RU2687389C2 - Particulates combustion catalyst (pcc or pccz) and coated particulates combustion catalyst (cpcc or cpccz) - Google Patents

Abstract

FIELD: machine building.

SUBSTANCE: device for catalytic treatment of exhaust gases includes a substrate formed by connection of multiple separate elements. Separate element comprises multiple cells. Substrate is a combination of three-dimensional (3D) structure and contains one or more: a) porous metal filler (PMF); b) microriffled metal grid; c) microriffled jagged foil; d) inorganic fiber woven matrix material. Said cells have cell density in range of 20 to 1,300 cells per square inch (cpsi), preferably 50 to 600 cpsi, and said elements of said substrate are combined to form different geometries, such as round, oval, square, rectangular, toroidal, banana-shaped, layered toroidal, etc., each with bypass channel or without it and for different sizes.

EFFECT: disclosed particulates combustion catalyst overcomes the risks of failure due to continuous accumulation of trapped solid impurities by creating an alternative open flow path in case of overfilling with soot, thereby limiting backpressure within tolerable limits.

31 cl, 23 dwg, 18 tbl

Description

TECHNICAL FIELD

The purpose of this invention is the removal or reduction of solid impurities in the exhaust of internal combustion engines. The invention relates to a catalyst for the combustion of solid particles (PCC), particulate filter and exhaust gas purification system. The invention in particular relates to a composition and device designed to remove particulate matter or soot from diesel exhaust gas, direct injection engines (HBT), etc. This invention also relates to methods for manufacturing said device.

BACKGROUND

Removal or reduction of particulate matter released from the exhaust of internal combustion engines during operation is always desirable. Well-known particulate filters with flow walls (DPF) can remove more than 95% particulate matter (TP) from diesel engine exhaust. Some filters are designed for single use, intended for disposal and replacement after filling with accumulated soot. Others are designed to burn accumulated solids either passively, by using a catalyst, or by active means, such as a fuel burner, which heats the filter to the soot combustion temperature.

Filters require more maintenance than catalytic converters. Constant accumulation of trapped particulate matter clogs the filter media, and thus leads to an increase in back pressure in such devices and adversely affects the engine efficiency and, consequently, compliance with emission standards. Soot is collected inside a porous metal filler and on a metal grid due to the principles of inertial collision. There is a constant need to develop efficient removal of solid particles, and this invention provides the means for this. This invention provides a device that generates less back pressure than conventional DPFs, with a large cross-flow and substrate use.

SUMMARY OF THE INVENTION

The inventors developed the PCC, which overcomes the risks of malfunction due to the constant accumulation of trapped particulate matter by creating an alternative open flow path in case of soot overflow, thus limiting the backpressure within acceptable limits. A simulation-based approach and field tests were used to research, design, and develop new cross-flow structures by estimating the pressure drop and capture efficiency. The design has been optimized to effectively trap soot without clogging up the main flow paths.

The invention discloses a three-dimensional device for the catalytic treatment of exhaust gases of motor vehicles, comprising a substrate formed by joining a plurality of elements of a honeycomb substrate, each of which has a structure in which a number of cells are arranged in parallel or in series or in parallel with each other.

Another aspect of the present invention is a substrate formed by a special combination of porous metal filler (PMN) and metal mesh with different hole shapes and different numbers of cells with or without corrugated or micro-edged material to form a three-dimensional (3D) structure.

Another aspect of the present invention is a combination of a corrugated or microfilled PMN with a corrugated or microfilled metal mesh with different hole shapes and different numbers of cells with or without corrugated or microfilled material to form a three-dimensional (3D) structure.

Another aspect of the present invention is a combination of a corrugated or microfused PMN with a non-grooved metal mesh with different apertures and different numbers of cells with or without corrugated or microfilament material to form a three-dimensional (3D) structure.

Another aspect of the present invention is that the non-grooved PMN can be combined in a special way with a corrugated or microfilled metal mesh with different hole shapes and different numbers of cells with or without corrugated or microfilled material to form a three-dimensional (3D) structure.

Another aspect of the present invention is that each cell within the substrate consists of a metal grid with different hole shapes and a different number of cells and / or a corrugated or microfilled jagged metal material and / or inorganic material and PMN as walls.

Another aspect of the present invention is that CPCC ^Z is coated with a special coating material of porous oxide, which is able to continuously create insitu nitrogen dioxide, which is necessary for the constant oxidation of the trapped soot particles, which leads to an increase in the efficiency of reducing the amount of solid impurities (TP).

BRIEF DESCRIPTION OF THE DRAWINGS

Distinctive features of the present invention will become apparent by the following description of the preferred embodiments of the invention together with the accompanying drawings, in which:

FIG. 1: Combination of PMN and metal mesh in PCCz - schematic illustration

FIG. 1.2: Improved mass and heat transfer in a turbulent corrugated channel

FIG. 1.3: Directly grooved substrate design

FIG. 1.4: Porous, straight corrugated metal filler with microfilament / jagged metal foil

FIG. 1.5: Direct corrugated foil with microdiffusion

FIG. 1.6: Diagonal grooved foil with higher cpsi with microfusion

FIG. 1.7: Diagonal grooved foil with lower cpsi with microfusion

FIG. 1.8: Diagonally grooved flat foil backing and diagonal + micro-foil backing

FIG. 1.9: Diagonal grooved + microfusion foil and microfusion foil with direct corrugation

FIG. 1.10: Porous metallic filler of turbulent type

FIG. 1.11: Diagonal grooved porous metal filler

FIG. 1.12: Flat / non-grooved porous metal filler

FIG. 1.13: Metal mesh with plain weave structure and square mesh holes

FIG. 1.14: Metal mesh with a twill structure and square mesh holes

FIG. 1.15: Structure of a rectangular grid

FIG. 1.16: The structure of the square grid

FIG. 2: Examples of different forms of solid particulate catalyst and coated solid particulate catalyst

FIG. 3.1-3.13: change in ΔP of selected samples, having different combinations, and with corrugation.

