US20070009400A1 - Porous sheet and substrate having porous sheet(s) for treating exhaust gases of combustion engines - Google Patents

Porous sheet and substrate having porous sheet(s) for treating exhaust gases of combustion engines Download PDF

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Publication number
US20070009400A1
US20070009400A1 US10/553,179 US55317904A US2007009400A1 US 20070009400 A1 US20070009400 A1 US 20070009400A1 US 55317904 A US55317904 A US 55317904A US 2007009400 A1 US2007009400 A1 US 2007009400A1
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United States
Prior art keywords
porous sheet
sheet
particles
metal substrate
support
Prior art date
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Abandoned
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US10/553,179
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English (en)
Inventor
Aulis Vakkilainen
Reijo Lylykangas
Ritva Heikkinen
Teuvo Maunula
Matti Harkonen
Ari Lievonen
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Dinex Ecocat Oy
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Individual
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=8566381&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=US20070009400(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Individual filed Critical Individual
Assigned to ECOCAT OY reassignment ECOCAT OY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MAUNULA, TEUVO, LIEVONEN, ARI, VAKKILAINEN, AULIS, LYLYKANGAS, REIJO, HEIKKINEN, RITVA, MARKONEN, MATTI
Assigned to ECOCAT OY reassignment ECOCAT OY CORRECTIVE COVERSHEET TO CORRECT THE NAME OF THE ASSIGNEE THAT WAS PREVIOUSLY RECORDED ON REEL 018267, FRAME 0248. Assignors: MAUNULA, TEUVO, LIEVONEN, ARI, VAKKILAINEN, AULIS, LYLYKANGAS, REIJO, HARKONEN, MATTI, HEIKKINEN, RITVA
Publication of US20070009400A1 publication Critical patent/US20070009400A1/en
Priority to US13/109,514 priority Critical patent/US8337762B2/en
Abandoned legal-status Critical Current

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/022—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01D53/8643—Removing mixtures of carbon monoxide or hydrocarbons and nitrogen oxides
    • B01D53/8646—Simultaneous elimination of the components
    • B01D53/865—Simultaneous elimination of the components characterised by a specific catalyst
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
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    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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    • B01J29/00—Catalysts comprising molecular sieves
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    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7615—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0246—Coatings comprising a zeolite
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/022—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
    • F01N3/0222—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous the structure being monolithic, e.g. honeycombs
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/033—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
    • F01N3/035—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors, e.g. catalysed diesel particulate filters
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2255/92—Dimensions
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    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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Definitions

  • the present disclosure relates to a porous sheet for treating exhaust gases of combustion engines in open channels and a substrate having said porous sheet(s).
  • the present disclosure also relates to methods for manufacturing said porous sheet and substrate having said porous sheet(s).
  • substrates having open or closed channels For the treatment of exhaust gases of combustion engines, substrates having open or closed channels, or combinations of those is used.
  • open channels the exhaust gas is directly flowing through the substrate.
  • exhaust gas is forced to flow through walls, e.g., through ceramic or metallic porous walls.
  • open channels reduction of gaseous impurities is often high but the reduction of impurity particles is low, e.g., from 10 to 15%.
  • closed channels the reduction of gaseous impurities is high and also the reduction of impurity particles is high, e.g., from 70 to 90%.
  • the problem in closed channels is the clogging of walls. Closed channels will gradually wholly clog if it is not cleaned. Pressure loss will also increase. One way to keep the channels open is to clean them continuously or periodically.
  • WO 03038248 A1 discloses a filter composite whereby a fluid can flow through the filter composite. It comprises at least one top layer made of an at least partially porous material with at least one edge area and comprises at least one fibrous layer made of a fibrous cloth.
  • the filter composite is characterized in that at least one fibrous layer forms an enclosure that encloses the fibrous layer so that the fibrous layer is permanently arranged inside the at least one top layer.
  • a porous sheet that efficiently reduces particles of exhaust gas in open channels has now been invented. Accordingly a substrate having said porous sheet(s) has also been invented.
  • An exemplary embodiment of a porous sheet for treating exhaust gases of combustion engines in open channels characterized in that at least part of the porous sheet ( 3 , 3 a , 3 b ) has a covering support ( 33 ) having the median pore size over 10 nm and coarse particles over 1.4 ⁇ m and the area mass of support ( 33 ) is from 20 to 200 g/m 2 and the BET specific surface area of support ( 33 ) is from 30 to 300 m 2 /g.
