbers and/or corrugated or micro corrugated notched metallic foil and/or inorganic fibrous woven matrix material to arrive at this three dimensional (3D) structure.
  • the PMM could be fleece.
  • a non-corrugated PMM can be uniquely combined with the corrugated or micro corrugated metallic screen with different shape of its openings, preferably , rectangular and different mesh numbers and/or corrugated or micro corrugated notched metallic foil and/or inorganic fibrous woven matrix material to arrive at this three dimensional (3D) structure.
  • every cell inside the substrate is composed of metallic screen with different shape of its openings, preferably rectangular and different mesh numbers and/pr corrugated or micro corrugated notched metallic foil and / or inorganic fibrous woven matrix material and PMM as its walls.
  • the cell density is preferred to be in the range from 20 to 1300 cells per square inch (cpsi), preferably from 50 - 600 cpsi.
  • the inorganic fibrous woven matrix material has a fiber thickness in the range of 5 to 22 micrometers.
  • the inorganic fibrous woven matrix material thickness is from 0.5 to 100 millimeter in a single layer, more preferably 0.5 - 10 millimeter and porosity is in the range of 70 to 95 %.
  • the PMM has a preferred porosity in the range of 70 - 95% and used in varying thickness of 0.1 mm to 1mm.
  • the members of the substrate are combined in unique ways to form different geometries such as circular, oval, square, rectangular, doughnut shaped, banana shaped, layered doughnut etc., each with or without a bypass and for different sizes and can either be solid fitted or can be partially open in radial and / or axial direction to give a variety of flow patterns.
  • the mesh numbers of the metallic screen of the substrate are preferred in the range of 120 - 20 meshes per inch, more preferably 90 -30 meshes per inch.
  • Metallic screen wire diameter is in the range of 0.08 - 0.3mm, preferably between 0.1 - 0.2 mm.
  • metallic foil has a thickness in the range of 20 - 110 micrometers, preferably between 40 - 80 micrometers.
  • the height of micro-corrugation is in the range of 0.01 - 0.5 mm, preferably between 0.02 - 0.2 mm. l o
  • the substrate of the invention exhibits high thermal and mechanical durability at all engine loads.
  • the invention discloses that it is possible to produce PCC Z /CPCC Z with cell densities ranging from 20 to 1300 cells per square inch (cpsi), preferably between 50 and 600 cpsi, with or without micro corrugation.
  • the corrugation is angular and corrugation angle is in the range of 10 to 60 degrees, preferably in the range of 32 - 40 degrees.
  • the corrugation can also be straight or turbulent.
  • CPCC Z which is the coated PCC Z is capable of oxidizing the trapped soot particles leading to increase PM reduction efficiency. It is further disclosed that CPCC Z & PCC 2 is capable of oxidizing the trapped soot particles with a volume substantially lower than that of prior art. A much lower back pressure is seen when compared to the existing devices when the substrate of the present invention is used in a device to increase the PM reduction efficiency.
  • the invention discloses that CPCC Z is coated with a washcoat material that is capable of continuously producing in-situ nitrogen dioxide, which is essential for continuous oxidation of trapped soot particles leading to increase PM reduction efficiency.
  • the invention discloses the unique washcoat material and method of preparing the same.
  • the unique coating of a washcoat is disclosed by the inventors.
  • the washcoat comprises of a combination 25 of catalytically inactive material and catalytically active material.
  • the washcoat is to be applied before or after the substrate is formed.
  • the catalytically inactive material of the washcoat includes a combination of a variety of oxides, nitrates, and hydroxides of aluminum, silicon, titanium, zirconium, hafnium, calcium, barium, strontium and rare earth metal oxides.
  • the catalytically inactive material has a specific surface area ranging between 100 to 260 sqm per g. 30
  • the washcoat comprises of fine particles having a median particle size distribution ranging between 0.5 - 3.5 microns.
  • the washcoat allows substantial in-situ generation of nitrogen dioxide in the range of 20% to 50% by volume, which continuously allows efficient oxidation of soot accumulated inside the body of the honeycomb structure during the operation of the engine.
