CN111425282B - Metal honeycomb carrier with tunnel type pore channel structure for catalytic purification of waste gas - Google Patents
Metal honeycomb carrier with tunnel type pore channel structure for catalytic purification of waste gas Download PDFInfo
- Publication number
- CN111425282B CN111425282B CN202010138784.XA CN202010138784A CN111425282B CN 111425282 B CN111425282 B CN 111425282B CN 202010138784 A CN202010138784 A CN 202010138784A CN 111425282 B CN111425282 B CN 111425282B
- Authority
- CN
- China
- Prior art keywords
- sine
- corrugated
- shaped
- corrugated plate
- tooth profile
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 60
- 239000002184 metal Substances 0.000 title claims abstract description 60
- 239000011148 porous material Substances 0.000 title claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 18
- 238000000746 purification Methods 0.000 title claims abstract description 13
- 239000002912 waste gas Substances 0.000 title abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 7
- 238000003466 welding Methods 0.000 claims description 7
- 238000005096 rolling process Methods 0.000 claims description 6
- 238000005219 brazing Methods 0.000 claims description 4
- 230000004907 flux Effects 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 6
- 230000009466 transformation Effects 0.000 abstract description 2
- 241000264877 Hippospongia communis Species 0.000 description 64
- 239000002131 composite material Substances 0.000 description 30
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 16
- 238000000576 coating method Methods 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 14
- 239000010948 rhodium Substances 0.000 description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 229910008651 TiZr Inorganic materials 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000272525 Anas platyrhynchos Species 0.000 description 1
- 241000124033 Salix Species 0.000 description 1
- 241000646858 Salix arbusculoides Species 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000004323 axial length Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- VQVDTKCSDUNYBO-UHFFFAOYSA-N neodymium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VQVDTKCSDUNYBO-UHFFFAOYSA-N 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- -1 oxygen ions Chemical class 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
-
- 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 monoliths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
- B23K1/0014—Brazing of honeycomb sandwich structures
-
- 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
- F01N3/2839—Arrangements for mounting catalyst support in housing, e.g. with means for compensating thermal expansion or vibration
- F01N3/2842—Arrangements for mounting catalyst support in housing, e.g. with means for compensating thermal expansion or vibration specially adapted for monolithic supports, e.g. of honeycomb type
-
- 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
- F01N2330/32—Honeycomb supports characterised by their structural details characterised by the shape, form or number of corrugations of plates, sheets or foils
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Combustion & Propulsion (AREA)
- General Engineering & Computer Science (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
The invention provides a metal honeycomb carrier with a tunnel type pore channel structure for catalytic purification of waste gas, and a manufacturing method and application thereof. The honeycomb carrier can reduce the cost of the catalyst and improve the catalytic efficiency and the utilization rate through the transformation of the internal structure of the carrier, and solves the problems of uneven airflow distribution, insufficient utilization rate of the catalyst and the like of the traditional straight-through pore structure carrier.
Description
Technical Field
The invention mainly relates to a metal carrier of a catalytic converter, in particular to a turbulent flow type high-performance metal honeycomb carrier of a tunnel-type pore channel structure, and more particularly relates to a metal honeycomb carrier of a tunnel-type pore channel structure for catalytic purification of waste gas.
Background
The metal catalytic converter for purifying the tail gas of the engine can effectively convert harmful substances such as CO, HC, NOx and the like in the tail gas into harmless CO through oxidation and reduction2、H2O and nitrogen, etc. The outside of catalytic converter is the stainless steel casing, and inside is metal honeycomb inner core. The prior art mainly includes a concentric circle form and a double S form. The inner honeycomb structure is formed by rolling a plurality of metal flat plates and sine wave-shaped plates, and the pore channels of the honeycomb inner core are not communicated with each other. When automobile exhaust passes through the inside of the carrier, airflow is diffused and distributed from the center to the periphery, the flow is diffused from the center to the periphery, the catalyst in the middle of the inner core is easy to age due to the pore channel structures which are not communicated with each other, the activity of the durable catalyst is obviously reduced, and meanwhile, precious metal resources are wasted.