  • An exemplary embodiment of a porous sheet for treating exhaust gases of combustion engines in open channels comprises a porous sheet including a plurality of openings, and a covering support, wherein the covering support covers at least a part of a surface of the porous sheet substrate, and wherein the covering support has pores with a median pore size over 10 nm and coarse particles with a median particle size over 1.4 ⁇ m.
  • An exemplary method for manufacturing a porous sheet for treating an exhaust gas of a combustion engine in open channels comprises at least partially covering a porous sheet with a covering support having pores with a median pore size over 10 nm and coarse particles with a median particle size over 1.4 ⁇ m.
  • FIG. 1 shows a substrate having flat porous sheet and smooth corrugated other sheets.
  • FIG. 2 shows a substrate having corrugated porous sheet and flat other sheet.
  • FIG. 3 shows a substrate having corrugated porous sheets and smooth corrugated other sheets.
  • FIG. 4 shows a substrate having corrugated porous sheets joined together.
  • FIG. 5 shows a substrate having corrugated porous sheet, fibrous sheet and smooth other sheet.
  • FIG. 6 shows a mesh sheet partially covered with a support having coarse particles and fibres.
  • FIG. 7 shows a mesh sheet partially covered with a support having coarse particles.
  • FIG. 8 shows a mesh sheet essentially covered with a coarse support.
  • FIG. 9 shows a photo of a mesh sheet essentially covered with a coarse support.
  • FIG. 10 shows cross-section of a mesh sheet.
  • FIG. 11 shows surface section of a mesh sheet.
  • FIG. 12 shows a three dimensional picture of mesh sheets joined together.
  • FIG. 13 shows test results with catalysts of prior art and of the invention.
  • FIG. 14 shows pore size distribution of support with and without coarse particles.
  • An embodiment of a porous sheet is at least partially covered with a support having pores over 10 nm and coarse particles over 1.4 ⁇ m.
  • essentially all pores of the porous sheet have been filled with said support.
  • the structure of coated porous sheet is simple, they are easy to manufacture and the reduction of particles is high compared, e.g., smooth sheet used in open channels.
  • porous sheet is that it is not clogging at all or the clogging is minimal. Therefore, the porous sheet can be used in most demanding conditions and is useful in many applications.
  • Porous sheet coated with material having pores and coarse particles acts as an effective open particle trap. This adds contacts of impurity gases and particles thus adding retention time and reduction of impurities. Impurity particles are also more often attached to porous sheet compared to smooth sheet.
  • porous sheet breaks down to gaseous impurities, which further decompose to harmless compounds. Part of gas can flow through pores of support in openings of porous sheet and particles attach on surfaces of support. Also this leads to better reduction of particles.
  • the porous sheet does not clog or the clogging is minimal and pressure loss and flow rate of gas are not reduced near the porous sheet. This reduces failure in operation thus adding efficiency of the porous sheet(s).
  • median pore size of said support is over 5 nm, preferably from 10 to 50 nm, such as from 15 to 20 nm.
  • Optimal pore size of the support also depends on exhaust gases and circumstances of gas flow near porous sheet. Exhaust gases can have e.g. median particle size from 5 to 200 nm and median pore size can e.g. be from 5 to 20 nm.
  • Porous sheet can be preferably mesh sheet or metal foam sheet, sintered metal sheet, knitted wire mesh, ceramic fiber sheet, etc.
  • the porous sheet is a mesh sheet.
  • the mesh number of the mesh sheet can be from 30 to 300.
  • At least part of exhaust gas can flow through the support having pores over 10 nm in the openings of mesh sheets. This leads to attachment of particles of exhaust gas to the surfaces of support giving essentially better reduction of particles.
  • the median opening size of mesh sheet is from 0.01 to 0.5 nm, preferably from 0.05 to 0.3 nm, such as from 0.08 to 0.2 nm.
  • openings of porous sheet can vary. Examples can include canal-like, square-like, diamond-like or hole-like, e.g., in diamond-like mesh sheet the wires can be at one level or they can be crosswise.
  • Porous sheet can be, e.g., corrugated or flat.
  • Preferably said porous sheet is a corrugated sheet, such as corrugated mesh sheet. This adds contacts of impurity gases and particles with support thus adding retention time and reduction of impurities.
  • the support comprises fibres, which are projecting out from the plane of said support. Also this adds reduction of particles by reducing flow rate of particles thus adding attachment of particles on support.
  • Rough support can be made e.g. by milling. Adding coarse particle fraction into the milling process remarkably changes the pore size distribution of the support.
  • Rough support material can be made e.g. by milling wash coat slurry and coarse alumina particles together by ball mill for 30 to 120 minutes, e.g., 40 to 60 minutes.
  • the median particle size of support is over 1 ⁇ m, preferably from 1.4 to 15 ⁇ m, such as from 2 to 10 ⁇ m.