  • the substrate provides .same or lower backpressure than that before washcoat coating. It was surprisingly found that the washcoat coating provides catalytic performance at much lower volumes leading to cost and pollution reduction.
  • the catalytically active material used in the washcoat comprises but is not limited to a combination of a 5 variety of salts of platinum, palladium, rhodium, ruthenium, osmium and iridium, preferably platinum, palladium and rhodium.
  • the catalytically active material is contained in the honeycomb body of the substrate preferably in the range of 0.5 to 30 g/cubic feet, more preferably from 1 - 10 g/cubic feet.
  • the coating of the washcoat has a thickness in the range of 0.5 to 10 micrometers, preferably from 1 - 5 micrometers.
  • the elements can be incorporated in pre-washcoated honeycomb body. The elements can be l o incorporated into the washcoat material directly, before carrying out the coating.
  • the washcoat is designed to have a high degree of adhesion to both the PM and metallic screen as well as metallic foil and inorganic material and its combinations thereof.
  • the washcoat exhibits high thermal and mechanical durability and resists poisoning due to sulfur present in the automotive exhaust gas, when the engine is in operation.
  • the substrate of the invention offers uniform flow distribution and has interacting three dimensional channel network, which allows quick dissipation of heat energy released during regeneration of such devices. There is improved heat and mass transfer efficiency leading to optimum internal diffusional and axial flows.
  • the substrate has interacting channels which effectively decelerates sticky and/or wet & dry particles alike, from the engine exhaust, on their surfaces that eventually are trapped inside the PMM and /or metallic mesh with 20 different shape of its openings, preferably rectangular and different mesh numbers and/or within the inorganic fibrous woven matrix.
  • the capturing of solid particles happens predominantly by impinging the collected particles from the engine exhaust, upon the interposed deflecting surface
  • the PMM and the metallic screen are also individually coated with a combination of catalytically inactive material and catalytically active material, before forming them into a 25 substrate
  • Figure 2.1 depicts schematically the PCC 2 combination of PMM & metallic screen of the present invention.
  • Figure 1.3 - 1.16 30 reveal the different embodiments of the substrate structure and combinations including straight/corrugated/micro corrugated / notched metallic foil/ angle corrugation/Turbulent/porous /Flat /un-corrugated/Metallic screen/rectangular screen/square screen
  • Figure 2 depicts examples of the different shapes of Particulate Combustion Catalyst and Coated Particulate Combustion Catalyst
  • substrate formed by the combination of flat PMM and straight channel 300 or 400 cpsi corrugated foil exhibits a lower ⁇ and a combination of flat PMM and straight channel 500 cpsi corrugated foil (1592/1), a combination of flat PMM and turbulent channel 350 cpsi corrugated foil (1597/1 ) exhibits the highest ⁇ values.
  • substrate formed by the combination of flat PMM and straight channel 100 cpsi corrugated foil (1588/1) exhibits a lower ⁇ and a combination of flat PMM and turbulent type channel 200 cpsi corrugated foil (1596/1) exhibits the highest ⁇ values.
  • ⁇ measured for a combination of flat PMM and turbulent channel 120 cpsi corrugated foil (1595/1) and a combination of flat PMM and straight channel 200 cpsi corrugated foil are about the same and lies in between.
  • Figure 3.9 describes the ⁇ behaviour of two distinct substrate structure types, formed by the (1 ) combination of flat PMM and straight channel 300 cpsi corrugated foil (1590/1_uc & 1590/1 _c) and (2) as well as that formed by another combination of flat PMM and turbulent type channel 350 cpsi corrugated foil (1597/1_uc & 1597/1_c).
  • substrate formed by the combination of flat PMM with straight channel 100 cpsi corrugated foil exhibits much lower ⁇ than a combination of flat PMM with turbulent type channel 120 cpsi corrugated foil (1595/1_uc & 1595/1_c).
  • the double crossing layered doughnut structure (1675) exhibits a clearly higher ⁇ compared to the single crossing layered doughnut structure (1674/1).