FIG. 4: Data on mass emission of pollutants for selected samples with different combinations and with corrugations.

FIG. 5: Process Flow Chart 1 for a Solid Particulate Combustion Catalyst (PCC) and a Solid Particulate Combustion Catalyst (SRCC);

FIG. 6: Flowchart 2 of a process for a solid particulate matter catalyst (PCC) and a coated solid particle catalyst (SRCC);

FIG. 7: Process Flow Chart 3 for Solid Particle Combustion Catalyst (PCC) and Coated Solid Particle Combustion Catalyst (SRSS)

FIG. 8: Flowchart for the manufacture of a porous oxide coating for a catalyst for the combustion of coated solid particles

FIG. 9-22: Comparative laboratory simulation graph for the oxidation of carbon monoxide oxidation reaction of propylene oxidation and formation of nitrogen dioxide with temperature for various combinations of ^Z and RCC SRSS ^Z (hereinafter referred to as catalytic activity), tested under various operating conditions.

FIG. 9a and 9b compare the conversion of CO, HC,%, and the formation of NO2,%, as a function of temperature with a bulk velocity of 30,000 h-1 for VF structures with one and two layers with a flat porous metal filler (PMN) and diagonally grooved metal mesh rectangular cells with the content of MT G (platinum group metals) 1, 2, 5, 10 and 20 g / ft ³ .

FIG. 10 compares the conversion of CO, HC,%, and the formation of NO2,%, as a function of temperature with a bulk velocity of 30,000 h-1 for a single layer VF structure with a flat porous metal filler (PMN) and a diagonal corrugated metal grid with rectangular cells containing PGM 1 g / ft ³ and for a single-layer VX structure of the prior art with an PGM content of 20 g / ft ³ .

FIG. 11a and 11b compares the conversion of CO, HC,%, and the formation of NO2,%, as a function of temperature, with a bulk velocity of 30,000 and 60000h-1 for single-layer VF structures with flat porous metal filler (PMN) and diagonally corrugated metal mesh with rectangular cells the content of PGM 1 and 5 g / ft ³ .

FIG. 12a and 12b compare the conversion of CO, HC,%, and the formation of NO2,%, as a function of temperature with a bulk velocity of 60000 h-1 for VF with one and two layers with a flat porous metal filler (PMN) and diagonally corrugated metal mesh with rectangular cells containing PGM 1, 5, 10 and 20 g / ft ³ .

FIG. 13a and 13b compare the conversion of CO, HC,%, and the formation of NO2,%, as a function of temperature, with a bulk velocity of 30,000 h-1 for uncoated structures with three different types of corrugations for porous metal filler (PMN) with flat / non grooved foil (UF ) or microfilament / jagged foil (MF).

FIG. 14a and 14b compare the conversion of CO, HC,%, and the formation of NO2,%, as a function of temperature, with a bulk velocity of 30,000 h-1 for single-layer structures with three different types of corrugations for porous metal filler (PMN) with flat / non-grooved foil (UF) or microfilament / jagged foil (MF). The content of PGM is the same in all cases - 1 g / ft ³ .

FIG. 15a and 15b compare the conversion of CO, HC,%, and the formation of NO2,%, as a function of temperature with a bulk velocity of 30,000 h-1 for single-layer structures with different types of corrugation for porous metal filler (PMN) with flat / non-grooved foil (UF) or microfilled / jagged foil (MF). The content of PGM is the same in all cases - 5 g / ft ³ .

FIG. 16a and 16b compare the conversion of CO, HC,%, and the formation of NO2,%, as a function of temperature with a bulk velocity of 30,000 and 60,000 h-1 for single-layer structures with a diagonal type of corrugation of porous metallic filler (PMN) with flat / non-woven foil (UF) or microfilament / jagged foil (MF). The content of PGM is 10 g / ft ³ .

FIG. 17a and 17b compare the conversion of CO, HC,%, and the formation of NO2,%, as a function of temperature with a bulk velocity of 60000 h-1 for structures with one layer with three different types of corrugation of porous metal filler (PMN) with flat / non-grooved foil (UF ) or with microfilled / jagged foil (MF). The content of PGM is 10 g / ft ³ .

FIG. 18a and 18b compares the conversion of CO, HC,%, and the formation of NO2,%, as a function of temperature with a bulk velocity of 30,000 h-1 for single-layer VX structures with 330 cpsi, a corrugated metal mesh has a PGM content of 1, 5 and 10 g / ft ³ .

FIG. 19 compares the conversion of CO, HC,%, and the formation of NO2,%, as a function of temperature with a bulk velocity of 30,000 and 60000 h-1 for single-layer structures with three different types of corrugations for foil (CF) with flat porous metal filler (PMN). The content of PGM is the same in all cases - 1 g / ft ³ .

FIG. 20 compares the conversion of CO, HC,%, and the formation of NO2,%, as a function of temperature with a bulk velocity of 30,000 and 60,000 h-1 for single-layer structures with three different types of corrugations for foil (CF) with a flat porous metal filler (PMN). The content of PGM is the same in all cases - 5 g / ft ³ .

FIG. 21 compares the conversion of CO, HC,%, and the formation of NO2,%, as a function of temperature with a bulk velocity of 30,000 and 60,000 h-1 for single-layer structures with three different types of corrugations for foil (CF) with flat porous metal filler (PMN). The content of PGM is the same in all cases - 10 g / ft ³ .

FIG. 22a and 22b compare the conversion of CO, HC,%, and the formation of NO2,%, as a function of temperature with a bulk velocity of 30,000 and 60,000 h-1 for single-layer structures with two different types of corrugations for porous metallic filler (PMN) with flat / non-woven foil ( UF) or microfilled / jagged foil (MF). The content of PGM is the same in all cases - 1 g / ft ³ .

FIG. 23.1 and 23.2 describes the parameters of the accumulation of soot as a function of the distance made by the samples of CPCC ^Z , having different structural combinations and different corrugations.

