Cylindrical member for exhaust gas treatment device, exhaust gas treatment device using said cylindrical member, and insulating layer used in said cylindrical member

The use of a glass-based insulating layer with controlled alkali metal content in exhaust gas processing devices addresses reactivity issues, ensuring high-temperature stability and effective purification performance.

JP7623850B2Active Publication Date: 2025-01-29NGK CORP
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Patent Information

Application Number
JP2021030168
Authority / Receiving Office
JP · JP
Patent Type
Patents
Current Assignee / Owner
Filing Date
2021-02-26
Publication Date
2025-01-29
Estimated Expiration
2041-02-26

AI Technical Summary

Technical Problem

Existing insulating layers for exhaust gas processing devices may react with the metal cylindrical members, leading to environmental impurities and reduced purification performance due to gaps and leaks.

Method used

A cylindrical member for exhaust gas processing devices with an insulating layer made of glass containing minimal alkali metal elements (≤1000 ppm) and specific compositions, ensuring high-temperature stability and adhesion, formed using a glass frit slurry application process.

Benefits of technology

The solution provides a stable, high-temperature-resistant cylindrical member with reduced environmental impurities and improved adhesion, maintaining efficient exhaust gas purification performance.

✦ Generated by Eureka AI based on patent content.

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Patent Text Reader

Abstract

To provide a cylindrical member for an exhaust gas treatment device capable of suppressing generation of an environmental load substance even at high temperature.SOLUTION: A cylindrical member 100 for an exhaust gas treatment device has a metallic cylindrical main body 10, and an insulation layer 20 disposed on at least an inner peripheral surface of the cylindrical main body 10. The insulation layer includes glass, and a content of an alkaline metal element in the glass is 1000 ppm or less.SELECTED DRAWING: Figure 1
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Description

[Technical field]

[0001] The present invention relates to a tubular member for an exhaust gas treatment device, an exhaust gas treatment device using the tubular member, and an insulating layer used in the tubular member. [Background technology]

[0002] In recent years, electrically heated catalysts (EHCs) have been proposed to improve the deterioration of exhaust gas purification performance immediately after engine start. EHCs are constructed by arranging electrodes in a honeycomb structure made of conductive ceramic, and heating the honeycomb structure itself by passing electricity through it, thereby raising the temperature of the catalyst supported on the honeycomb structure to an activation temperature before or when the engine is started.

[0003] Typically, an EHC is housed in a metallic cylindrical member (also referred to as a can) to constitute an exhaust gas treatment device. When an electric current is applied to the EHC, the exhaust gas purification efficiency at the time of starting the vehicle can be improved as described above, but there are cases where electricity leaks from the EHC to the piping, resulting in a decrease in purification performance. To solve this problem, a technique is known in which an insulating layer (typically containing a glass component) is formed on the inner peripheral surface of the can to prevent leakage current (Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 5408341 [Patent Document 2] JP 2012-154316 A Summary of the Invention [Problem to be solved by the invention]

[0005] Regarding the insulating layers described in Patent Documents 1 and 2, depending on the constituent material of the can, the glass of the insulating layer may react with the constituent components of the can under high temperatures, possibly generating environmentally hazardous substances. A primary object of the present invention is to provide a tubular member for an exhaust gas treatment device capable of suppressing the generation of environmentally hazardous substances even at high temperatures. A further object of the present invention is to provide an exhaust gas treatment device using such a tubular member and an insulating layer used in such a tubular member. [Means for solving the problem]