The applicant's prior application CN110318851A discloses a monolithic honeycomb carrier with a multi-cell structure, which has an inflow-side end face and an outflow-side end face and has a plurality of channels flowing in one direction, and has a core composed of at least one thin flat plate and at least one partially structured corrugated thin plate arranged in layers, the structure of the corrugated thin plates constituting cell walls of the channels in the flow direction, the monolithic honeycomb carrier having a plurality of different segments in the flow direction, and corrugated thin plates of sinusoidal waveform being spaced between adjacent structured corrugated thin plates. The integral honeycomb carrier enables the prepared catalyst device to be more uniform in air flow distribution in the tail gas purification process, and can improve the utilization rate of the catalyst. The entire contents of this application are incorporated herein by reference.
CN109072754A discloses a honeycomb body for an exhaust gas aftertreatment unit, having a plurality of layers stacked on top of each other, wherein flow channels are formed between the layers, which flow channels extend along the axial extent of the honeycomb body and are capable of flowing in the axial direction through the flow channels, wherein the honeycomb body has a first structured layer, wherein the structure is formed by successive peaks and valleys, wherein the mutually adjacently arranged wave troughs of the first structured layer form protrusions in the direction of these wave crests belonging to the respective layer, characterized in that channel-like structures extending in the circumferential direction of the honeycomb body are formed in the first structured layer by means of the projections of the first structured layer which are arranged adjacent to one another, into which channel-like structures a second layer is placed such that the second layer is fixed in the axial direction relative to the first structured layer.
CN101203309B discloses a metal honeycomb catalyst carrier, which comprises: a wound honeycomb body comprising a plurality of strip plates, which extend in a longitudinal direction and are provided with: a corrugated portion on one side of the belt plate in a longitudinal direction; an end flat portion on the other side of the belt plate in the longitudinal direction; and a central flat portion at an intermediate position of the belt plate in the longitudinal direction; and a hollow cylindrical member housing the wound honeycomb body therein; wherein a plurality of the strip plates are stacked one on top of another in such a manner that the corrugated portion of one strip plate overlaps the flat portion of another strip plate, and are wound together from the central flat portion to form the wound honeycomb body, wherein the central flat portion of the strip plate is wound to form a central cylindrical portion having a diameter D, and wherein a longitudinal length of the central flat portion is at least 4.14D, and a length of the central flat portion in the longitudinal direction is constituted by a first length provided on the one side with respect to a center line of the strip plate and a second length provided on the other side with respect to the center line, the first length being equal to the second length.
CN1303321A discloses a monolithic honeycomb body for flow through a fluid in a flow direction, having an inflow-side end face and an outflow-side end face spaced apart therefrom, which comprises a plurality of at least partially structured sheets arranged in layers. The structure of the sheets constitutes the walls of the channel in the direction of flow. The number or size of the channels, seen in the flow direction, is different in the sections in the front-rear position, at least a part of the structured lamellae extending from the inflow-side end face to the outflow-side end face. Each of the sheets has at least first and second structures of different dimensions, at least one of which extends along only a segment of the axial length of the honeycomb body. Additional webs are arranged between successive webs, which in the partial region form a greater number of channels per unit cross-sectional area.
CN101370583A discloses a method for catalytic coating of a ceramic honeycomb body having parallel flow channels through the body from the inlet end face to the outlet end face, which are separated from each other by channel walls having an open pore structure, wherein the coating is carried out with a catalyst suspension comprising solids suspended in a carrier liquid, characterized in that the flow channels are temporarily closed alternately at the inlet end face and at the outlet end face, so that the catalyst suspension flows through the body from the inlet face to the outlet face, and subsequently the alternately closed flow channels are opened again.
WO2008/094889a1 discloses a gas treatment article comprising: a flow-through substrate comprising an inlet axial end, an outlet axial end, a wall element having a length extending from the inlet axial end to the outlet axial end, the wall having a porosity of at least 50% and an average pore size of at least 5 microns and less than 100 microns, a surface of the wall having an average roughness defined by open pores on the wall surface, and more than one axially enclosed, open-ended channel defined by the wall element; and a composite catalyst in the form of a washcoat containing particles having an average particle size greater than 3 microns deposited substantially within the wall elements, wherein the average roughness of the surface of the wall elements remains substantially unchanged compared to before loading of the catalyst within the walls.
EP2010/052465a discloses a honeycomb body having channels, an axial main direction, a flat front face, a flat end face and a circumferential face arranged parallel to the axial main direction, wherein at least the front face or the end face is arranged obliquely to the axial main direction, the honeycomb body being formed from at least two honeycomb body sections each having at least one flat end face which is normal to the axial main direction, the normal end faces of the at least two honeycomb body sections being arranged facing one another.