  • the prior art substrate structure with 292 cpsi angular corrugation (1687) & a combination of flat PMM with angle corrugated 263 cpsi screen (1676) exhibits the highest ⁇ .
  • the typical inlet gas composition gas comprises of (1) CO: 1000 - 1500 PMM, propylene propane: 500 - 800 ppm, 0 2 : 12 - 14 %, NO: 500 - 800 ppm, 6 - 10 % C02, 7 - 12% steam & balance nitrogen. Regulated flow of preheated mixture of these gases are fed into a reactor containing the sample under evaluation. Space velocities are controlled by regulating the flow of the gas mixture entering the reactor. The output gases from the reactor are analyzed by a state of the art multi gas analyzer.
  • PCC Z and CPCC Z formed by unique combinations of corrugated or micro corrugated PMM and/or corrugated or micro corrugated metallic screen with different shape of its openings, preferably rectangular and different mesh numbers and/or corrugated or micro corrugated notched metallic foil and/or inorganic fibrous woven matrix material, with different precious metal loadings, varied washcoat layers, were evaluated at different space velocities.
  • PCC z was formed by combining a flat PMM with an angle corrugated metallic screen with rectangular mesh.
  • the so formed PCC Z was converted to CPCC Z by coating the former with a combination of catalytically inactive material, in such a manner to achieve a coating thickness of 2 micrometers.
  • Four samples of this said GPCC Z were then each coated with 1 g/cft, 5g/cft, 10g/cft & 20 g/cft of PGM.
  • Figure 9 compares catalytic activity, specifically the light-off temperature curves of the CPCC Z at space velocities of 30,000 /h.
  • the corrugation angle of 34° was selected for all the angle corrugated samples combinations.
  • VF20 on two layer washcoat gives the best efficiencies and with 30.000 lr 1 SV since the whole washcoat layer is available for the catalytic reaction.
  • VF5 on one layer and VF20 on two layer have the best in situ NO2 formations. From the cost point of view the best solution is VF5 in one layer.
  • CPCC Z having 5 g/ft 3 of PGM in one layer VF structure (VF1) exhibits better light-off behaviour than that having 20 g/ft 3 of PGM in prior art VX honeycomb structure (VX20).
  • VF1 gives also better in-situ N0 2 -formation efficiency.
  • VF5 80 % cheaper solution in PGM-cost.
  • Figure 13 shows the light-off curves for samples P-1661 to P1666 as following blank/uncoated structures (PCC Z ): Turbulent type of corrugated PMM with UF as flat (P-1661) and with MF as Micro corrugated (P-1662); Straight channel corrugated PMM with UF as flat (P-1663) and with MF as Micro corrugated (P- 664); Angle corrugated PMM with UF as flat (P-1665) and with MF as Micro corrugated (P-1666).
  • PCC Z blank/uncoated structures
  • Figure 14a shows the light-off curves for samples P-1661 to P1666 as following coated structures (CPCC Z ): ; Turbulent type of corrugated PMM with UF as flat (P-1661) and with MF as Micro corrugated (P-1662); Straight channel corrugated PMM with UF as flat (P-1663) and with MF as Micro corrugated (P-1664) ⁇ Angle corrugated PMM with UF as flat (P-1665) and with MF as Micro corrugated (P-1666).
  • the catalyst efficiency is superior for micro corrugated foil structures as compared to flat uncorrugated foil structures as evaluated at a space velocity of 30.000 fv 1 and with a PGM-loading 1 g/ft 3 .
  • the light off curves show the advantage of micro corrugation, especially at temperatures greater than 300°C, where the fnass and heat transfer phenomena begins to control catalytic reactions.
  • Figure 14b shows the light-off curves for samples for only Straight channel corrugated PMM with UF as flat (P- 1663) and with MF as micro corrugated (P-1664). It is clear that the catalyst efficiency is better for micro corrugated foil structure compared to flat uncorrugated foil structures evaluated at a space velocity of 30.000 h' 1 SV and with PGM-loading 1 g/ft 3 . The results show how micro corrugation helps especially at over 300 °C temperatures where mass and heat transfer start to control catalytic reactions. ,
  • Figure 15a shows the light-off curves for samples for Straight channel corrugated PMM with UF as flat (P-1663) and with MF as Micro corrugated (P-1664). It is evident that the catalyst efficiency is superior for Micro corrugated foil structure compared to flat uncorrugated foil structure evaluated at 30.000 fv 1 SV and with PGM- loading of 5 g/ft 3 .