DETAILED DESCRIPTION OF THE INVENTION

Other objects and aspects of the invention will be apparent from the following description of embodiments of the invention with reference to the accompanying drawings, which are attached below. Embodiments of the present invention can be variously modified. Thus, the scope of the present invention should be construed as not limited to the embodiments described herein. Embodiments are presented for better explanation of this invention to those skilled in the art. Further, the elements and areas of the drawings are depicted approximately, and the scope of the present invention is not limited to the respective sizes, shapes and spaces in the drawings.

The list below presents the full forms of abbreviations used in this specification:

The described device of the present invention is intended for the catalytic treatment of exhaust gases, which consists of a substrate formed by the combination of many individual elements, characterized in that the said individual elements contain a plurality of cells. A separate element may have a honeycomb body. A plurality of cells are arranged in parallel or in series or in parallel in sequence with respect to each other.

The invention discloses a substrate formed by a special combination of porous metal filler (PMN) and metal mesh with different hole shapes and different numbers of cells with or without corrugated or micro-edged material to form a three-dimensional (3D) structure. The invention provides a significant capture of solid impurities released from the engine.

Corrugated or microfilament PMN is combined with a corrugated or microfilament metal mesh with different apertures and different numbers of cells and / or a corrugated or microfabric jagged metal foil and / or inorganic fiber woven matrix material to produce a three-dimensional (3D) structure.

In an alternative embodiment of the invention, a corrugated or microfilament PMN is combined with a non-grooved metal mesh with different orifices, preferably rectangular, and different numbers of cells and / or corrugated or micro-grooved jagged metal foil and / or inorganic fiber woven matrix material to produce such a three-dimensional (3D) structure . PMN can be fleece.

Alternatively, the non-grooved PMN can be specifically combined with a corrugated or micro-fiber metal mesh with different hole shapes, preferably rectangular, and a different number of cells and / or fluted or micro-tongue jagged metal foil and / or inorganic fiber woven matrix material to produce such three-dimensional (3D) structures.

The invention further discloses that each cell within the substrate consists of a metal grid with different hole shapes, preferably rectangular, and a different number of cells and / or a grooved or microfilled jagged metal foil and / or inorganic fiber woven matrix material and PMN as its walls. Cell density is preferred in the range from 20 to 1300 cells per square inch (cpsi), preferably from 50 to 600 cpsi. The inorganic fiber woven matrix material has a fiber thickness of 5 to 22 micrometers. The thickness of the inorganic fiber woven matrix material is 0.5-100 millimeters in a separate layer, more preferably 0.5-10 millimeters, and the porosity is from 70 to 95%. PMN has a preferred porosity of 70-95% and is used with different thicknesses from 0.1 mm to 1 mm.

The elements of the substrate are combined in a special way, forming different geometries, such as round, oval, square, rectangular, toroidal, banana-shaped, layered toroidal, etc., each with or without a bypass channel and for different sizes, and can either have a continuous fit, or be partially open in the radial and / or axial direction, which provides a variety of flow patterns.

The number of cells of the metal mesh of the substrate is preferably 120-20 cells per inch, more preferably 90-30 cells per inch. The diameter of the wire metal mesh is 0.08-0.3 mm, preferably 0.1-0.2 mm, while the metal foil has a thickness of 20-110 micrometers, preferably 40-80 micrometers. The height of the microfusion is 0.01-0.5 mm, preferably 0.02-0.2 mm.

The substrate of the invention exhibits high thermal and mechanical stability at all engine loads.

The invention shows that it is possible to manufacture PCC ^Z / CPPS ^Z with cell densities varying from 20 to 1300 cells per square inch (cpsi), preferably from 50 to 600 cpsi, with or without microfusion. The corrugation is diagonal, the angle of the corrugation is from 10 to 60 degrees, preferably 32-40 degrees. Corrugation can also be direct or turbulent.

SRSS ^Z, which is coated with PCC ^Z, is capable of oxidizing the trapped soot particles, resulting in improved efficiency of reducing the amount of TP. Further discloses that SRSS ^Z and ^Z RCC able to oxidize the trapped carbon particles with a volume significantly lower than in the prior art. Significantly lower back pressure is observed when compared with existing devices, when the substrate of this invention is used in the device to increase the efficiency of reducing the number of TP.

The invention shows that SRSS ^Z is coated with a porous oxide coating material, which is able to continuously create insitu nitrogen dioxide, which is necessary for the constant oxidation of trapped soot particles, which leads to an increase in the efficiency of reducing the amount of TP. The invention discloses a special coating material of a porous oxide and a method of manufacturing such.

A special coating of porous oxide disclosed by the inventors. The porous oxide coating comprises a combination of a catalytically inactive material and a catalytically active material. The porous oxide coating must be applied before or after the substrate is formed.

The catalytically inactive material of the porous oxide coating includes a combination of a number 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 varying from 100 to 260 square meters. m per g. The porous oxide coating consists of particles having an average particle diameter distribution from 0.5 to 3.5 microns.

The porous oxide coating provides substantial insitu formation of nitrogen dioxide in the range from 20% to 50% by volume, which continuously ensures the effective oxidation of soot accumulated inside the body of the honeycomb structure during engine operation. The substrate provides the same or lower back pressure than before the coating of a porous oxide. Unexpectedly, it was found that the coating of porous oxide provides catalytic efficiency with significantly smaller volumes, which leads to lower costs and pollution.

The catalytically active material used in the porous oxide coating contains, but is not limited to, a combination of a number of platinum, palladium, rhodium, ruthenium, osmium and iridium salts, preferably platinum, palladium and rhodium. The catalytically active material is contained in the honeycomb body of the substrate, preferably in the range of 0.5-30 g / cu. foot, more preferably 1-10 g / cu. foot.

The porous oxide coating has a thickness in the range of 0.5-10 micrometers, preferably 1-5 micrometers. The elements may be incorporated into a pre-coated porous oxide honeycomb body. Elements may be incorporated into the porous oxide coating material directly prior to coating.