[0006] The present invention provides a cylindrical member for an exhaust gas treatment device, comprising a metal cylindrical body and an insulating layer provided on at least an inner peripheral surface of the cylindrical body, the insulating layer including glass, the glass having an alkali metal element content of 1000 ppm or less. In one embodiment, the tubular body comprises chromium. In one embodiment, the alkali metal element comprises one or more elements selected from sodium, potassium and combinations thereof. In one embodiment, the tubular body is made of stainless steel. In one embodiment, the insulating layer has a thickness of 30 μm to 800 μm. In one embodiment, the insulating layer has an indentation deformation temperature of 600°C or higher, as defined below: the indentation deformation temperature is the temperature at which the insulating layer is deformed by 10% in the thickness direction of the insulating layer when the insulating layer is heated at a temperature increase rate of 10°C / min while being pressed at a pressure of 0.1 MPa using an alumina needle with a diameter of 1 mm. In one embodiment, the glass comprises silicon, boron and magnesium. In one embodiment, the glass comprises barium and lanthanum, zinc, or a combination thereof. According to another aspect of the present invention, there is provided an exhaust gas treatment device comprising: an electrically heated catalyst carrier capable of heating exhaust gas; and the above-mentioned cylindrical member for an exhaust gas treatment device that houses the electrically heated catalyst carrier. According to yet another aspect of the present invention, there is provided an insulating layer that can be disposed on at least an inner circumferential surface of a cylindrical body of a cylindrical component for an exhaust gas treatment device, the insulating layer including glass, the glass having an alkali metal element content of 1000 ppm or less. Effect of the Invention

[0007] According to an embodiment of the present invention, it is possible to realize a cylindrical member for an exhaust gas treatment device that can suppress the generation of environmentally hazardous substances even at high temperatures. [Brief description of the drawings]

[0008] [Figure 1] 1 is a schematic cross-sectional view of a tubular member for an exhaust gas treatment device according to one embodiment of the present invention, taken in a direction perpendicular to the flow path direction of exhaust gas. [Diagram 2] 1 is a schematic cross-sectional view of an exhaust gas treatment device according to one embodiment of the present invention, taken in a direction parallel to the flow path direction of exhaust gas. [Diagram 3] 3 is a schematic cross-sectional view of the exhaust gas treatment device of FIG. 2 in a direction perpendicular to the flow path direction of the exhaust gas (schematic cross-sectional view seen from the direction of arrow III in FIG. 2). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Hereinafter, embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited to these embodiments.

[0010] A. Cylindrical member for exhaust gas treatment equipment A-1. Overall configuration of the cylindrical member for exhaust gas treatment equipment FIG. 1 is a schematic cross-sectional view of a cylindrical member for an exhaust gas treatment device according to one embodiment of the present invention (hereinafter, sometimes simply referred to as a cylindrical member) in a direction perpendicular to the flow path direction of exhaust gas. The cylindrical member 100 in the illustrated example has a cylindrical main body 10 and an insulating layer 20 provided on at least the inner circumferential surface of the cylindrical main body 10. The insulating layer may be provided only on the inner circumferential surface of the cylindrical main body as in the illustrated example, or may be provided on both the inner circumferential surface and the outer circumferential surface of the cylindrical main body (not shown). By providing the insulating layer on both the inner circumferential surface and the outer circumferential surface of the cylindrical main body, it is possible to suppress the possibility of leakage caused by unburned deposits that may accumulate near the upstream end of the electrically heated catalyst carrier. In an embodiment of the present invention, the insulating layer 20 contains glass, and the content of alkali metal elements in the glass is 1000 ppm or less. With such a configuration, it is possible to realize a cylindrical member for an exhaust gas treatment device that can suppress the generation of environmental load substances even at high temperatures. The cylindrical member 100 has a cavity (hollow portion) 30 defined in the center in a cross section perpendicular to the flow direction of the exhaust gas. An electrically heated catalyst carrier is accommodated in the cavity 30 to form an exhaust gas treatment device. The cylindrical member 100 in the illustrated example is cylindrical (the cross section perpendicular to the flow direction of the exhaust gas is circular), but the shape of the cylindrical member can be appropriately designed depending on the purpose. For example, the cylindrical member 100 may be a cylinder having a polygonal (e.g., rectangular, hexagonal, octagonal) or elliptical cross section. The cylindrical body and the insulating layer will be specifically described below. The electrically heated catalyst carrier and the exhaust gas treatment device will be described in detail in Section B below.

[0011] A-2. Cylindrical body The cylindrical body 10 is typically made of metal. Such a configuration provides excellent manufacturing efficiency and allows easy storage or installation of the electrically heated catalyst carrier. Examples of materials that can be used to form the cylindrical body include stainless steel, titanium alloys, copper alloys, aluminum alloys, and brass. Among these, stainless steel is preferred because of its high durability, reliability, and low cost.