"development and selection of catalyst carrier for vehicle", Anqin, etc., environmental protection, 1999 11, reviewed the current catalytic converter for treating automobile exhaust emission, indicating that the carrier is the most basic and key factor, and in order to meet increasingly demanding emission regulations and service life requirements, the carrier requires large geometric surface area, small pressure difference, low thermal expansion coefficient, good oxidation resistance, excellent high temperature mechanical properties, and how to achieve good balance of these properties has difficulty.
The honeycomb body in the prior art has the problems of nonuniform gas flow distribution, insufficient catalyst utilization rate and the like.
Disclosure of Invention
The invention uses a tunnel-type metal honeycomb carrier which is formed by sequentially rolling two groups (also referred to as two) or more than two groups (also referred to as more than two) of different sine tooth-shaped groups, changes the original single flow mode of waste gas, solves the technical defects of uneven distribution of air flow of the carrier with the traditional straight-through type pore channel structure and the like, and improves the catalytic conversion efficiency of the carrier. In order to effectively solve the above technical problems of the prior art, the present inventors have made intensive studies and joint development based on the prior application (e.g., CN110318851A, the entire content of which is incorporated herein by reference), and have provided the following technical solutions.
In one aspect of the present invention, a metal honeycomb carrier with a tunnel type pore channel structure for catalytic purification of exhaust gas is provided, which is characterized in that: the metal honeycomb carrier is formed by overlapping and rolling a corrugated plate (4) and a flat thin plate (not shown), and the corrugated plate (4) is formed by combining two or more corrugated plates with different sine tooth shapes.
Preferably, the corrugated plate (4) and the flat sheet are overlapped and then rolled in an S shape, so that the metal honeycomb carrier (2) is an S-shaped metal honeycomb body (2).
Preferably, the outer ring of the honeycomb carrier is fixed by using a metal shell (3), and the honeycomb carrier is integrally formed as a catalyst metal carrier by welding.
In a preferred embodiment of the invention, the corrugated plate (4) is formed by combining 1 corrugated plate with a first sinusoidal tooth profile and more than 2 corrugated plates with a second sinusoidal tooth profile, wherein the first sinusoidal tooth profile is the same as or different from the second sinusoidal tooth profile.
More preferably, the first sine tooth profile is different from the second sine tooth profile.
More preferably, the 2 or more corrugated plates having the second sine-wave shape are alternately stacked on the 1 corrugated plate having the first sine-wave shape. Further preferably, the 2 or more corrugated plates with the second sine-shaped tooth profiles are uniformly and alternately superposed on the 1 corrugated plate with the first sine-shaped tooth profile. In other words, the corrugated plate portion having the first sine-wave tooth profile is covered with the corrugated plate having the second sine-wave tooth profile, and the portion not covered with the corrugated plate having the second sine-wave tooth profile is uniformly spaced apart (in the exhaust gas flow direction, i.e., the honeycomb channel direction) by the covered portion.
When stacked at even intervals (i.e., the same separation distance), the wave plate contains at least two regions of different structural shape (A, B). When more than 2 corrugated plates with a second sinusoidal profile are used, the at least two areas of different structural shape are arranged alternately, for example ABAB … ….
When the first sine tooth profile is the same as the second sine tooth profile, the corrugated plate with the first sine tooth profile and the corrugated plate with the second sine tooth profile are superposed in a mode of buckling in the reverse direction. In this case, each region (A, B) contains two differently sized wavy tooth formations (7, 8, 9, 10), 8 being the same as 9 and 7 being the same as 10.
More preferably, the wavy small teeth (7) on the A group of columns are correspondingly combined with the wavy large teeth (9) on the B group of columns; the wavy large teeth (8) on the A group of columns are correspondingly combined with the wavy small teeth (10) on the B group of columns.
In a particularly preferred embodiment of the invention, the combination of 1 corrugated sheet with a first sinusoidal profile and more than 2 corrugated sheets with a second sinusoidal profile results in the formation of "wicker-like" perforations (6) of the same size between the two corrugated sheets. The "willow-leaf-like" broken pores are formed on both sides of each large pore as viewed from the honeycomb end face direction. It can be understood that in this case, the formation of such a structure is independent of whether the first sine tooth profile and the second sine tooth profile are identical.