  • the value partly depends on median particle size of exhaust gases and flow rates of gases near surfaces of porous sheets. It also depends on pore size of the porous sheet(s).
  • the area mass of coarse support can be, e.g., 20 to 200 g/m 2 , such as preferably 20 to 80 g/m 2 , e.g., 35 to 50 g/m 2 .
  • the specific surface area of the support measured by BET-method, can be, e.g., from 30 to 300 m 2 /g, such as preferably from 150 to 250 m 2 /g, e.g., from 150 to 200 m 2 /g.
  • Coarse particles can be, e.g., alumina-, silica, zirconia-, ceria- or/and titania-particles. Also other particles suitable to exhaust gas treatment can be used. The most suitable particles can be, e.g., coarse alumina particles that can easily be milled by ball milling. These selected alumina particles are round shaped as origin, thus the suitable effect for gas purification is maintained by milling. The original median particle size can be from 100 to 250 ⁇ m, e.g., from 150 to 200 ⁇ m, such as 170 ⁇ m.
  • the support comprises catalytically inert coarse alumina-, silica, zirconia-, ceria- or/and titania-particles.
  • at least part of support has been made by milling catalytically active fine support material and catalytically inactive coarse particles together.
  • said support comprises coarse material that is easy to mill.
  • the pore volume is from 0.3 to 0.8 cm 3 /g, e.g., 0.4 cm 3 /g.
  • the support comprises catalytically active fine material.
  • the support comprises catalytically inert coarse material.
  • Catalyst wash coats prepared namely for oxidation purposes will be the most suitable ones. Although any wash coat can be roughened by selected coarse particles. Typical oxidation wash coat is like in FIG. 8 .
  • the BET specific surface area can be, e.g., 230 m 2 /g, median particle size can be, e.g., from 1.5 to 3.5 ⁇ m, area mass of the support can be, e.g., 40 g/m 2 .
  • a substrate having open channels comprises at least one porous sheet.
  • said sheet is a corrugated sheet. More preferably said sheet is a corrugated mesh sheet.
  • the substrate having said porous sheet(s) acts as an effect open particle trap and this adds the reduction of particles.
  • open channels of the substrate do not clog or the clogging is minimal and pressure loss in substrate and flow rate of gas are not reduced. This reduces failure in operation thus adding efficiency of the substrate.
  • Said substrate can comprise also other sheet(s) other than the disclosed porous sheet(s).
  • Other sheet(s) can be, e.g., flat, corrugated, smooth, perforated, mesh sheet, wire mesh sheet or fibrous sheet.
  • the other sheet(s) is a corrugated sheet(s).
  • said other sheet(s) is a corrugated mesh sheet(s).
  • the other sheet(s) is a wire mesh sheet(s).
  • wire mesh sheet(s) in substrate the reduction of particles can be improved by adding retention time of particles in said substrate.
  • the other sheet(s) is a fibrous sheet(s).
  • fibrous sheet(s) in substrate the reduction of particles can be improved by adding retention time of particles in said substrate.
  • the other sheet(s) has been at least partially covered with a support.
  • That support can be same support used for porous sheet or it can be different support.
  • Preferable support for other sheet comprises coarse particles and/or fibres, which are projecting out from the plane of said support.
  • the support on the other sheet(s) has the median particle size over 0.4 ⁇ m, such as from 1.5 to 3.5 ⁇ m. This essentially adds the adhesion of particles thus improving the reduction of particles in said substrate.
  • the other sheet(s) is essentially covered with a support having the median particle size over 1.4 ⁇ m and/or having pores over 10 nm. This also improves reduction of impurity particles by adding attachment of particles to sheets.
  • the porous sheets and/or other sheet(s) have impressions and/or projections. This adds collision of gas and impurity particles to surfaces of the substrate thus adding reduction of particles. This leads to better reduction values of impurity particles of exhaust gas. Collision of gas also leads to better contact of gas with catalytically active material thus improving reduction of gaseous impurities.
  • Particles of exhaust gas of combustion engines are efficiently treated with substrate having porous sheet(s) as disclosed herein.
  • the reduction of impurity particles is surprisingly high compared to traditional substrates. Also the reduction of gaseous impurities is high.
  • the porous sheet(s) does not clog or the clogging is minimal so that it does not have effect s on flowing rate of exhaust gas in substrate. Also pressure loss in substrate is minimal.
  • the substrate can, e.g., be a pre-oxicatalyst or SCR-catalyst. It can also be a hydrolysis catalyst.
  • the substrate can be used to purify impurity particles of exhaust gases of combustion engines.