[0012] In one embodiment, the cylindrical body contains chromium. Chromium can be typically introduced to impart corrosion resistance to the cylindrical body (e.g., stainless steel). The chromium content in the cylindrical body can be, for example, 10.5% by mass or more, and can be, for example, 12% by mass to 20% by mass. When the cylindrical body contains chromium, the effect of the embodiment of the present invention becomes significant. More specifically, it is as follows. When the cylindrical body contains chromium, the possibility of generating environmental load substances increases significantly when it reacts with the glass component of the insulating layer at high temperatures. According to the embodiment of the present invention, even in such a case, the generation of environmental load substances can be well suppressed.

[0013] The thickness of the cylindrical body may be, for example, 0.1 mm to 10 mm, or may be, for example, 0.3 mm to 5 mm, or may be, for example, 0.5 mm to 3 mm. If the thickness of the cylindrical body is within such a range, it can have excellent durability and reliability.

[0014] The length of the cylindrical body can be appropriately set depending on the purpose, the length of the electrically heated catalyst carrier, etc. The length of the cylindrical body can be, for example, 30 mm to 600 mm, or, for example, 40 mm to 500 mm, or, for example, 50 mm to 400 mm. Preferably, the length of the cylindrical body is longer than the length of the electrically heated catalyst carrier. In this case, the electrically heated catalyst carrier can be arranged so that the electrically heated catalyst carrier is not exposed from the cylindrical body.

[0015] The inner peripheral surface of the cylindrical body may be surface-treated as necessary. A typical example of the surface treatment is a roughening treatment such as blasting. The roughening treatment can improve the adhesion between the insulating layer and the cylindrical body.

[0016] The cylindrical body may have a double structure having an outer cylindrical part and an inner cylindrical part arranged coaxially (not shown). In this case, the insulating layer may be provided between the outer cylindrical part and the inner cylindrical part (the inner peripheral surface of the outer cylindrical part or the outer peripheral surface of the inner cylindrical part), or may be provided on the inner peripheral surface of the inner cylindrical part, or may be provided on both.

[0017] A-3. Insulating layer The insulating layer 20 provides electrical insulation between the cylindrical member 100 and an electrically heated catalyst carrier (described later). Here, the electrical insulation typically satisfies JIS standard D5305-3 in order to suppress leakage to surrounding drains, and the insulation resistance per unit voltage is, for example, 100 Ω / V or more. The insulating layer 20 preferably further has moisture impermeability and moisture non-absorption properties. That is, the insulating layer 20 can be configured to be dense and not permeable to water and not absorb water. As for the denseness, the porosity of the insulating layer can be, for example, 10% or less, or, for example, 8% or less.

[0018] In the embodiment of the present invention, the insulating layer 20 contains glass as described above. Preferably, the insulating layer contains glass containing crystalline matter. By containing crystalline matter in the glass, an insulating layer that is difficult to soften and deform even at high temperatures (for example, 750°C or higher) can be formed. The insulating layer can maintain a pressure of 0.1 MPa, which is considered to be necessary for holding an electrically heated catalyst carrier when it is housed in an environment of, for example, 750°C or higher. Therefore, in an exhaust gas treatment device, it is possible to suppress the displacement of the electrically heated catalyst carrier, movement to an undesired position, etc. As a result, it is possible to realize a cylindrical member for an exhaust gas treatment device that can stably maintain an exhaust gas treatment (representatively, purification) function even at high temperatures. Furthermore, by containing crystalline matter in the glass, an insulating layer that has excellent adhesion to the cylindrical main body can be formed. This is because the difference in thermal expansion coefficient with the metal (cylindrical main body) can be reduced, and the thermal stress generated during heating can be reduced. The presence or absence of crystalline matter (crystals) can be confirmed by X-ray diffraction.

[0019] The glass typically contains silicon and boron. With such a configuration, the flowability during the formation of the insulating layer is excellent, and a predetermined crystal can be formed, so that a uniform insulating layer can be formed, and an insulating layer that is difficult to soften and deform even at high temperatures (e.g., 750°C or higher) can be formed. Silicon can be contained in the glass in the form of, for example, SiO2; boron can be contained in the glass in the form of, for example, B2O3. In other words, the glass can be, for example, a SiO2-B2O3-based glass.