Certainly, when first sine profile of tooth with the second sine profile of tooth is different, the compound mode of the buckled plate that has first sine profile of tooth and the buckled plate that has the second sine profile of tooth makes to have formed the aperture that the size is the same between two kinds of buckled plates can. That is, the two corrugated sheets are stacked in a non-perfect fit manner. The small holes are 'willow leaf-shaped' broken holes (6) with the same size.
Preferably, the S-shaped metal core is formed by rolling the wave plates (4) with different sine tooth-shaped sequences and the flat thin plates in an overlapping mode, the inner core pore channels are communicated in a staggered mode in the same laminar flow plane, and all connecting points are connected in a brazing mode through applying welding fluxes.
The wave plate and the flat sheet are preferably made of metal independently.
The inventor of the invention finds that the S-shaped metal honeycomb core body is formed by rolling a corrugated thin plate and a flat thin plate which are sequentially arranged by two or more groups of different sine tooth-shaped groups, the outer ring is fixed by a metal shell, and the corrugated thin plate and the flat thin plate are integrally formed by welding to serve as a metal honeycomb carrier. Because the tooth shapes of different rows have different sizes, a willow leaf-shaped broken hole structure between the rows is formed, the structure changes the original single straight-through type hole channel, and when exhaust gas passes through the carrier, turbulent flow is realized in the same laminar flow plane. Meanwhile, the metal carrier with the structure can greatly improve the turbulent flow effect of gas, and can also be used for an SCR mixer.
Further preferably, the surfaces of the corrugated plate with the first sine-wave shape and the corrugated plate with the second sine-wave shape contain a catalyst layer. Of course, those skilled in the art will recognize that metallic honeycomb supports that do not contain a catalyst layer may already be sold or used as a stand-alone item.
Particularly preferably, the surface of the corrugated plate with the first sinusoidal tooth profile and the surface of the corrugated plate with the second sinusoidal tooth profile contain the same or different catalyst layers.
In a preferred embodiment, the first catalyst layer having a corrugated plate surface with a first sinusoidal profile is formed by: and the alumina coating is loaded with Rh loaded by Pd-doped CeZrNd composite oxide. That is, an alumina coating is applied to the surface of the corrugated plate, and then the Pd-doped CeZrNd composite oxide-supported Rh catalyst is applied to the alumina coating.
Preferably, the alumina content is from 9 to 15g/L, more preferably 10g/L, per liter of volume of the metal honeycomb support.
Preferably, the content of Rh, i.e., Pd-doped CeZrNd composite oxide-supported Rh catalyst supported by Pd-doped CeZrNd composite oxide is 50 to 120g/L, more preferably 80g/L
As is generally understood in the art, the volume refers to the macroscopic volume of the metal honeycomb support.
The Pd-doped CeZrNd composite oxide can be prepared by a coprecipitation method. Specifically, cerium nitrate hexahydrate, zirconyl nitrate solution, neodymium nitrate hexahydrate and palladium nitrate solution are dissolved in deionized water, ammonia water is added to adjust the pH value to precipitate, and the precipitate is dried (for example, 120 ℃ C. and 160 ℃ C.) and then calcined in air (for example, 600 ℃ C. and 650 ℃ C.) for 3-5 hours to obtain Pd-doped CeZrNd composite oxide powder.
In the Pd-doped CeZrNd composite oxide, PdO and CeO2∶ZrO2∶Nd2O32-5: 10-15: 60-90: 10-15 (mass ratio).
The Pd-doped CeZrNd composite oxide powder is impregnated by Rh salt (such as rhodium nitrate solution), and then drying (such as 120-. The drying and calcination are preferably carried out in an air atmosphere.
Based on the total weight of the Pd-doped CeZrNd composite oxide-loaded Rh catalyst, the Rh content is 0.2-2.0 wt%.
Applying the Pd-doped CeZrNd composite oxide-supported Rh catalyst powder on the alumina coating. The application can be carried out by application means customary in the art, for example by coating methods, for example with zirconia sol as binder.
Preferably, the alumina coating is a Pd-modified alumina coating. More preferably, the Pd content is 0.5-3.0 wt%, based on the total weight of the alumina coating. The modification can be carried out by a conventional modification method, for example, mixing the pseudoboehmite with a Pd salt, and then drying and calcining. The Pd in the modified alumina and the Pd in the CeZrNd composite oxide can mutually migrate to a certain degree in the use of the catalyst, thereby playing a role of mutual supplement.