The porous oxide coating is designed to have a high degree of adhesion with PMN and metal mesh, as well as with metal foil and inorganic material and a combination thereof. The porous oxide coating exhibits high thermal and mechanical stability and is resistant to the sulfur pollution present in the exhaust gas of the car when the engine is running.

The substrate of the invention offers a uniform flow of the stream and has an interconnecting three-dimensional network of channels, which provides rapid dissipation of thermal energy produced during the regeneration of such devices. The efficiency of heat and mass transfer is improved, which leads to optimal internal diffusion and axial fluxes.

The substrate has interacting channels that effectively slow down sticky and / or wet and dry similar particles from the engine exhaust on their surfaces, which over time are trapped inside the PMN and / or metal mesh with different shape of holes, preferably rectangular, and different numbers of cells and / or inside an inorganic fiber woven matrix material. The capture of solid particles occurs predominantly by pushing the captured particles from the engine exhaust on an intermediate reflective surface.

In another embodiment of the invention, PMN and metal mesh are also individually coated with a combination of a catalytically inactive material and a catalytically active material before forming the substrate from them.

The various features of the invention are further described in non-limiting examples for a better understanding of the invention.

FIG. 1.1 schematically depicts a combination of PMN and metal mesh for PCCz of the present invention. FIG. 1.2 explains the improved mass and heat transfer in the channel with turbulent type corrugation. FIG. 1.3-1.16. Various embodiments of the substrate structure and combinations are disclosed, including straight / grooved / myricuffle / notched metal foil / diagonal grooved / turbulent / porous / flat / non-grooved / metal mesh / rectangular mesh / square mesh.

FIG. 2 depicts examples of different forms of solid particulate catalyst and coated solid particulate catalyst.

Backpressure Rating:

From FIG. 3.1 it can be seen that the substrate formed by the combination of a flat PMN and a diagonally grooved mesh with 330 cpsi clearly demonstrates the highest ΔP (1448). The second in terms of indicators - with flat PMN and diagonally grooved 330 cpsi (1401/1).

This is followed by a substrate formed by a combination of flat PMN and 330 diagonally grooved mesh having a smaller volume (1461).

Both structures of the prior art (1394/3 and 1405) show a lower ΔP with 33 grid grooves and with square and rectangular cells.

From FIG. 3.2 shows that the substrate formed by the combination of flat PMN and diagonally grooved mesh (1448) with 330 cpsi shows the highest ΔР, while the combination of flat PMN and diagonally grooved mesh (1461) with 400 cpsi shows the lowest ΔР.

Another combination of the substrate structure of the prior art (1405 + 1407) and the combination of flat PMN and diagonal grooved with 330 cpsi (1401/1) are in between.

From FIG. 3.3 it can be seen that the substrate formed by a combination of diagonally corrugated PMN with 330 cpsi and a diagonal corrugated grid with 330 cpsi gives the maximum ΔР (1436/1). The second substrate of the previous level of technology with a diagonal corrugated grid (1394/3) with 330 cpsi gives the same ΔР with both square and rectangular cells (1405).

The lowest ΔР is demonstrated by the substrate formed by the combination of a corrugated turbulent mesh with 200 cpsi and PMN (1444) with grooves.

From FIG. 3.4 it can be seen that the prior art, containing a corrugated 330 cpsi mesh, obviously gives the highest ΔP (1394/3). It can also be seen that the structure formed by the combination of diagonally corrugated PMN with 100 cpsi and flat mesh (1401/4) shows a higher ΔP than the structure formed by the combination of flat PMN and diagonally corrugated mesh (1401/3) with 100 cpsi.

From FIG. 3.5 it is seen that the substrate (1583/1) of the prior art with a 400 cpsi grid gives the highest ΔР and 1582/1 with a grid with 33p cpsi has the highest ΔР. Both flat substrates PMN, 1584/1 and 1585/1, with 330 and 400 cpsi, respectively, have intermediate indicators.

From FIG. 3.6 it can be seen that the substrate (1581/1) of the prior art with a 400 cpsi grid shows the highest ΔP. The substrate formed by the combination of a flat PMN and a straight corrugated mesh with 300 cpsi gives the lowest ΔP. The effectiveness of the accumulation of carbon black substrate of the prior art with a grid (1580/1) with 330 cpsi has intermediate performance.

From FIG. 3.7 shows that the substrate formed by the combination of flat PMN and corrugated foil (1590/1 and 1591/1) with direct corrugation with 300 or 400 cpsi, shows the lowest ΔР, and the combination of flat PMN and foil (1592/1) with direct corrugation with 500 cpsi, the combination of flat PMN and foil (1597/1) with turbulent corrugated type with 350 cpsi shows the highest ΔР values.

From FIG. 3.8 shows that the substrate formed by the combination of flat PMN and foil (1588/1) with direct corrugation with 100 cpsi shows a lower ΔР, and the combination of flat PMN and foil (1596/1) with corrugation of a turbulent type with 200 cpsi shows the highest ΔP values ΔP, measured for a combination of flat PMN and foil (1595/1) with a 120 cpsi turbulent type corrugation and a combination of flat PMN and a direct corrugated foil with 200 cpsi, is approximately the same between the extreme values.

FIG. 3.9 describes the ΔP parameters of two different types of substrate structures formed by (1) a combination of flat PMN and corrugated foil (1590 / 1_uc & 1590 / 1_c) with straight corrugated 300 cpsi, and (2) also a substrate formed by another combination of flat PMN and foil (1597 / 1_uc & 1597 / 1_с) with turbulent type corrugation with 350 cpsi.

In this graph, the combination of flat PMN and turbulent type corrugations shows a higher ΔP. In both structures, the coating does not increase ΔP.

From FIG. 3.10 shows that the substrate formed by the combination of flat PMN and foil (1588 / 1_uc & 1588 / 1_c) with direct corrugation with 100 cpsi, shows a much lower ΔР than the combination of flat PMN with foil (1595 / 1_uc & 1595 / 1_c) corrugation turbulent type with 120 cpsi.