[0020] Silicon (substantially SiO2) is a component that forms the skeleton of glass. More specifically, silicon is a component that causes crystals to precipitate by heat treatment, and is a component that widens the vitrification range to facilitate vitrification and improves water resistance and heat resistance. The silicon content in glass is preferably 5 mol% to 50 mol%, more preferably 7 mol% to 45 mol%, and even more preferably 10 mol% to 40 mol%. Boron (substantially B2O3) is a component that increases melting property and fluidity as well as devitrification resistance. The boron content is preferably 5 mol% to 60 mol%, more preferably 7 mol% to 57 mol%, and even more preferably 8 mol% to 55 mol%. If the silicon and boron contents are within such ranges, the above effect (formation of an insulating layer that is uniform and does not easily soften or deform even at high temperatures) becomes more remarkable. In this specification, the "content of an element in glass" refers to the molar ratio of the atom of the element when the amount of all atoms in the glass excluding oxygen atoms is taken as 100 mol%. The amount of atoms of each element in glass can be measured, for example, by inductively coupled plasma (ICP) emission spectrometry.

[0021] The glass may further contain magnesium. Magnesium may be contained in the glass in the form of MgO, for example. Magnesium (substantially MgO) is a constituent component of crystals and is a component that reduces high-temperature viscosity and enhances melting property and fluidity. When the glass contains magnesium, it is less likely to soften or deform even at high temperatures, and a uniform insulating layer can be formed. When magnesium is contained in the glass, the content is preferably 20 mol% to 40 mol%, more preferably 22 mol% to 37 mol%, and further preferably 25 mol% to 35 mol%.

[0022] The glass may further contain barium. In this case, the glass may further contain lanthanum, zinc or a combination thereof. Barium may be contained in the glass in the form of BaO, for example; lanthanum may be contained in the glass in the form of La2O3, for example; zinc may be contained in the glass in the form of ZnO, for example. Barium (substantially BaO) and zinc (substantially ZnO) are each a constituent component of a crystal. Lanthanum (substantially La2O3) is a component for improving fluidity. When the glass contains barium and, if necessary, further contains lanthanum, zinc or a combination thereof, an insulating layer having extremely excellent adhesion to the cylindrical body can be formed. When barium is contained in the glass, the content is preferably 3 mol% to 30 mol%, more preferably 5 mol% to 25 mol%, and even more preferably 6 mol% to 20 mol%. The content of lanthanum is preferably 2 mol% to 25 mol%, more preferably 2 mol% to 20 mol%, and even more preferably 2 mol% to 18 mol%. The zinc content is preferably 2 mol% to 20 mol%, more preferably 2 mol% to 18 mol%, and further preferably 3 mol% to 16 mol%. The total content of lanthanum and zinc is preferably 7 mol% to 20 mol%.

[0023] The glass may further contain other metal elements. Examples of such metal elements include aluminum, calcium, and strontium. These metal elements may be contained in the glass alone or in combination of two or more. The other metal elements may also be contained in the glass in the form of metal oxides (e.g., Al2O3, CaO, SrO) like the above elements. The content of these metal elements in the glass may be defined as the remainder excluding the above elements and unavoidable impurities. Aluminum (substantially Al2O3) is a component that forms the skeleton of the glass, increases the strain point, adjusts the viscosity, and further suppresses phase separation. Calcium (substantially CaO) is a component that widens the vitrification range to facilitate vitrification, and is a component that lowers the high-temperature viscosity without lowering the strain point to enhance melting and fluidity. Strontium (substantially SrO) is a component that widens the vitrification range to facilitate vitrification, and is a component that suppresses phase separation and enhances devitrification resistance. The aluminum content may be, for example, 5 mol % to 15 mol %; the calcium content may be, for example, 3 mol % to 7 mol %; and the strontium content may be, for example, 8 mol % to 12 mol %.

[0024] In an embodiment of the present invention, the content of alkali metal elements in the glass is 1000 ppm or less, preferably 800 ppm or less, more preferably 500 ppm or less, further preferably 200 ppm or less, and particularly preferably 100 ppm or less, as described above. The content of alkali metal elements is preferably as small as possible, and may be, for example, substantially zero (below the detection limit). By making the content of alkali metal elements in the glass very small, it is possible to realize a cylindrical member for an exhaust gas treatment device that can suppress the generation of environmental load substances even at high temperatures. In this specification, the "content of alkali metal elements in the glass" means the total amount of alkali metal elements contained in the glass. Examples of alkali metals include lithium, sodium, potassium, rubidium, cesium, and francium. The alkali metal elements contained in the glass may be, for example, sodium, potassium, or a combination thereof; or may be, for example, sodium. The content of alkali metal elements may be measured, for example, by inductively coupled plasma (ICP) emission spectrometry.