In a preferred embodiment, the second catalyst layer having a corrugated plate surface with a second sinusoidal profile is formed by: an alumina coating on which Pt supported by a mixture of a CeZr composite oxide and a TiZr composite oxide is supported.
Preferably, the weight ratio of the CeZr composite oxide to the TiZr composite oxide is 1:4 to 1: 8.
Preferably, the alumina content is 5 to 15g/L, more preferably 10g/L, per liter of the volume of the metal honeycomb support.
Preferably, the content of the mixture of the CeZr composite oxide and the TiZr composite oxide is 100-200g/L, more preferably 150g/L, per liter of the volume of the metal honeycomb carrier.
Preferably, the Pt content is 0.1-2.0g/L per liter of the metal honeycomb carrier volume.
The mixture of different composite oxides is used as a carrier of Pt, so that the oxygen storage amount of the oxide is increased, the oxygen storage speed is increased, the lattice points existing in different composite oxides complement each other, the movement of oxygen ions between the surface of the oxide and the inside of the oxide is facilitated, and the catalyst can adapt to different application scenes such as whether an engine is idling or not.
In the present invention, the preferred catalyst zone arrangement allows for the formation of distinct catalytic regions (such as regions A, B shown in the drawings) on the honeycomb body (i.e., on the honeycomb channels) in the direction of exhaust gas flow.
The combination of the different catalyst regions described above is particularly significant, for example, in the case where the air-fuel ratio of the exhaust gas suddenly becomes excessively large at low or idling speeds of the automobile, the first catalyst layer and the second catalyst layer function together, the exhaust gas (particularly NOx) that has not been completely purified in the first catalyst layer can be efficiently purified by the catalyst metal supported by the high-performance oxygen storage material in the second catalyst layer, and when the high-speed running, that is, the running condition is normal, the first catalyst layer can usually achieve better purification of NOx, thereby reducing the use of the second catalyst and improving the service life thereof.
Further, it has been found that by providing the second catalyst layer, it is possible to advantageously prevent the Pd and Rh in the first catalyst layer from being undesirably alloyed, and to prevent the Pd and Rh from being thermally deteriorated and poisoned (for example, from being poisoned by S or P), thereby effectively improving the life of the catalyst produced with the metallic honeycomb carrier.
In another aspect of the present invention, there is provided a method of manufacturing the honeycomb carrier according to the foregoing, the method comprising the steps of: step 1: combining 1 corrugated plate with a first sine tooth profile and more than 2 corrugated plates with a second sine tooth profile to obtain a corrugated plate (4), wherein the first sine tooth profile is the same as or different from the second sine tooth profile; step 2: the corrugated plate (4) and the flat sheet are superposed and then rolled according to an S shape to prepare an S-shaped metal honeycomb body (2); and step 3: the outer ring of the S-shaped metal honeycomb body (2) is fixed by a metal shell (3) and is welded to form a whole body as a catalyst metal carrier.
Preferably, the application of the catalyst layer may be performed before step 1.
The application of the catalyst layer can be carried out by brushing, spraying, dipping, and the like.
In the above method of the present invention, preferably, the welding is brazing.
In a preferred embodiment of the present invention, the 1 corrugated plate having the first sinusoidal tooth profile and 2 or more corrugated plates having the second sinusoidal tooth profile are combined in a stacked manner.
In a further aspect of the invention, there is provided the use of the honeycomb substrate for catalytic purification of exhaust gases. Preferably, the exhaust gas is engine exhaust gas.
The honeycomb bodies according to the invention achieve outstanding technical results compared with the prior art. Through the transformation of the internal structure of the carrier, the cost of the catalyst can be reduced, the catalytic efficiency and the utilization rate can be improved, and the problems of uneven airflow distribution, insufficient utilization rate of the catalyst and the like of the traditional straight-through pore channel structure carrier are solved.