In both structures, the coating does not increase ΔP.

From FIG. 3.11 it is seen that the substrate structures of a layered toroidal type, formed by a combination of flat PMN and diagonal grooved mesh (1674/1) with 263 cpsi and another combination of flat inorganic fiber woven matrix with a diagonal grooved mesh with 263 cpsi, give the lowest ΔР value.

The double intersecting layered toroidal structure (1675) shows a clearly higher ΔP compared to the single intersecting layered toroidal structure (1674/1).

The structure (1687) of a prior art substrate with a diagonal grooved 292 cpsi and the combination of a flat PMN with a diagonal grooved mesh (1676) with 263 cpsi shows the highest ΔР.

From FIG. 3.12 it is seen that the structures of the substrate of a layered toroidal type, formed by the combination of a flat PMN with a diagonal corrugated grid (1669) with 263 cpsi, demonstrate the lowest ΔР.

Another combination of planar PMN with diagonal grooved, mesh (1669) with 263 cpsi demonstrates the highest ΔР, and the substrate (1682) of the prior art with diagonally grooved mesh with 263 cpsi is between them.

From FIG. 3.13 it is seen that the structures of the substrate of a layered toroidal type, formed by the combination of a flat PMN with a diagonal corrugated grid (1673) with 263 cpsi, demonstrate the lowest ΔР.

Another combination of planar PMN with diagonal grooved, substrates with a corrugated mesh (1659) with 263 cpsi and (1660) with 303 cpsi shows approximately the same and the highest ΔР.

Research to assess the effectiveness of a dynamometer (mass emission):

The catalytic activity in terms of mass emission of pollutants for various combinations of SRSS ^Z was evaluated on a chassis dynamometer. Investigated samples were collected in the exhaust assembly in the test vehicle assembly, which was then set in motion in a test cycle simulating a driving circuit in a typical Indian city. During this operation, the predominant pollutants consisting of carbon monoxide, hydrocarbon, nitrogen oxides and particulate matter released from the engine were continuously monitored and measured in grams of data emitted pollutants per kilometer passed by the test vehicle.

FIG. 4 compares the mass emission of pollutants for the structure of the substrate of the prior art with the substrate (SRSS ^Z ) formed by various combinations of flat PMN and diagonally corrugated mesh at different volume levels, namely 1.817 l (prior art) and 0.374 l (this invention), respectively .

The data show that despite the smaller volume (4.85 times) than the substrate of the prior art, the substrate formed by various combinations of flat PMN and diagonally corrugated mesh shows lower mass emissions of pollutants, especially for solid impurities.

Evaluation studies on a gas simulation test bench:

All studies of the catalytic activity described in the examples were carried out on a gas simulator test bench. The typical composition of the inlet gas contains (1) CO: 1000-1500 PMN, propane-propylene: 500-800 ppm, O2: 12-14%, NO: 500-800 ppm, 6-10% CO2, 7-12% steam and nitrogen balance.

A controlled stream of preheated mixture of these gases is fed to the reactor containing the sample under study. Volumetric flow rates are controlled by controlling the flow of the gas mixture entering the reactor. The effluent gases from the reactor are analyzed by a multigas analyzer of the current level of technology.

The result of the evaluation is the graphs of oxidation reactions for the oxidation of carbon monoxide, the oxidation of propylene and the formation of nitrogen dioxide with temperature.

PCC ^Z and CPCC ^Z, formed by special combinations corrugated or mikroriflenogo PMN and / or corrugated or mikroriflenoy metal grid with a different form of holes, preferably rectangular, and different numbers of cells and / or corrugated or mikroriflenoy serrated metal foil and / or inorganic fiber woven matrix material with different contents of precious metals, different layers of porous oxide coating, were evaluated at different volumetric speeds.

PCC ^{Z was} formed by combining planar PMN with diagonally corrugated metal mesh with rectangular cells. The thus formed was converted to PCC ^{Z Z} SRSS by coating a first combination of a catalytically inactive material so as to obtain a coating thickness of 2 micrometer. Four samples of this mentioned SRSS ^{Z were} then each coated with PGM at 1 g / ft ³ , 5 g / ft ³ , 10 g / ft ³ and 20 g / ft ³ .

The above substrate was dried, calcined, and evaluated for catalytic activity. FIG. 9 compares the catalytic activity, in particular, the starting temperature curves of SRSS ^Z at volumetric speeds of 30,000 / h.

A 34 ° corrugation angle was selected for all combinations of diagonally corrugated samples.

From FIG. 9a shows that with a space velocity of 30,000 h-1 SV, SRC ^Z with a PGM of 5 g / ft ^{3, it} demonstrates the best CO and HC start-up curves for a single-layer VF structure (VF0, VF1, VF5, VF10, VF20 , VF5) also shows the largest NO2 production among all analyzed series.

From FIG. 9b shows that with a space velocity of 60.000 h-1 SV, SRSS ^Z with a PGM of 20 g / ft ³ demonstrates the best starting curves for a VF structure with two layers (VF0, VF1, VF5, VF10, VF20, VF5), in particular, in the case of the formation of NO2 at 38% at a temperature of 350 ° C.

VF20 on a porous oxide bilayer coating gives the greatest efficiency even at 30,000 h-1 SV, since the complete coating of porous oxide is available for the catalytic reaction.

VF5 on one layer and VF20 on two layers have the best insitu NO2 formation.

In terms of cost, the best solution is VF5 on one layer.

Empty (uncoated and without PGM) PCC2 samples show only very low conversion.

From FIG. 10 - it can be seen that SRSS ^Z , which has a PGM of 5 g / ft ³ in a single-layer VF structure (VF1), demonstrates better start-up parameters than the one that has a PGM of 20 g / ft ^{3 of the} prior art in the VX structure of cellular type (VX20).

This implies a 95% reduction in IPY costs.

VF1 also gives a higher in-situ NO2 production efficiency.