[0025] Representative compositions of glass that can be used in the embodiments of the present invention are shown in Table 1 below. In the glass, each element is contained within the range shown in Table 1, and the total of each element is 100. In Table 1, the content of each element is "mol %". In each composition, the content of alkali metal elements is 1000 ppm or less, and in certain compositions among them, the content is below the detection limit.

[0026] [Table 1]

[0027] The thickness of the insulating layer is preferably 30 μm to 800 μm, more preferably 50 μm to 600 μm, and further preferably 100 μm to 550 μm. If the thickness of the insulating layer is within this range, it is possible to achieve both excellent electrical insulation properties and excellent adhesion to the cylindrical main body.

[0028] The indentation deformation temperature of the insulating layer is preferably 600°C or higher, more preferably 700°C or higher, even more preferably 800°C or higher, and particularly preferably 850°C or higher. The upper limit of the indentation deformation temperature may be, for example, 1200°C. If the indentation deformation temperature of the insulating layer is within this range, an insulating layer that is not easily softened even at high temperatures (for example, 750°C or higher) can be formed. The indentation deformation temperature is the temperature at which the insulating layer is deformed by 10% in the thickness direction of the insulating layer when the insulating layer is heated from room temperature (25°C) at a temperature increase rate of 10°C / min while being pressed with a pressure of 0.1 MPa using an alumina needle with a diameter of 1 mm.

[0029] In one embodiment, the insulating layer satisfies the following (1) and / or (2) after a predetermined peel test: (1) elements originating from the insulating layer are present on the inner peripheral surface of the cylindrical body; (2) The insulating layer contains elements originating from the cylindrical body. The peeling test includes repeatedly exchanging the cylindrical member for an exhaust gas treatment device between environments of 900°C and 150°C in accordance with JIS H 8451:2008 until the insulating layer peels off. With such a configuration, excellent adhesion between the cylindrical body and the insulating layer can be realized. From the above (1) or (2), it is inferred that an intermediate layer is formed at the interface between the cylindrical body 10 and the insulating layer 20. The intermediate layer can typically be a compatible layer in which the constituent components of the cylindrical body and the constituent components of the insulating layer are mixed. The intermediate layer can be formed, for example, by the constituent components of the cylindrical body migrating to the insulating layer and the constituent components of the insulating layer migrating to the cylindrical body. In some cases, the intermediate layer can contain a chemical reaction product between the constituent components of the cylindrical body and the constituent components of the insulating layer. The intermediate layer can have a concentration gradient in which the constituent components of the cylindrical body decrease from the cylindrical body side toward the insulating layer side, and / or the constituent components of the insulating layer decrease from the insulating layer side toward the cylindrical body side. It is presumed that when such an intermediate layer is formed, the interface between the cylindrical body and the insulating layer becomes unclear, and the adhesion is improved. However, such a presumption does not restrict the embodiment and the mechanism of the present invention. Note that such an insulating layer can be realized by introducing, for example, barium and, if necessary, lanthanum, zinc, or a combination thereof.

[0030] The insulating layer may be a part (constituent element) of the cylindrical member for an exhaust gas treatment device as described above, or may be provided in a form that can be distributed as an insulating layer. When the insulating layer is a part of the cylindrical member for an exhaust gas treatment device, the insulating layer can be typically formed by applying an insulating layer forming material to the cylindrical main body, drying, and firing. The method of forming the insulating layer will be described later in Section A-4. Examples of forms that can be distributed as an insulating layer include a laminate in which an insulating layer is formed on any suitable base material, a glass sheet of an insulating layer, and a glass roll of an insulating layer. Any of these can be attached to the cylindrical main body by any suitable means. Specific examples of attachment include bonding via an adhesive or the like, and mechanical fixation.