  • Figure 15a shows the light-off curves for CPCC Z samples with Straight channel corrugated PMM with UF as flat (P-1663) and with MF as Micro corrugated (P-1664). Angle corrugated PMM with UF as flat (P-1665) and with 5 MF as Micro corrugated (P-1666).
  • the catalyst efficiencies are found better for micro corrugated foil structures compared to flat uncorrugated foil structures evaluated at 30.000 tv 1 SV and with PGM-loading of 1 g/ft 3 .
  • Figure 16a shows the light-off curves for CPCC Z samples with Angle corrugated PMM with UF as flat (P-1665) and with MF as Micro corrugated P-1666 evaluated at a space velocity of 30.000 fr 1 SV and 60.000 fr 1 SV is shown in Figure 16b. Results show that when the space velocity increases from 30.000rr 1 to 60.000 ft 1 the light- l o offs move to higher temperature regime but at both the space velocities, the micro corrugated foil structures show better catalytic efficiencies compared to flat uncorrugated foil structures with PGM-loading of 10 g/ft 3 .
  • NO2 formation is at good level at the space velocity of 30,000 for (P-1666) with MF and with a PGM-loading 10 g/ft 3 .
  • This kind of in situ NO2 formation gives good basis to reach efficient soot regeneration for diesel exhaust PM starting from about temperatures of 230°C.
  • Figure 17a shows the light-off curves for CPCC Z samples with Straight channel corrugated PMM with UF as flat
  • Figure 17b shows the light-off curves for CPCC Z samples with Turbulent type Of corrugated PMM with UF as flat
  • results show that the micro corrugated foil structures MF show better efficiencies compared to flat uncorrugated foil structures UF in both turbulent type and angle corrugated PMM with PGM-loading 10 g/ft 3 and at a ispace 5 velocity Of 60.000 fv 1 . Also it can be seen that the angle corrugated PMM with MF gives the best efficiencies in all studied respects (CO, HC and N0 2 ).
  • Figure 18a shows the light-off curves for CPCC Z samples with both VX and VL prior art structures with PGM- loadings of 1 , 5 and 10 g/ft 3 with one layer coating.
  • Figure 18a shows the light-off curves for CPCC Z samples VX1 & VL10.
  • the catalytic 30 performance of the former is far poorer as compared to that for VL10, which is the best.
  • Both the samples have one layer coating.
  • VX and VL the efficiencies improves as PGM-loading increases.
  • VL10 and VL5 are the best in this set of comparison.
  • Figure 19 shows the light-off curves for CPCC Z samples with Straight channel corrugated foil CF with flat PMM (P-1700) Turbulent type corrugated foil CF with fiat PMM (P-1701); Angle corrugated foil CF with flat PMM (P- 1702).
  • the turbulent channel corrugation exhibits superior catalytic efficiency, while the Straight channel corrugations is the second best, followed by the Angle corrugation, which is comparatively inferior or in this set of comparison.
  • Figure 20 shows the light-off curves for CPCC Z samples with Straight channel corrugated foil CF with flat PMM (P-1700); Turbulent type corrugated foil CF with flat PMM (P-1701); Angle corrugated foil CF with flat PMM (P- 1702).
  • N0 2 formation % are still rather low for all cases, because higher PGM-loadings are needed to give higher efficiency in this respect.
  • Turbulent corrugation P-1701 gives the NO2 formation-%.
  • Figure 21 shows the light-off curves for CPCC Z samples with Straight channel corrugated foil CF with flat PMM (P-1700); Turbulent type corrugated foil CF with flat PMM (P-1701); Angle corrugated foil CF with flat PMM (P- 1702).