From FIG. 11a and 11b, it can be seen that with a space velocity of 30,000 / h, the CPCC ^Z , which has a PGM of 5 g / ft ³ , shows the best starting parameters (VF5, 30K).

However, with a space velocity of 60.000 / h, SRSS ^Z , with a PGM content of 1 g / ft ³ , is approximately at the same level as this single-layer VF structure (VF5, 60K).

In terms of cost, VF5 is a solution that is 80% cheaper with PGM costs.

From FIG. 12a, it is clear that SRSS ^Z , which has an PGM content of 1 g / ft ³ , gives the best starting parameters for a single-layer VF structure.

It was also noted that SRSS ^Z , which has a PGM content of 20 g / ft ³ , shows very poor starting parameters for a single-layer VF structure, which can be explained by the fact that the density of PGMs is too high for this single-layer VF structure.

From FIG. 12b shows that with a space velocity of 60,000 / h VF10 (SRSS ^Z , having a PGM content of 10 g / ft ³ ) on a two-layer VF structure gives the highest efficiency, because the density of the PGM is better than that of which the PGM content is 20 g / ft ³ when the entire full layer of porous oxide coating is not used for catalytic activity.

In terms of cost, the best solution is VF1 in a single layer.

FIG. 13 shows the start-up curves for samples P-1661-P1666 as the following empty structures / structures without coating (PCC ^Z ): Corrugated PMN of turbulent type with UF as flat (P-1661) and with MF as microlended (P-1662); corrugated PMN with straight corrugation with UF as flat (P-1663) and with MF as micro-fused (P-1664); diagonally corrugated PMN with UF as flat (P-1665) and with MF as microtissue (P-1666).

From FIG. 13 clearly shows that without a coating or without a PGM structure with a combination of different corrugated PMN and flat (non-grooved) or micro-foil foil, there are no noticeable transformations.

FIG. 14a depicts the launch curves for samples P-1661-P1666 as the following coated structures (SRSS ^Z ). Corrugated PMN of turbulent type with UF as flat (Р-1661) and with MF as microfilament (P-1662); corrugated PMN with straight corrugation with UF as flat (P-1663) and with MF as micro-fused (P-1664); diagonally corrugated PMN with UF as flat (P-1665) and with MF as microtissue (P-1666).

In all three types of corrugation, it can be seen that the efficiency of the catalyst is the highest for microfusion foil compared to flat non-grooved foil structures when evaluated with a bulk velocity of 30,000 h-1 and with an PGM content of 1 g / ft ³ . Start-up curves show the advantages of microfusion, especially at temperatures in excess of 300 ° C, where mass and heat transfer phenomena begin to control catalytic reactions. When using a microfilament substrate, the layered type of flow at the catalytic surface (boundary layer) can be disturbed, thus improving the mass transfer between the exhaust gas and the wall, which leads to an increase in catalytic efficiency.

FIG. 14b shows the start-up curves for specimens only for PMN with straight corrugation with UF as flat (P-1663) and with MF as microfilament (P-1664). It is obvious that the efficiency of the catalyst is higher for the structure of the microfilament foil as compared with the flat non-grooved foil structures when evaluated with a bulk velocity of 30,000 h-1 SV and with an PGM content of 1 g / ft ³ . The results show how microfusion helps, especially at temperatures above 300 ° C, where mass and heat transfer phenomena begin to govern catalytic reactions.

FIG. 15a shows the start-up curves for samples for PMN with direct corrugation with UF as flat (P-1663) and with MF as microfilament (P-1664). It is obvious that the efficiency of the catalyst is the highest for the structure of the microfusion foil as compared to the flat non-ribbed foil structures when evaluated with 30.000 h-1 SV and with an PGM content of 5 g / ft ³ .

FIG. 15a shows the start-up curves for SRSS ^Z samples with PMN with straight corrugation with UF as flat (P-1663) and with MF as microfilament (P-1664). Diagonally corrugated PMN with UF as flat (P-1665) and with MF as microfilament (P-1666). It has been found that the catalyst efficiency is higher for micro-foil structures compared to flat non-grooved foil structures when evaluated with 30,000 h-1 SV and with an PGM content of 1 g / ft ³ .

FIG. 16a shows start-up curves for SRSS ^Z samples with diagonal rippled PMN with UF as flat (P-1665) and with MF as micro-threaded P-1666, assessed from 30.000 h-1 SV, and from 60.000 h-1 SV are shown in FIG. 16b. The results show that when the space velocity increases from 30.000h-1 to 60.000 h-1, the launch shifts towards a higher temperature mode, but at both volumetric speeds the structure of the microfused foil exhibit higher catalytic efficiency compared to the structures of the flat non-drifted foil containing PGM at 10 g / ft ³ .

It was also obvious that the formation of NO2 is at a good level with a space velocity of 30,000 for (P-1666) with MF and with a PGM content of 10 g / ft ³ . This type of educationNO2insitu provides a good basis for achieving effective soot regeneration for exhausting diesel particulate matter, starting at temperatures of 230 ° C.

FIG. Figure 17a shows the start-up curves for SRSS ^Z samples with PMN with direct corrugation with UF as flat (P-1663) and with MF as microtreamine (P-1664).

From testing this SRSS ^Z with straight corrugation, it is clear that the efficiency of the CO and NA catalyst is slightly higher, and NO2 is obviously better for the structure of a flat non-groomed UF foil compared to the structure of a micro-foil MF foil with a space velocity of 60,000 h-1 SV and an MPG content of 10 g / ft ³ .

FIG. 17b shows start-up curves for SRSS ^Z samples with corrugated PMN of turbulent type with UF as flat (P-1661) and with MF as microfilament (P-1662); diagonally corrugated PMN with UF as flat (P-1665) and with MF as microtissue (P-1666).

The results show that the MF microfilament foil structures show higher efficiency compared to UF flat non-foil structures in PMN with turbulent corrugation and in PMN diagonal corrugated with PGM content of 10 g / ft ³ and at a volume velocity of 60.000 h- one. It can also be seen that diagonally corrugated PMN with MF gives the highest efficiency in all studied aspects (CO, HC and NO2).