[0031] A-4. Method for forming insulating layer The insulating layer may be formed by any suitable method. Typically, the insulating layer is formed by applying and drying a slurry (dispersion) containing a glass source to form a coating film, and then firing the coating film. The slurry may contain raw materials as the glass source, or may contain glass frit. Below, as a representative example, a method of forming an insulating layer using a slurry containing glass frit as the glass source will be described.

[0032] The forming method of the present embodiment typically includes the steps of: producing glass frit from a glass source (raw material); preparing a raw material slurry containing the glass frit; forming a coating film of the slurry; and firing the coating film to form an insulating layer containing glass.

[0033] Specific examples of raw materials include silica sand (silicon source), dolomite (magnesium and calcium source), alumina (aluminum source), barium oxide, lanthanum oxide, zinc oxide (zinc oxide), and strontium oxide. The raw materials are not limited to oxides, and may be, for example, carbonates or hydroxides. Glass frit is typically produced by synthesizing glass from glass raw materials and pulverizing the obtained glass (for example, pulverizing in two stages of coarse pulverization and fine pulverization). When synthesizing glass, melting is performed for a long time at high temperatures (typically 1200°C or higher).

[0034] The glass frit and the solvent are mixed to prepare a raw material slurry (dispersion). The solvent may be water or an organic solvent. The solvent is preferably water or a water-soluble organic solvent, more preferably water. The solvent may be mixed at a ratio of preferably 50 to 300 parts by mass, more preferably 80 to 200 parts by mass, per 100 parts by mass of the glass frit. When preparing the raw material slurry, a slurry aid (e.g., a resin, a plasticizer, a dispersant, a thickener, various additives) may be further mixed. The type, number, combination, amount, etc. of the slurry aid may be appropriately set according to the purpose. In this specification, the term "solvent" refers to a liquid medium contained in the raw material slurry, and is a concept that includes a solvent and a dispersion medium.

[0035] Next, the raw material slurry is applied and dried to form a coating film. The coating film may be formed on the inner circumferential surface of the cylindrical body, or on any suitable substrate. Any suitable method may be used as the coating method. Specific examples of the coating method include spraying, immersion with the cylindrical body or substrate masked except for the portion where the insulating layer is to be formed, and bar coating. The coating thickness may be adjusted according to the desired thickness of the insulating layer. The drying temperature is, for example, 40°C to 120°C, or, for example, 50°C to 110°C. The drying time is, for example, 1 minute to 60 minutes, or, for example, 10 minutes to 30 minutes.

[0036] Finally, the coating film is baked to form an insulating layer. The baking temperature is preferably 1100° C. or lower, more preferably 600° C. to 1100° C., and further preferably 700° C. to 1050° C. The baking time is, for example, 5 minutes to 30 minutes, or, for example, 8 minutes to 15 minutes.

[0037] In the manner described above, the insulating layer can be formed. When the insulating layer is to be formed on both the inner peripheral surface and the outer peripheral surface of the cylindrical main body, the insulating layer may be formed on the outer peripheral surface in the same manner as described above.

[0038] B. Exhaust gas treatment equipment FIG. 2 is a schematic cross-sectional view of an exhaust gas treatment device according to one embodiment of the present invention in a direction parallel to the flow path direction of exhaust gas; and FIG. 3 is a schematic cross-sectional view of the exhaust gas treatment device of FIG. 2 as viewed from the direction of arrow III. The illustrated example of an exhaust gas treatment device 300 includes an electrically heated catalyst carrier (hereinafter, may be simply referred to as a catalyst carrier) 200 capable of heating exhaust gas; and a cylindrical member 100 that houses the catalyst carrier 200. The cylindrical member 100 is the cylindrical member for an exhaust gas treatment device according to the embodiment of the present invention described in section A above and in FIG. 1. The exhaust gas treatment device is installed midway through an exhaust gas flow path for passing exhaust gas from an engine. The catalyst carrier heated to the activation temperature of the catalyst comes into contact with the exhaust gas, and CO, NO, and the like in the exhaust gas passing through the catalyst carrier are reduced in size and reduced in temperature. x It is possible to convert hydrocarbons and other fuels into harmless substances through catalytic reactions.