Drawings
Fig. 1 is a schematic perspective view of a metal honeycomb carrier with a tunnel-shaped channel structure according to the present invention, wherein 1 refers to the metal honeycomb carrier with the tunnel-shaped channel structure, and a and B refer to regions with different structural shapes, respectively;
fig. 2 is a schematic end face tooth form view of a metal honeycomb carrier with a tunnel-shaped pore channel structure according to the present invention, wherein 2 is an S-shaped metal honeycomb, 3 is a metal shell, 5 is a "willow-leaf-shaped" broken pore channel, and 6 is a "willow-leaf-shaped" broken pore;
fig. 3 is a schematic structural view of a tunnel-shaped pore carrier metal wave plate according to the present invention, wherein 4 is a metal wave plate, 7 is wavy small teeth on a group a column, 8 is wavy large teeth on a group a column, 9 is wavy large teeth on a group B column, and 10 is wavy small teeth on a group B column.
Fig. 4 is a schematic end view of a tunnel-shaped porous carrier metal wave plate structure according to the present invention, wherein 6 is a "willow-leaf-shaped" broken hole.
Detailed Description
Example 1
Referring to attached figures 1-4, a tunnel-shaped pore channel metal carrier (1) is prepared, and comprises an S-shaped metal honeycomb core body formed by sequentially arranging and combining at least two or more groups of sine tooth-shaped groups with different tooth shapes and a flat plate, wherein due to different tooth shapes among the groups, willow-leaf-shaped broken pore channels (5) with the same size are formed among the groups in the core body, and the pore channels are communicated in the same laminar flow plane to achieve the turbulent flow effect. The outer ring of the honeycomb core body is fixed by a metal shell (3) and is welded to form a whole body as a metal honeycomb carrier.
Example 2
In the manufacture of the metallic honeycombs of example 1, gamma-Al was dip coated on the internal surfaces of the corrugated and flat sheets according to conventional methods in the art2O3Coating and then dipping the active component Pt-Rh-Pd three-way catalyst. The method comprises the steps of carrying out a tail gas catalysis bench test (detected in a detection center of a motor vehicle in Hachen of Duck mountain) by using a Kagawa (gasoline car, 2004), adding the metal honeycomb body containing the catalyst to a tail gas outlet of the car, carrying out detection under an idling condition, controlling the contents of CO, HC and NOx compounds in the tail gas by adjusting the rotating speed of the engine, controlling the temperature of a catalyst bed layer by using a temperature controller, detecting the contents of CO, HC and NOx compounds at an inlet and an outlet of the catalyst bed layer by using an ALTAS-100 type automobile tail gas analyzer, calculating corresponding conversion rate, and detecting that HC is reduced by 53.5%, CO is reduced by 47.36% and NOx is reduced by 71.1% compared with the condition before adding the tail gas purification device.
Comparative example 1
Comparative example 1 differs from comparative example 1 only in that the honeycomb carrier used is a commercially available honeycomb carrier (available from Degussa, Degussa) made of conventional single sine wave plates alternately stacked and rolled with flat plates. Bench tests were carried out in the same manner as in example 2, and it was found that HC was decreased by 42.1%, CO was decreased by 33.23%, and NOx was decreased by 57.60%, as compared with those before the exhaust gas purifying apparatus was added.
It can be known from the comparison of the effects of the above examples and comparative examples that the honeycomb carrier of the present invention can reduce the cost of the catalyst and improve the catalytic efficiency and utilization rate by changing the internal structure of the carrier by changing the existing single pore structure form, and solves the problems of uneven gas flow distribution, insufficient catalyst utilization rate, etc. of the conventional straight-through pore structure carrier. According to the requirement of the emission standard of the engine, the conversion rate of CO, HC and NOx in the exhaust emission is obviously improved, so that the emission standard of the engine can be obviously improved, and the latest European standard and national six standards for the exhaust emission of the engine are met.
Example 3
Example 2 was repeated with the only difference that the first catalyst layer of the corrugated plate surface with the first sinusoidal tooth profile was composed of: the catalyst comprises an alumina coating, Rh loaded on the alumina coating and loaded by Pd-doped CeZrNd composite oxide, wherein the alumina content is 10g/L in terms of volume of each liter of metal honeycomb carrier, the content of Rh catalyst loaded on the Pd-doped CeZrNd composite oxide is 80g/L, and PdO to CeO in the Pd-doped CeZrNd composite oxide2∶ZrO2∶Nd2O3The mass ratio of the catalyst to the Pd-doped CeZrNd composite oxide loaded Rh catalyst is 5: 10: 70: 15, and the Rh content is 1.0 wt%; the second catalyst layer with the corrugated plate surface with the second sine tooth shape is formed by the following components: the alumina coating is loaded with Pt loaded by a mixture of CeZr composite oxide and TiZr composite oxide, the weight ratio of the CeZr composite oxide to the TiZr composite oxide is 1:5, the alumina content is 10g/L in terms of volume of each liter of metal honeycomb carrier, the content of the mixture of the CeZr composite oxide and the TiZr composite oxide is 150g/L, and the Pt content is 1.0 g/L. Compared with the exhaust gas purification device before the exhaust gas purification device is added, HC is reduced by 61.1%, CO is reduced by 55.49%, and NOx is reduced by 90.2%.