  • the catalyst efficiency is better for micro corrugated foil structures compared to flat uncorrugated foil structures with both SVs and PGM-loading 1 g/ft 3 .
  • the light off curves show the advantage of micro corrugation, especially at temperatures greater than 300°C, where the mass and heat transfer phenomena typically starts to control catalytic reactions.
  • Soot loading studies were carried out on some of the selected samples, as described in figures 23.1 & 23.2.
  • the said samples were fitted into the exhaust assembly of the test vehicle, which was then driven to a distance of 200 km on a driving cycle simulating a typical Indian city driving pattern. During this operation, soot emancipating from the engine, enters the sample structure and gets collected therein. This process is termed as soot loading.
  • Figure 23.1 shows that, for catalysts placed in the close coupled position, flat PMM and angle corrugated screen yields the highest soot collection efficiency up to 150 Km. After that, the prior art substrate 1394/2 collects the most.
  • the lowest soot loading efficiency is displayed by the substrate formed by the combination of flat PMM and straight channel corrugated foil with 200 cpsi.
  • Table 17 Structural information from Prior Art nominal (Ref. 1) and front DOC (1675) and Prior Art VL-substrate (1687) and Current invention Layered doughnut structures with Flat PM + Layered doughnut Corrugated Screen (1674/1) and Flat inorganic fibrous woven matrix + Anqle Corrugated Screen (1674/2)
  • the mass emission tests were carried out on an Indian three wheeler test vehicle with BSIII and BSIV driving cycles with or without EGR system.
  • the mass emission of the said vehicle were measured in hot 5 condition on BSIII driving cycle and in cold condition on BSIV driving cycle. From Figure 18 it can be seen that the current invention with Layered doughnut type of PMM or with inorganic Fibrous woven matrix gives competitive mass emissions, especially in the case of particulate matter, with only 39.2 % catalyzed volume as compared to the prior art structure, when tests are done with the same preceding DOC.

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Abstract

La présente invention concerne un catalyseur de matière particulaire de combustion et un catalyseur revêtu de matière particulaire de combustion qui évitent les risques de défaillance dûs à l'accumulation continue de matière particulaire piégée en permettant un autre trajet d'écoulement ouvert en cas de saturation de suie, ce qui maintient la contre-pression dans des limites acceptables. La présente invention concerne également un dispositif tridimensionnel pour le traitement catalytique des gaz d'échappement de véhicules automobiles, comprenant un substrat unique en son genre.
PCT/IB2016/000027 2015-01-16 2016-01-18 Catalyseur de matière particulaire de combustion (pct ou pccz) et catalyseur revêtu de matière particulaire de combustion (cpcc oucpccz) Ceased WO2016113631A1 (fr)

Priority Applications (1)

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RU2017122627A RU2687389C2 (ru) 2015-01-16 2016-01-18 КАТАЛИЗАТОР СГОРАНИЯ ТВЕРДЫХ ЧАСТИЦ (РСС ИЛИ PCCz) И КАТАЛИЗАТОР СГОРАНИЯ ТВЕРДЫХ ЧАСТИЦ С ПОКРЫТИЕМ (СРСС ИЛИ CPCCz)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0341832A2 (fr) * 1988-05-13 1989-11-15 Johnson Matthey Inc. Traitement de gaz d'échappement de moteur diesel
US7625538B2 (en) * 2003-07-02 2009-12-01 Haldor Topsoe A/S Diesel particulate filter

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2059841C1 (ru) * 1993-08-24 1996-05-10 Малое предприятие "Технология" Фильтр для очистки выхлопных газов двигателей внутреннего сгорания
DE10153284A1 (de) * 2001-10-29 2003-05-15 Emitec Emissionstechnologie Filterverbund und Verfahren zu seiner Herstellung

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0341832A2 (fr) * 1988-05-13 1989-11-15 Johnson Matthey Inc. Traitement de gaz d'échappement de moteur diesel
US7625538B2 (en) * 2003-07-02 2009-12-01 Haldor Topsoe A/S Diesel particulate filter

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