[0039] The catalyst carrier 200 may have a shape corresponding to the shape of the tubular member 100. For example, when the tubular member 100 is cylindrical, the catalyst carrier 200 may be cylindrical. The catalyst carrier 200 is housed in the cavity 30 of the tubular member 100, typically coaxially. The catalyst carrier may be housed directly in the tubular member (i.e., without any other member), or may be housed, for example, via a retaining mat (not shown). When the catalyst carrier is housed directly in the tubular member, the catalyst carrier may be, for example, fitted into the tubular member. The retaining mat is typically an insulating material (e.g., alumina) formed into a mat shape. The retaining mat typically covers the entire outer circumferential surface of the catalyst carrier, and the tubular member may hold the catalyst carrier via the retaining mat.

[0040] The catalyst carrier 200 includes a honeycomb structure section 220 and a pair of electrode sections 240 arranged on the side surfaces of the honeycomb structure section 220 (typically, facing each other across the central axis of the honeycomb structure section). The honeycomb structure section 220 has an outer peripheral wall 222 and partition walls 224 arranged inside the outer peripheral wall 222 and extending from a first end face 228a to a second end face 228b to define a plurality of cells 226 that form an exhaust gas flow path. The outer peripheral wall 222 and the partition walls 224 are typically made of conductive ceramics. The pair of electrode sections 240, 240 are each provided with a metal terminal 260, 260. One metal terminal is connected to the positive pole of a power source (e.g., a battery), and the other metal terminal is connected to the negative pole of the power source (e.g., a battery). Covers 270, 270 made of an insulating material are provided around the metal terminals 260, 260 so as to insulate the cylindrical body 10 and the insulating layer 20 from the metal terminals.

[0041] The catalyst is typically supported on the partition walls 224. By supporting the catalyst on the partition walls 224, the CO, NO x, hydrocarbons, etc. can be converted into harmless substances by catalytic reaction. The catalyst may preferably contain a precious metal (e.g., platinum, rhodium, palladium, ruthenium, indium, silver, gold), aluminum, nickel, zirconium, titanium, cerium, cobalt, manganese, zinc, copper, tin, iron, niobium, magnesium, lanthanum, samarium, bismuth, barium, and combinations thereof. The amount of the catalyst supported may be, for example, 0.1 g / L to 400 g / L.

[0042] When a voltage is applied to the honeycomb structure section 220, electricity is passed therethrough, and the honeycomb structure section 220 can generate heat by Joule heat. This allows the catalyst supported on the honeycomb structure section (substantially the partition walls) to be heated to an active temperature before or at the time of engine start. As a result, exhaust gas can be sufficiently treated (representatively, purified) even at the time of engine start.

[0043] The catalyst carrier may have a structure well known in the art, and a detailed description thereof will be omitted. EXAMPLES

[0044] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The evaluation items in the examples are as follows.

[0045] (1) Alkali metal element content The insulating layers prepared in the examples and comparative examples were weighed out on a platinum plate, decomposed by heating with hydrofluoric acid and perchloric acid, and the residue was dissolved in hydrochloric acid. The alkaline components in this solution were measured using an inductively coupled plasma (ICP) emission spectrometer (Hitachi High-Technologies Corporation PS3520UV-DD) to determine the content of the alkali metal elements.

[0046] (2) Indentation deformation temperature The insulating layers produced in the examples and comparative examples were pressed with a 1 mmΦ alumina needle at a pressure of 0.1 MPa while being heated from room temperature (25°C) at a heating rate of 10°C / min. The temperature at which the insulating layer was deformed by 10% in the thickness direction relative to the thickness of the insulating layer was recorded as the indentation deformation temperature.

[0047] (3) Environmentally hazardous substances The cylindrical members obtained in the examples and comparative examples were held in an electric furnace at 900°C for 1 hour and then cooled to room temperature. The cylindrical members were then washed with 100 ml of pure water, and the liquid recovered after washing was used as the test liquid. This test liquid was subjected to diphenylcarbazide absorptiometry to measure the content (μg / L) of environmentally hazardous substances (chromium compounds).