The effect of this example is particularly significant in NOx reduction as compared with example 2. The air-fuel ratio of the exhaust gas at idling is large, the first catalyst layer and the second catalyst layer function together, the exhaust gas which is not completely purified in the first catalyst layer, particularly NOx, can be efficiently purified by the catalyst metal supported by the high-performance oxygen storage material in the second catalyst layer,
this written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to make and use the invention. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims. All citations referred to herein are incorporated herein by reference to the extent that no inconsistency is made.
Claims (8)
1. A tunnel type pore structure metal honeycomb carrier for exhaust gas catalytic purification, its characterized in that: the metal honeycomb carrier is formed by overlapping and rolling corrugated plates and flat sheets, each corrugated plate is formed by combining 1 corrugated plate with a first sine tooth profile and more than 2 corrugated plates with a second sine tooth profile, and the first sine tooth profile is the same as the second sine tooth profile; the more than 2 corrugated plates with the second sine tooth profiles are uniformly and alternately superposed on the 1 corrugated plate with the first sine tooth profile; the corrugated plate with the first sine tooth profile and the corrugated plate with the second sine tooth profile are superposed in a mode of buckling in opposite directions; each corrugated plate is provided with two wavy tooth-shaped structures with different sizes, wavy large teeth and wavy small teeth are alternately arranged, the wavy small teeth on the first sinusoidal tooth-shaped corrugated plate are correspondingly combined with the wavy large teeth on the second sinusoidal tooth-shaped corrugated plate, and the wavy large teeth on the first sinusoidal tooth-shaped corrugated plate are correspondingly combined with the wavy small teeth on the second sinusoidal tooth-shaped corrugated plate, so that salix-leaf-shaped broken holes with the same size are formed between the two corrugated plates, and the salix-leaf-shaped broken holes are formed on two sides of each large hole when observed from the end face direction of the honeycomb body; the corrugated plates (4) with different sine tooth-shaped sequence arrangement and the flat sheet are rolled to form an S-shaped metal core body, inner core pore channels are communicated in a staggered mode in the same laminar flow plane, and all connecting points are connected in a brazing mode through applying welding fluxes.
2. The honeycomb carrier according to claim 1, wherein the corrugated sheet (4) and the flat sheet are stacked and then rolled in an S-shape, so that the metal honeycomb carrier (2) is an S-shaped metal honeycomb body (2).
3. The honeycomb carrier according to claim 1 or 2, wherein the outer ring of the honeycomb carrier is fixed using a metal casing (3) and is formed as a monolithic body by welding as a catalyst metal carrier.
4. The honeycomb carrier according to claim 1 or 2, wherein the surface of the corrugated sheet having the first sine wave profile and the corrugated sheet having the second sine wave profile contains a catalyst layer.
5. A method of manufacturing the honeycomb carrier according to any one of the preceding claims, characterized in that the method comprises the steps of:
step 1: combining 1 corrugated plate with a first sine tooth profile with more than 2 corrugated plates with a second sine tooth profile to obtain a corrugated plate (4), wherein the first sine tooth profile is the same as the second sine tooth profile;
step 2: the corrugated plate (4) and the flat thin plate are overlapped and then are rolled according to an S shape to prepare an S-shaped metal honeycomb body (2); and
and step 3: the outer ring of the S-shaped metal honeycomb body (2) is fixed by a metal shell (3) and is welded to form a whole body as a catalyst metal carrier.