FIG. 18a shows the curves for the samples starting with ^Z SRSS VX-VL-structure and the structure of the prior art with the PGM content of 1, 5 and 10 g / ft ³ with a single layer coating.

FIG. 18a shows the start curves for CPC ^Z VX1 and VL10 samples. As you can see, the catalytic efficiency of the first one is much worse than the efficiency for the VL10, which is the best. Both samples are coated in one layer.

In both cases - VX and VL - the efficiency increases as the PGM content increases. VL10 and VL5 are the best in this comparison group.

FIG. 19 shows the start-up curves for CPC ^Z specimens with a straight ribbed CF flat-foil CF (P-1700) foil; turbulent type CF corrugated foil with flat PMN (P-1701); diagonally corrugated CF flat foil PMN (Р-1702).

It is obvious from all three cases of corrugation that the efficiency of the catalyst is higher at a space velocity of 30,000 h-1 SV than at a speed of 60,000 h-1 with a PGM content of 1 g / ft ³ .

Of the various grooves studied, the turbulent corrugation shows the highest catalytic efficiency, with the direct corrugations being second in efficiency, followed by diagonal corrugations, which are relatively worse in this comparison group.

The formation of NO2,%, is quite low in all cases, because higher PGM contents are necessary to ensure higher efficiency in this regard. Turbulent ribbing P-1701 produces NO2,%.

FIG. 20 shows the start-up curves for CPCC ^Z samples with a straight ribbed CF flat-foil (R-1700) foil; turbulent type CF corrugated foil with flat PMN (P-1701); diagonally corrugated CF flat foil PMN (Р-1702).

From all three cases of corrugation, it can be seen that the efficiency of the catalyst is higher with a space velocity of 30,000 h-1 SV than at 60,000 h-1 with a PGM content of 5 g / ft ³ .

Of all three different estimated corrugations, turbulent corrugation gives the highest efficiency, straight corrugations the second in efficiency, and diagonal corrugation is the worst in this comparison at 30,000 h-1 SV. However, with 60.000 h-1 SV, the direct structure is the best.

The formation of NO2,%, is still quite low in all cases, because higher PGM contents are necessary to ensure higher efficiency in this regard. Turbulent ribbing P-1701 produces NO2,%.

FIG. 21 shows the start-up curves for SRSS ^Z samples with a straight corrugated CF flat-foil CF (R-1700); turbulent type CF corrugated foil with flat PMN (P-1701); diagonally corrugated CF flat foil PMN (Р-1702).

From all three cases of corrugation, it can be seen that the efficiency of the catalyst is higher at a space velocity of 30,000 h-1 SV than at a speed of 60,000 h-1 with a PGM content of 10 g / ft ³ .

Out of all three different estimated corrugations, direct corrugation gives the highest efficiency, turbulent type corrugations are second in efficiency, and diagonal corrugation is the worst in this comparison at 30,000 h-1 SV. However, with a volume velocity of 60,000 h-1, the structure of the turbulent type P-1701 demonstrates the highest efficiency.

The formation of NO2 at 28% is maximum, and direct corrugation is best with a PGM content of 10 g / ft ³ . For direct ribbing of the P-1700, NO2 formation improves when the PGM content rises from 1 to 5 and 10 g / ft ³ , but the turbulent type P-1701 corrugation gives the best NO2 production,%, with an PGM content of 5 g / ft ³ and is at the same level as the straight ribbing of the P-1700 with a content of 10 g / ft ³ .

FIG. 22a and 22b are shown starting curves for SRSS ^Z samples with PMN with straight corrugation with UF as flat (P-1663) and with MF as micro-gleam (P-1664); diagonally grooved PMN with UF as flat (P-1665) and with MF as micro-fused (P-1666) at bulk speeds of 30,000 h-1 and 60,000 h-1, respectively.

From all types of corrugations, it is clear that the catalyst efficiency is higher for the structure of the microtreated foil compared to flat non-grooved foil structures with both SV and a PGM content of 1 g / ft ³ .

Start-up curves show the advantages of microfusion, especially at temperatures in excess of 300 ° C, where mass and heat transfer phenomena usually begin to control catalytic reactions.

In the case of diagonally corrugated PMN with MF (P-1666), the effect of increasing efficiency is evident with a space velocity of 60,000 h-1, compared with 30,000 h-1. When using a microfilament substrate, the layered type of flow at the catalytic surface (boundary layer) can be disturbed, thus improving the mass transfer between the exhaust gas and the wall, which leads to an increase in catalytic efficiency.

Carbon black studies

Carbon black studies were carried out on several selected samples, as described in FIG. 23.1 and 23.2. These samples were inserted into the exhaust assembly in the test vehicle assembly, which was then set in motion in a 200 km test cycle simulating a driving circuit in a typical Indian city. During the operation, the soot released from the engine enters the sample structure and accumulates in it. This process is called soot accumulation.

FIG. 23.1 it is shown that for catalysts placed in a position with a deaf compound, a flat PMN and diagonally corrugated grid demonstrate the highest efficiency of soot accumulation up to 150 km. After that, the substrate 1394/2 of the prior art accumulates the most.

Underground prior art (1395/2) underfloor (PP) catalyst exhibits the lowest carbon black content.

FIG. 23.2 it is shown that a flat PMN and a grid (1586/1) with direct corrugation demonstrate the highest efficiency of soot accumulation, the next after this is a substrate formed by a combination of flat PMN and a turbulent type foil (1597/1). The next most effective soot accumulation is the substrate formed by the combination of flat PMN and direct corrugated foil with 400 cpsi (1591/1).

The lowest soot accumulation efficiency is demonstrated by the substrate formed by the combination of flat PMN and direct corrugated foil with 200 cpsi.

The results of the experiments on some samples are presented in the tables below.