[0048] <Examples 1 to 7 and Comparative Examples 1 to 6> The inner peripheral surface of a metal pipe made of SUS430 was subjected to sandblasting treatment using alumina abrasive grains of #24 to #60. The treatment time was 1 minute. The surface roughness Ra of the metal pipe after sandblasting treatment was 2.0 μm to 6.5 μm. The metal pipe obtained in this way was used as a cylindrical main body. On the other hand, raw materials selected from silica sand (Si source), B2O3, Mg(OH)2, Al2O3, BaCO3, zircon (Zr source), La2O3, petalite (Li source), Na2CO3, potassium feldspar (K source), zinc oxide (Zn source) and Cs2CO3 were melted to prepare glass frit so that the resulting glass composition would be the composition shown in Table 2. 100 parts by mass of water was added to 100 parts by mass of glass frit and wet mixed in a ball mill to prepare a glass raw material dispersion (slurry). The composition and impurities of the glass were measured by inductively coupled plasma (ICP) emission spectrometry. Whether the glass was crystalline or amorphous was determined by the presence or absence of a diffraction peak in X-ray diffraction (XRD). The glass raw material dispersion was sprayed onto the inner circumferential surface of the cylindrical body obtained above to form a coating film, which was then dried at 50° C. The cylindrical body on which the dried coating film was formed was fired at 860° C. to form an insulating layer (thickness 400 μm). The alkali metal element content and indentation deformation temperature of the insulating layer were as shown in Table 2. In this manner, a cylindrical member was formed. The obtained cylindrical member was subjected to the evaluation of "(3) Environmentally hazardous substances" above. The results are shown in Table 2.

[0049] [Table 2]

[0050] As is clear from Table 2, the cylindrical members of the examples of the present invention significantly suppress the generation of environmental load substances at high temperatures compared to the comparative examples. [Industrial Applicability]

[0051] The cylindrical member for an exhaust gas treatment device according to the embodiment of the present invention can be suitably used for treating (purifying) exhaust gas from an automobile. [Explanation of symbols]

[0052] 10 Cylindrical body 20 Insulating layer 30 cavities 100 Cylindrical member for exhaust gas treatment device 200 Electrically heated catalyst carrier 220 Honeycomb structure 240 Electrode section 260 Metal terminal 300 Exhaust gas treatment equipment

Claims

1. The insulating layer is formed on at least an inner circumferential surface of the cylindrical body. the insulating layer contains glass, and the content of alkali metal elements in the glass is 900 ppm or less; A cylindrical member for an exhaust gas treatment device.

2. 2. The cylindrical member for an exhaust gas treatment device according to claim 1, wherein the alkali metal element includes one or more elements selected from sodium, potassium, and combinations thereof.

3. 3. The tubular member for an exhaust gas treatment device according to claim 1, wherein the tubular body is made of stainless steel.

4. 4. The cylindrical member for an exhaust gas treatment device according to claim 1, wherein the insulating layer has a thickness of 30 μm to 800 μm.

5. The cylindrical member for an exhaust gas treatment device according to any one of claims 1 to 4, wherein the insulating layer has an indentation deformation temperature of 600°C or higher, as defined below: The indentation deformation temperature is the temperature at which the insulating layer is deformed by 10% in the thickness direction of the insulating layer when the insulating layer is heated at a temperature increase rate of 10°C / min while being pressed with a 1 mmΦ alumina needle at a pressure of 0.1 MPa.

6. 6. The cylindrical member for an exhaust gas treatment device according to claim 1, wherein the glass contains silicon, boron and magnesium.

7. The cylindrical member for an exhaust gas treatment device according to claim 1 , wherein the glass contains barium, and lanthanum, zinc, or a combination thereof.

8. An electrically heated catalyst carrier capable of heating exhaust gas; A cylindrical member for an exhaust gas treatment device according to any one of claims 1 to 7, which houses the electrically heated catalyst carrier; An exhaust gas treatment device comprising:

9. An insulating layer that can be disposed on at least an inner circumferential surface of a chromium-containing metal cylindrical body of a cylindrical member for an exhaust gas treatment device, the insulating layer contains glass, and the content of alkali metal elements in the glass is 900 ppm or less; Insulating layer.

10. 10. The insulating layer of claim 9, wherein the alkali metal element comprises one or more elements selected from sodium, potassium and combinations thereof.

11. The insulating layer according to claim 9 or 10, having a thickness of 30 μm to 800 μm.

12. 12. The insulating layer of claim 9, wherein the glass comprises silicon, boron and magnesium.

13. 13. The insulating layer of claim 9, wherein the glass comprises barium and lanthanum, zinc, or a combination thereof.

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