  • the structure of substrate can vary. It can be, e.g., wound or stacked.
  • the catalyst is coated on one or several catalytic substrates made from metallic, ceramic, metal oxide, SiC and/or Si nitride material(s).
  • the catalyst coating can be pre- or post-coated on normal ceramic or metallic cells or substrates where shapes of cells, such as a square, a triangle, cell density (10-2000 cpsi, cells per square inch, a term familiar to those skilled in the art), or wall thicknesses (10-500 ⁇ m), can vary widely according to the application. Very large channel sizes can be used in the catalyst ( ⁇ 100 cpsi) if the effluent gas contains high amounts of particles or sulfur compounds.
  • very small channel sizes can be used in the cell (such as >500 cpsi).
  • a typical cell number is from 50 to 600 cpsi.
  • the values of these variables can also vary within the cell, or in the next cells, this being advantageous due to efficient mixing, low pressure drop, or mechanical strength.
  • the cell to be coated can also serve as a kind of a statical mixing structure either having mixing zones (for instance, bents, flow obstacles, or throttlings) in separate channels, or the structure being made by superimposing corrugated, curved foils or plates in a manner where the directions of wave crests deviate from that of the incoming gas, the wave crests of the superimposed plates being, respective, oriented in different directions.
  • the wave crests of corrugated foils are parallel with one another, and with the main flow direction.
  • the substrate is coated on one or several cell-like, or porous structure(s).
  • the channels thereof can be parallel with the flow direction and/or have a different orientation.
  • the substrate is coated on one or several particle separating and/or mixing structure(s).
  • the substrate is combined with a particle trap, or filter made of ceramic, metallic, metal oxide, SiO 2 , SiC and/or Si nitride material(s).
  • Mixing efficiency can be controlled by altering the angle between the wave crest and the main flow direction.
  • mixing structure mixing of the flow is provided in radial direction of the pipe.
  • higher separation rates for particles compared to normal cell structures are obtained.
  • the structure to be coated can partly or totally consist of a metal mesh, sintered porous metal, fiber, or a particle trap.
  • the catalyst can also be coated on two or several of the described catalyst structures located in series or parallel in flow direction. Catalyst structures of different, or of same sizes can be incorporated into a single catalyst converter, or they can be present in separate converters connected by necessary piping.
  • the compositions of the catalysts of the invention, noble metal loads thereof (e.g., Pt), cell numbers (geometrical surface areas), or structures can be identical or different.
  • the catalyst coatings can also be assembled in forms divided into smaller structures where the exhaust gas temperature is maximized for initiating reactions in the catalyst. Therefore, it is preferable to use, for instance, one or several small catalyst cell(s) or other structures (metal fiber, mixer) upstream of the turbo (preturbo catalyst) or immediately downstream thereof (precatalyst).
  • the catalyst coating can also be situated at any point of the pathway of the exhaust gas, on the walls of piping or constructions (wings of the turbo, outlets from cylinders or from the turbo).
  • the particle separator can be made of ceramic, metallic, metal oxide, carbide (e.g., SiC), nitride material (SiH 2 ), nitride or a mixture thereof.
  • the structure can be a cell-like particle trap or a rod-like structure where the gas flows through the holes on the walls, the particles being retained in the inlet side of the separator, in flow direction.
  • Other particle separators include fiber-like, mesh-like, foamy or plate-like structures that can also be coated with the catalyst of the invention. In addition to particle separation, such structures can be used for cost reasons or due to low pressure drops caused by them.
  • the catalyst can be composed of several coated superimposed layers, at least one of which is a layer as disclosed herein.
  • the catalyst can be coated with another layer as disclosed herein, the upper, or the surface layer being free of active metal.
  • This protective layer can prevent the fully active metal from leaving from the catalyst, protect lower layers against deactivation, promote adsorption of particles to the surface, and/or alter electrical properties (electrical conductivity, charging, etc.) of the surface layer in comparison to the lower layer.
  • the catalyst can comprise, e.g., Sc, Ti, Cr, Mn, Fe, Co, Cu, La, Au, Ag, Ga, In and/or Ce as catalytically active material.
  • the substrate can preferably have corrugated sheets stacked together having oblique angles relative to each other.
  • the angle of profiles is from 5 to 30 degrees. They can preferably be joined together at cross over points by resistance welding. In the open channels like this the mass and heat transfer are very high compared to straight channels.
  • the substrate can also be a wounded substrate having impressions and/or projections. This leads to swirling motion resulting better mass and heat transfer compared, e.g., to straight channels.
  • Uneven flow rate in substrate can promote the reduction of particles on the porous sheet(s) by adding flowing of gas through pores of the support. This flowing is due to pressure differences between next to channels. Also impressions and depressions cause pressure differences in substrate thus adding gas flow through the porous sheets according to the invention. This phenomenon leads to attachments of particles on support and better reduction of particles from exhaust gas.
  • the substrate can be conical or tubular.
  • the shape of the substrate depends, e.g., on engine and exhaust gas.
  • substrate 1 comprises flat mesh sheets 3 a and smooth corrugated other sheet 2 a joined together so that there are open channels 4 between them.
  • substrate 1 comprises corrugated mesh sheets 3 b and smooth flat sheets 2 b joined together so that there are open channels 4 between them.
  • substrate 1 comprises corrugated mesh sheets 3 b and smooth corrugated other sheet 2 a joined together so that there are open channels 4 between them.
  • substrate 1 comprises corrugated mesh sheets 3 b , which are joined together so that there are open channels 4 between them.
  • substrate 1 comprises corrugated mesh sheet 3 b , wire mesh sheet 5 and smooth flat sheet 2 b , which are joined together so that there are open channels 4 between them.
  • gas can flow through open channels and depending on pressure differences and fluid circumstances gas is also flowing through the sheets coated by coarse material and particles of exhaust gas are attached to support. Particles are also attached to support due to collision with coarse particles and fibres. Preferably there are open channels with both sizes of said porous sheet.
  • FIGS. 6 to 8 is shown a mesh sheet 3 having wires 31 , which have square openings 32 .
  • the mesh sheet 3 is partially covered with support 33 having coarse particles and fibres.
  • the mesh sheet 3 is partially covered with support 33 having coarse particles.
  • the openings 32 of the mesh sheet 3 are essentially covered with support 33 having coarse particles.
  • FIG. 9 is a photo of a mesh sheet 41 covered with coarse support 43 having median particle size about 2 ⁇ m.
  • mesh sheet 3 has been covered with a support 33 having fine 33 f and coarse particles 33 c .
  • Coarse support essentially covers both wires 31 and openings 32 of the mesh sheet 3 .
  • Exhaust gas G can flow through the mesh sheet via pores 35 of the support 33 .
  • Particles of exhaust gas are preferably attached on surfaces of the support.
  • substrate 1 has corrugated mesh sheets 3 b joined together. These mesh sheets can be covered with a coarse support. Between these mesh sheets there are open channels 4 in said substrate 1 allowing open flowing of exhaust gas through said substrate 1 .
  • This embodiment is very preferably in deducing particles of the exhaust gas.
  • Prior art conventional catalyst has flat and corrugated smooth sheets rolled together and joined with needles.
  • the support has median particle size about 1.0 ⁇ m and there were no coarse particles in it.
  • the disclosed catalysts had coarse support having median particle size 2 ⁇ m.
  • POC-18534 had flat mesh sheet and smooth corrugated sheet rolled together and having impressions.
  • POC-18535 had corrugated mesh sheets stacked together having oblique 20 degrees angles relative to each other. Mesh sheets were joined together at cross over points by resistance welding.
  • FIG. 14 is shown measuring results of support.
  • W6500 is a conventional support having median particle size 1.4 ⁇ m and median pore size is 8 nm.
  • support comprises coarse particles and median particle size is 3.0 ⁇ m and median particle pore size is over 10 nm.
  • the surface of the sheet can intentionally be rough, thus promoting mass and heat transfer and/or particle removal/reactions.
  • Roughness is provided for instance with rough starting materials such as with 30-100 ⁇ m fibers and/or coating methods.
  • Roughness, support thickness and/or the number of catalytically active layers can preferably vary in axial direction of one or more of the catalysts.
  • the catalyst can be present in several structures assembled parallel or in series with respect to the flow direction.

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  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
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FI20035047A (fi) 2004-10-18
US8337762B2 (en) 2012-12-25
US20110217215A1 (en) 2011-09-08
FI118418B (fi) 2007-11-15
KR20060003024A (ko) 2006-01-09
EP1613845A1 (en) 2006-01-11
KR101113917B1 (ko) 2012-02-29
WO2004091782A1 (en) 2004-10-28
CN1777740B (zh) 2011-01-26
CN1777740A (zh) 2006-05-24
WO2004092553A1 (en) 2004-10-28
JP2006523526A (ja) 2006-10-19
ATE462873T1 (de) 2010-04-15
EP1613845B1 (en) 2010-03-31
FI20035047A0 (fi) 2003-04-17
JP4709138B2 (ja) 2011-06-22
EP1613429A1 (en) 2006-01-11
DE602004026285D1 (de) 2010-05-12

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