FIG. 17 shows structural information on substrates of the prior art and structures of the present invention. Obviously, for substrates made of structures of a layered toroidal type, the catalytic volume is only (0.323 + 0.103) = 0.426 dm ³ compared to the diagonally grooved structure of the prior art (0.323 + 0.763) = 1.086 dm ³ , which is only 39, 2%.

Mass emission tests were carried out on an Indian three-wheeler test vehicle in BSIII and BSIV test cycles with or without an EGR system. The mass emissions of the vehicle mentioned were measured hot on the BSIII test cycle and cold on the BSIV test cycle. From FIG. 18 that the present invention with a layered toroidal PMN type or an inorganic fiber woven matrix provides competitive mass emissions of pollutants, especially in the case of solid impurities, with only 39.2% of the catalyzed volume compared to the prior art structure when the tests were carried out with the same preceding CODE.

Various embodiments of the invention are possible, other than those described above, and easily understood by a person skilled in the art. The invention covers all such embodiments in the scope of this invention. Although this invention has been described in relation to certain preferred embodiments of the invention, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the scope of the invention as defined in the claims.

Claims (36)

1. Device for catalytic treatment of exhaust gases, containing a substrate formed by combining many individual elements, characterized in that said individual element contains many cells, said substrate is a combination of three-dimensional (3D) structure and contains one or more: a) porous metal filler (PMN); b) microfilament metal mesh; c) microfused jagged foil; d) inorganic fiber woven matrix material, said cells have a density of cells in the range from 20 to 1300 cells per square inch (cpsi), preferably from 50 to 600 cpsi, and the above-mentioned elements of the said substrate are combined in a special way to form different geometries, such as round, oval, square, rectangular , toroidal, banana-shaped, layered toroidal, etc., each with or without a bypass channel and for different sizes. 2. The device according to claim 1, characterized in that said separate element of said substrate forms a honeycomb body. 3. The device according to claim 1, characterized in that the plurality of cells is arranged in parallel, or sequentially, or in parallel in sequence with respect to each other. 4. The device according to claim 1, characterized in that said elements of said substrate may either have a continuous fit or be partially open in the radial and / or axial direction in order to create a variety of flow patterns. 5. The device according to claim 1, characterized in that said PMN is fleece. 6. The device according to p. 4, characterized in that the said forms of holes are square or rectangular, preferably rectangular. 7. The device according to claim 1, characterized in that the said corrugation is either direct, or diagonal, or turbulent. 8. The device according to claim 7, characterized in that said diagonal ribs have a diagonal angle in the range of 10-60 degrees, preferably in the range of 32-40 degrees. 9. The device according to claim 1, characterized in that said inorganic fiber woven matrix material has a total thickness in the range of 0.5-100 millimeters in one layer, preferably 0.5-10 millimeters. 10. The device according to claim 1, characterized in that said inorganic fiber woven matrix material has a porosity in the range of 70-95%. 11. The device according to claim 1, characterized in that said PMN has a porosity in the range of 70-95% and is used with a different thickness from 0.1 mm to 1 mm. 12. The device according to p. 1, characterized in that the said metal mesh has a different number of cells in the range from 120 to 20 cells per inch, preferably 90-30 cells per inch. 13. The device according to claim 1, characterized in that said metal mesh has a wire diameter in the range of 0.08-0.3 mm, preferably 0.1-0.2 mm. 14. The device according to claim 1, characterized in that said metal foil has a thickness in the range of 20-110 micrometers, preferably 40-80 micrometers. 15. The device according to claim 1, characterized in that the height of said microfusion is 0.01-0.5 mm, preferably 0.02-0.2 mm. 16. The device according to claim 1, characterized in that said substrate exhibits high thermal and mechanical stability at all engine loads. 17. The device according to claim 1, characterized in that said inorganic fiber woven matrix material has a thickness of fibers in the range of 5-22 micrometers. 18. The device according to PP. 1-17, characterized in that the said substrate further comprises a coating of porous oxide, characterized in that said coating of porous oxide contains a combination of a catalytically inactive material and a catalytically active material. 19. The device according to p. 18, characterized in that the coating of porous oxide is applied before or after the substrate is formed. 20. The device according to p. 18, characterized in that the said catalytically inactive material includes a combination of a number of oxides, nitrates and hydroxides of aluminum, silicon, titanium, zirconium, hafnium, calcium, barium, strontium and oxides of rare earth metals. 21. The device according to p. 18, characterized in that the said coating of porous oxide consists of small particles having a distribution of an average particle diameter of from 0.5 to 3.5 microns. 22. The device according to claim 18, characterized in that said catalytically inactive material has a specific surface area varying from 100 to 260 square meters. m per year 23. The device according to p. 18, characterized in that the said coating of porous oxide provides significant in situ formation of nitrogen dioxide in the range from 20% to 50% by volume, which continuously provides effective oxidation of soot accumulated inside the body of the honeycomb structure during operation engine 24. The device according to p. 18, characterized in that the said coating of porous oxide on said substrate provides the same or lower back pressure than before coating. 25. The device according to p. 18, characterized in that the said coating of porous oxide provides catalytic efficiency at low volume. 26. The device according to p. 18, characterized in that the said catalytically active material includes a combination of a number of salts of platinum, palladium, rhodium, ruthenium, osmium and iridium, preferably platinum, palladium and rhodium. 27. The device according to claim 26, characterized in that said catalytically active material is contained in said cellular body in the range of 0.5-30 g / cub. ft, preferably 1-10 g / cu. ft 28. The device according to p. 18, characterized in that the said coating of porous oxide has a thickness in the range of 0.5-10 micrometers, preferably 1-5 micrometers. 29. The device according to claim 1, characterized in that the substrate is PMN, said PMN contains one or more of the following: non-edged PMN, or corrugated PMN, or microfreeded PMN. 30. The device according to p. 1, characterized in that the substrate is a microfilament metal mesh in combination with nemistriam metal mesh, or corrugated metal mesh, or both. 31. The device according to claim 1, characterized in that the substrate is a microfilament jagged metal foil in combination with a non-microfiltered metal foil, or microfilament metal foil, or both.

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