6. The method of claim 5, wherein the welding is brazing.
7. Use of a honeycomb carrier according to any one of claims 1-4 for catalytic purification of exhaust gases.
8. Use according to claim 7, the exhaust gas being engine exhaust gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010138784.XA CN111425282B (en) | 2020-03-03 | 2020-03-03 | Metal honeycomb carrier with tunnel type pore channel structure for catalytic purification of waste gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010138784.XA CN111425282B (en) | 2020-03-03 | 2020-03-03 | Metal honeycomb carrier with tunnel type pore channel structure for catalytic purification of waste gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111425282A CN111425282A (en) | 2020-07-17 |
| CN111425282B true CN111425282B (en) | 2022-02-22 |
Family
ID=71551974
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010138784.XA Active CN111425282B (en) | 2020-03-03 | 2020-03-03 | Metal honeycomb carrier with tunnel type pore channel structure for catalytic purification of waste gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111425282B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115007220B (en) * | 2022-06-11 | 2024-05-31 | 亿达天地环保技术股份有限公司 | Honeycomb carrier for tail gas purification and processing technology |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4024942A1 (en) * | 1990-08-06 | 1992-02-13 | Emitec Emissionstechnologie | MONOLITHIC METAL HONEYCOMB WITH VARIOUS CHANNEL NUMBER |
| DE4201111C2 (en) * | 1992-01-17 | 1994-03-10 | Daimler Benz Ag | Exhaust filter, in particular soot particle filter |
| JP3610720B2 (en) * | 1997-03-03 | 2005-01-19 | 日産自動車株式会社 | Metal catalyst carrier structure |
| DE19823469A1 (en) * | 1998-05-26 | 1999-12-02 | Emitec Emissionstechnologie | Monolithic metallic honeycomb body with varying number of channels |
| DE102005027582A1 (en) * | 2005-06-14 | 2006-12-28 | Unimet Gmbh | Textured foil |
| CN202506394U (en) * | 2011-10-26 | 2012-10-31 | 台州欧信环保净化器有限公司 | Sine wave type metal honeycomb carrier of catalyst for purifying tail gas of motor vehicle |
| CN110318851A (en) * | 2019-04-10 | 2019-10-11 | 亿达天地环保技术股份有限公司 | A kind of integral honeycomb carrier with polynary cellular structure |
-
2020
- 2020-03-03 CN CN202010138784.XA patent/CN111425282B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111425282A (en) | 2020-07-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6431051B2 (en) | Three-way catalytic converter | |
| US9581063B2 (en) | Pollutant abatement system for gasoline vehicles | |
| CN113874108B (en) | Layered catalytic article and method of making a catalytic article | |
| US9782753B2 (en) | Catalytic converter | |
| US20080081762A1 (en) | Catalyst For Purifying Exhaust Gases | |
| RU2018126874A (en) | GASOLINE SOLID PARTICLE FILTER | |
| CN104937225A (en) | Automotive catalyst composites having a two-metal layer | |
| EP3192584B1 (en) | Exhaust gas purification catalyst | |
| CN113260454A (en) | Layered three-way conversion (TWC) catalysts and methods of making the same | |
| US20200232362A1 (en) | Phosphorus resistant three-way catalyst | |
| WO2020263806A1 (en) | Catalytic article and method of manufacturing the catalytic article | |
| JP2017104825A (en) | Catalytic converter | |
| JP2023106415A (en) | Base metal doped zirconium oxide catalyst support materials | |
| US20080292513A1 (en) | Catalyst carrier | |
| US20030101718A1 (en) | Method and device for the catalytic conversion of gaseous pollutants in the exhaust gas of combustion engines | |
| EP1300193A1 (en) | Method and device for the catalytic conversion of gaseous pollutants in the exhaust gas of combustion engines | |
| US20220001370A1 (en) | Layered catalysts composition and catalytic article and methods of manufacturing and using the same | |
| CN111425282B (en) | Metal honeycomb carrier with tunnel type pore channel structure for catalytic purification of waste gas | |
| WO2020128786A1 (en) | Layered catalyst composition and catalytic article and methods of manufacturing and using the same | |
| WO2014115420A1 (en) | Catalytic converter | |
| US20040116288A1 (en) | Catalyst support with intersecting channel network, catalysis reactor comprising same and method for making same | |
| KR20220102619A (en) | Emission Controlled Catalyst Articles Having Enriched PGM Zones | |
| CN110318851A (en) | A kind of integral honeycomb carrier with polynary cellular structure | |
| WO2018123286A1 (en) | Exhaust gas purification catalyst | |
| WO2023232929A1 (en) | Zoned three-way conversion catalysts comprising platinum, palladium, and rhodium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |