WO2013098889A1 - 通電加熱式触媒装置及びその製造方法 - Google Patents
通電加熱式触媒装置及びその製造方法 Download PDFInfo
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- WO2013098889A1 WO2013098889A1 PCT/JP2011/007328 JP2011007328W WO2013098889A1 WO 2013098889 A1 WO2013098889 A1 WO 2013098889A1 JP 2011007328 W JP2011007328 W JP 2011007328W WO 2013098889 A1 WO2013098889 A1 WO 2013098889A1
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- Prior art keywords
- carrier
- surface electrode
- electrically heated
- catalyst device
- heated catalyst
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- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 238000000034 method Methods 0.000 title claims description 6
- 230000003197 catalytic effect Effects 0.000 title abstract 2
- 229910052751 metal Inorganic materials 0.000 claims abstract description 127
- 239000002184 metal Substances 0.000 claims abstract description 127
- 239000003054 catalyst Substances 0.000 claims abstract description 76
- 239000000919 ceramic Substances 0.000 claims abstract description 9
- 229910045601 alloy Inorganic materials 0.000 claims description 28
- 239000000956 alloy Substances 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000005507 spraying Methods 0.000 claims description 10
- 238000003892 spreading Methods 0.000 claims description 9
- 238000007751 thermal spraying Methods 0.000 claims description 7
- 230000002093 peripheral effect Effects 0.000 claims description 6
- 238000007788 roughening Methods 0.000 claims description 6
- 229910001256 stainless steel alloy Inorganic materials 0.000 claims description 5
- 229910018487 Ni—Cr Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 230000005611 electricity Effects 0.000 abstract 1
- 230000008646 thermal stress Effects 0.000 description 18
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 9
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 5
- 229910010271 silicon carbide Inorganic materials 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000005422 blasting Methods 0.000 description 4
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- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003779 heat-resistant material Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- 241000270666 Testudines Species 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
-
- B01J35/56—
-
- 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
- F01N3/18—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 methods of operation; Control
- F01N3/20—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 methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
- F01N3/2006—Periodically heating or cooling catalytic reactors, e.g. at cold starting or overheating
- F01N3/2013—Periodically heating or cooling catalytic reactors, e.g. at cold starting or overheating using electric or magnetic heating means
-
- 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
- F01N3/2825—Ceramics
- F01N3/2828—Ceramic multi-channel monoliths, e.g. honeycombs
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/28—Apparatus or processes specially adapted for manufacturing resistors adapted for applying terminals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49082—Resistor making
- Y10T29/49083—Heater type
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49082—Resistor making
- Y10T29/49099—Coating resistive material on a base
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49345—Catalytic device making
Definitions
- the present invention relates to an electrically heated catalyst device and a manufacturing method thereof.
- EHC Electrically-Heated-Catalyst
- the EHC disclosed in Patent Document 1 is a cylindrical carrier having a honeycomb structure on which a catalyst such as platinum or palladium is supported, and is electrically connected to the carrier and arranged opposite to the outer peripheral surface of the carrier. A pair of surface electrodes.
- the support is energized and heated between the pair of surface electrodes to activate the catalyst supported on the support.
- unburned HC (hydrocarbon), CO (carbon monoxide), NOx (nitrogen oxide) and the like in the exhaust gas passing through the carrier are purified by the catalytic reaction.
- the surface electrode material is required to have not only electrical conductivity but also heat resistance, oxidation resistance at high temperature, and corrosion resistance in an exhaust gas atmosphere.
- a metal material such as a Ni—Cr alloy or a MCrAlY alloy (where M is at least one of Fe, Co, and Ni) is used.
- the surface electrode is formed on the carrier by thermal spraying.
- a ceramic material such as SiC (silicon carbide) is used as the material of the carrier. For this reason, during energization heating, thermal stress is generated due to a difference in linear expansion coefficient between the metal material constituting the surface electrode and the ceramic material constituting the carrier.
- the inventor has found the following problems.
- the surface electrode of the EHC extends in the axial direction of the cylindrical carrier. Further, a metal wiring is connected to the center portion of the surface electrode in the carrier axial direction, and current is supplied. When this current spreads in the direction of the carrier axis in the surface electrode, the entire carrier is energized and heated between the pair of surface electrodes. When energization heating is repeated, cracks in the circumferential direction of the carrier are generated in the surface electrode due to the above-described thermal stress, and current spreading in the direction of the carrier axis is inhibited. As a result, the vicinity of the connection portion between the surface electrode and the metal wiring ( There was a problem that the central part in the axial direction of the carrier was heated intensively.
- the present invention has been made in view of the above, and provides an electrically heated catalyst device capable of maintaining a current spread in a carrier axial direction even when a crack in the carrier circumferential direction occurs on a surface electrode. With the goal.
- the electrically heated catalyst device is A carrier made of ceramics carrying a catalyst; A pair of surface electrodes extending in the axial direction of the carrier while facing each other on the outer peripheral surface of the carrier; Wiring for supplying electric power to the surface electrode from the outside, and an electrically heated catalyst device for electrically heating the carrier through the surface electrode, A metal extending member extending in the axial direction of the carrier is embedded in the surface electrode. Even if a crack in the circumferential direction of the carrier occurs on the surface electrode, it is possible to provide an energization heating type catalyst device that maintains the spread of current in the direction of the carrier axis.
- the extending member is any one of a mesh, a wire, and a punched plate. Thereby, the spread of current in the direction of the carrier axis is reliably maintained.
- the surface electrode is preferably formed by thermal spraying. Furthermore, it is preferable that a cavity is formed between the carrier and the extension member. Thereby, thermal stress is relieved.
- the said extending member is provided with the junction part joined to the said surface electrode, and the non-joining part which is not joined to the said surface electrode.
- the stretch member is preferably made of any one of a stainless steel alloy, a Ni base alloy, and a Co base alloy.
- connection region to which the wiring is connected in the surface electrode is located in a central portion in the axial direction of the carrier. It is preferable that the ceramic contains SiC.
- the surface electrode is preferably made of a Ni—Cr alloy (provided that the Cr content is 20 to 60% by mass) or a MCrAlY alloy (where M is at least one of Fe, Co, and Ni).
- a method for producing an electrically heated catalyst device includes: A method for producing an electrically heated catalyst device in which the carrier is energized and heated via a surface electrode formed on the surface of a carrier made of ceramics on which a catalyst is supported, Forming a pair of surface electrodes extending in the axial direction of the carrier so as to face each other on the outer peripheral surface of the carrier; and Connecting a wiring for supplying electric power from the outside to the surface electrode, In the step of forming the surface electrode, A metal extending member extending in the axial direction of the carrier is embedded in the surface electrode.
- the extending member is any one of a mesh, a wire, and a punched plate.
- the step of forming the surface electrode includes a spraying step of spraying from above the spreading member placed on the carrier. Furthermore, it is preferable that a cavity is formed between the carrier and the extension member.
- the step of forming the surface electrode preferably includes a roughening step of roughening the surface of the spreading member placed on the carrier before the spraying step.
- a roughening step it is preferable that the bonding portion to be bonded to the surface electrode is roughened and the non-bonding portion that is not bonded to the surface electrode is not roughened.
- an energization heating type catalyst device in which the spread of current in the direction of the support axis is maintained even if cracks in the support circumferential direction occur on the surface electrode.
- FIG. 1 is a perspective view of an electrically heated catalyst device 100 according to Embodiment 1.
- FIG. FIG. 3 is a plan view seen from directly above the surface electrode 31 of the electrically heated catalyst device 100 according to the first embodiment. It is sectional drawing by the III-III cutting line in FIG. It is sectional drawing by the IV-IV cutting line in FIG. 2 is a cross-sectional photograph of a bonding interface between a carrier 20 and a surface electrode 31.
- 6 is a graph showing the dependence of the minimum temperature in the carrier 20 on the input power. 6 is a graph showing the dependence of the maximum temperature difference in the carrier 20 on the input power. 6 is a plan view seen from directly above a surface electrode 31 of an electrically heated catalyst device 200 according to Embodiment 2.
- FIG. 6 is a plan view seen from directly above a surface electrode 31 of an electrically heated catalyst device 200 according to a modification of the second embodiment.
- FIG. 6 is a plan view seen from directly above a surface electrode 31 of an electrically heated catalyst device 200 according to a modification of the second embodiment.
- FIG. 6 is a plan view seen from directly above a surface electrode 31 of an electrically heated catalyst device 200 according to a modification of the second embodiment.
- FIG. 5 is a plan view seen from directly above a surface electrode 31 of an electrically heated catalyst device 300 according to a third embodiment. It is a top view of the punching metal plate 31d of the electrically heated catalyst device 300 according to the third embodiment.
- FIG. 10 is a plan view of a punched metal plate 31d of an electrically heated catalyst device 300 according to a modification of the third embodiment.
- FIG. 10 is a plan view of a punched metal plate 31d of an electrically heated catalyst device 300 according to a modification of the third embodiment.
- FIG. 1 is a perspective view of an electrically heated catalyst device 100 according to the first embodiment.
- FIG. 2 is a plan view seen from directly above the surface electrode 31 of the electrically heated catalyst device 100 according to the first embodiment.
- FIG. 3 is a cross-sectional view taken along the line III-III in FIG. 2 and is a cross-sectional view at a portion where the fixed layer 33 is formed.
- 4 is a cross-sectional view taken along the line IV-IV in FIG.
- the electrically heated catalyst device 100 is provided on an exhaust path of, for example, an automobile and purifies exhaust gas discharged from the engine. As shown in FIG. 1, the electrically heated catalyst device 100 includes a carrier 20, a surface electrode 31, a wiring 32, and a fixed layer 33. In FIG. 2, the positional relationship among the carrier 20, the wiring 32, and the fixed layer 33 is shown for one surface electrode 31, but the same applies to the other surface electrode 31.
- the carrier 20 is a porous member that supports a catalyst such as platinum or palladium. Further, since the carrier 20 itself is energized and heated, it is made of a ceramic having conductivity, specifically, for example, SiC (silicon carbide). As shown in FIG. 1, the carrier 20 has a substantially cylindrical outer shape and has a honeycomb structure inside. As indicated by the arrows, the exhaust gas passes through the inside of the carrier 20 in the axial direction of the carrier 20.
- the surface electrode 31 is a pair of electrodes disposed on the outer surface of the carrier 20 so as to face each other.
- the surface electrode 31 has a rectangular planar shape and extends in the carrier axis direction.
- the surface electrode 31 is not formed near both ends in the carrier axis direction.
- the surface electrode 31 is connected to a power source such as a battery via a wiring 32. Then, a current is supplied to the carrier 20 through the surface electrode 31 and heated by energization.
- One of the pair of surface electrodes 31 is a positive electrode and the other is a negative electrode.
- any surface electrode 31 may be a positive electrode or a negative electrode. That is, the direction of the current flowing through the carrier 20 is not limited.
- a metal mesh 31a is embedded in the surface electrode 31 as a metal extending member extending in the carrier axis direction. 3 and 4 that the metal mesh 31a is embedded in the surface electrode 31. Details of the metal mesh 31a will be described later.
- the plurality of wirings 32 are disposed on each of the pair of surface electrodes 31.
- the plurality of wirings 32 are ribbon-like thin metal plates that are in physical contact with and electrically connected to the surface electrode 31.
- the wiring 32 is preferably made of a heat-resistant (oxidation-resistant) alloy such as a stainless alloy, a Ni-based alloy, or a Co-based alloy.
- the plurality of wirings 32 are extended over the entire formation region of the surface electrode 31 in the carrier circumferential direction. Further, all the wirings 32 are extended from one side of the formation region of the surface electrode 31 and are integrated at the protruding end. On the other hand, the plurality of wirings 32 are arranged on the surface electrode 31 at substantially equal intervals along the carrier axis direction. In the electrically heated catalyst device 100 according to the present embodiment, twelve wirings 32 are provided in the central portion in the axial direction of the carrier 20 on each surface electrode 31. As a matter of course, the number of the wirings 32 is not limited to 12, but is determined as appropriate.
- the carrier 20 is fixed and held on the exhaust path by a mat (not shown) made of a heat-resistant material in the vicinity of both ends in the carrier axial direction.
- a mat (not shown) made of a heat-resistant material in the vicinity of both ends in the carrier axial direction.
- FIG. 3 is a cross-sectional view taken along the line III-III in FIG. 2, and is a cross-sectional view at a portion where the fixed layer 33 is formed.
- the surface electrode 31 is a sprayed coating having a thickness of about 50 to 200 ⁇ m formed on the outer peripheral surface of the carrier 20. The surface electrode 31 is in physical contact with the carrier 20 and is electrically connected.
- the fixing layer 33 is a button-shaped sprayed coating formed so as to cover the wiring 32 in order to fix the wiring 32 to the surface electrode 31.
- the fixed layer 33 is button-shaped in order to relieve stress based on the difference in coefficient of linear expansion between the surface electrode 31 and the fixed layer 33 that are metal-based thermal sprayed coatings and the carrier 20 made of ceramics. It is. That is, the stress is relieved by making the fixed layer 33 as small as possible.
- the fixed layer 33 is in physical contact with and electrically connected to the wiring 32 and the surface electrode 31.
- the fixing layer 33 is provided at two locations on each wiring 32 so as to fix the wiring 32 to the surface electrode 31 at substantially both ends in the carrier circumferential direction. Further, as shown in FIG. 3, in the wirings 32 adjacent to each other, the fixed layer 33 is arranged so as to be shifted in the carrier circumferential direction. In other words, on each surface electrode 31, along the two long sides of the rectangular surface electrode 31, twelve fixing layers 33 on each side are arranged in a zigzag manner in the carrier axis direction.
- the thermal spray coating constituting the surface electrode 31 and the fixed layer 33 is energized similarly to the wiring 32, it needs to be a metal base.
- the metal that forms the matrix of the thermal spray coating is a Ni-Cr alloy with excellent oxidation resistance at high temperatures (with a Cr content of 20-60 mass%) to withstand use at high temperatures of 800 ° C or higher. ), MCrAlY alloy (where M is at least one of Fe, Co and Ni).
- the NiCr alloy and MCrAlY alloy may contain other alloy elements.
- the thermal spray coating constituting the surface electrode 31 and the fixed layer 33 may be porous. By being porous, the function to relieve stress is enhanced.
- the carrier 20 is electrically heated between the pair of surface electrodes 31, and the catalyst supported on the carrier 20 is activated.
- unburned HC (hydrocarbon), CO (carbon monoxide), NOx (nitrogen oxide) and the like in the exhaust gas passing through the carrier 20 are purified by the catalytic reaction.
- the metal mesh 31 a is embedded over substantially the entire surface of the surface electrode 31 formation region.
- Such a configuration can be obtained by placing the metal mesh 31a on the carrier 20 and forming the surface electrode 31 made of a thermal spray coating thereon.
- the metal mesh 31a extending in the carrier axis direction is embedded in the surface electrode 31, a crack in the carrier circumferential direction is formed in the surface electrode 31. Even if this occurs, the spread of current in the direction of the carrier axis is maintained through the metal mesh 31a. Therefore, the vicinity of the central portion in the axial direction of the carrier 20 is not intensively heated, and thermal stress cracking due to this intensive heating can be avoided.
- the carrier 20 is fixed and held on the exhaust path by a mat (not shown) made of a heat resistant material in the vicinity of both ends in the carrier axial direction.
- a mat (not shown) made of a heat resistant material in the vicinity of both ends in the carrier axial direction.
- the metal mesh 31a is in physical contact with and electrically connected to the surface electrode 31.
- the metal mesh 31a is made of, for example, a wire rod having a diameter of 0.1 mm or less made of a heat-resistant (oxidation-resistant) alloy such as a stainless steel alloy, a Ni base alloy, or a Co base alloy. It is preferable to be configured.
- the metal mesh 31a is placed on the carrier 20, and the surface electrode 31 made of a sprayed coating is formed thereon, thereby fixing the metal mesh 31a to the carrier 20.
- the weaving method of the metal mesh 31a is preferably a weaving method having a certain amount of space between adjacent metal wires, such as a plain weave, a flat top weave, a rhombus weave, and a turtle shell weave.
- the mesh size is preferably 50 or less.
- FIG. 5 is a cross-sectional photograph of the bonding interface between the carrier 20 and the surface electrode 31.
- the surface electrode 31 is formed by thermal spraying from above the metal mesh 31a, a cavity 35 is formed immediately below the metal mesh 31a. That is, the metal mesh 31 a is not joined to the carrier 20.
- the cavity (non-joined part) 35 is formed immediately below the metal mesh 31a, the thermal stress due to the difference in linear expansion coefficient between the surface electrode 31 and the metal mesh 31a made of a metal material and the carrier 20 made of a ceramic material. Can be relaxed.
- the cavity 35 is formed along the shape of the metal mesh 31a, the surface electrode 31 has a pseudo segment structure, and thermal stress can be effectively suppressed.
- the joint between the metal mesh 31a and the surface electrode 31 can ensure electrical conductivity.
- the non-joining part between the metal mesh 31a and the surface electrode 31 can relieve the thermal stress between the surface electrode 31 and the metal mesh 31a. Accordingly, when the surface of the metal mesh 31a is shot blasted, a part of the metal mesh 31a may not be shot blasted by using a mask or the like. Thereby, the balance between the conductivity and the relaxation of thermal stress can be optimized.
- FIG. 6 is a graph showing the dependence of the minimum temperature in the carrier 20 on the input power.
- FIG. 7 is a graph showing the dependence of the maximum temperature difference in the carrier 20 on the input power. 6 and 7, the horizontal axis represents input power (kW).
- the vertical axis in FIG. 6 is the minimum temperature (° C.) in the carrier 20, and the vertical axis in FIG. 7 is the maximum temperature difference (° C.) in the carrier 20.
- Each graph shows a qualitative tendency because specific numerical values are omitted.
- the input power necessary for setting the minimum temperature in the carrier 20 to be equal to or higher than the target value is a comparative example even in the initial stage. Smaller than the initial of. In addition, the input power hardly increases even after use corresponding to 30 km travel. On the other hand, in the comparative example, as indicated by an arrow in the graph, the input power is significantly increased after use as compared with the initial stage.
- the input power is small. Therefore, the larger the maximum input power that can make the maximum temperature difference below the target value, the better.
- the maximum input power is larger than that in the comparative example even in the initial stage. Moreover, the maximum input power does not decrease even after use.
- the maximum input power is significantly reduced after use as compared with the initial stage.
- the input power that satisfies both target values simultaneously does not exist after use.
- the input power that satisfies both target values simultaneously exists even after use. That is, in the embodiment, even if the surface electrode 31 deteriorates (corresponding to the use in FIGS. 6 and 7), the current spread in the carrier axis direction is secured by the metal mesh 31a, and the minimum temperature in the carrier 20 is kept high. And the maximum temperature difference can be kept small.
- FIG. 8 is a plan view seen from directly above the surface electrode 31 of the electrically heated catalyst device 200 according to the second embodiment.
- 9 is a cross-sectional view taken along the line IX-IX in FIG.
- a metal wire 31b is embedded in the electrically heated catalyst device 200 according to the second embodiment.
- a metal wire 31 b having a rectangular cross section is embedded inside the surface electrode 31.
- the cross-sectional shape of the metal wire 31b may be circular or other shapes.
- a plurality of metal wires 31b are buried over substantially the entire surface of the surface electrode 31 formation region.
- Each metal wire 31b extends over the entire region where the surface electrode 31 is formed in the carrier axis direction.
- the plurality of metal wires 31b are arranged on each surface electrode 31 at substantially equal intervals along the circumferential direction of the carrier.
- seven metal wires 31 b are provided in parallel in the surface electrode 31.
- the number of the metal wires 31b is not limited at all.
- the metal wire 31b is preferably made of a heat-resistant (oxidation-resistant) alloy such as a stainless steel alloy, a Ni-base alloy, or a Co-base alloy.
- the cross-sectional dimensions are preferably 0.2 mm or less in diameter in the case of a circular cross section, and 0.2 mm or less in thickness and 5 mm or less in width in the case of a rectangular cross section.
- the metal wire 31b extending in the carrier axial direction is embedded in the surface electrode 31, so that the crack in the carrier circumferential direction is formed in the surface electrode 31. Even if this occurs, the spread of current in the direction of the carrier axis is maintained through the metal wire 31b. Therefore, the heat is not concentrated in the vicinity of the central portion of the carrier 20 in the axial direction, and thermal stress cracking due to this concentrated heating can be avoided.
- the metal wire 31b is embedded in the surface electrode 31, so that friction is not generated between the metal wire 31b and the mat due to a thermal cycle load. There is no fear of disconnection.
- the surface electrode 31 is formed by thermal spraying from above the metal wire 31b, a cavity (not shown) is formed immediately below the metal wire 31b. That is, the metal wire 31 b is not joined to the carrier 20. As described above, since a cavity (non-joined portion) is formed immediately below the metal wire 31b, thermal stress due to a difference in linear expansion coefficient between the surface electrode 31 and the metal wire 31b made of a metal material and the carrier 20 made of a ceramic material is generated. Can be relaxed.
- the surface of the metal wire 31b needs to be roughened by shot blasting before the surface electrode 31 is sprayed.
- the junction between the metal wire 31b and the surface electrode 31 can ensure electrical conductivity.
- the non-joining part between the metal wire 31b and the surface electrode 31 can relieve the thermal stress between the surface electrode 31 and the metal wire 31b. Therefore, when the surface of the metal wire 31b is shot blasted, a part of the metal wire 31b may not be shot blasted by using a mask or the like. Thereby, the balance between the conductivity and the relaxation of thermal stress can be optimized. Since other configurations are the same as those of the first embodiment, description thereof is omitted.
- FIGS. 10 to 12 are plan views as viewed from directly above the surface electrode 31 of the electrically heated catalyst device 200 according to the modification of the second embodiment. Any of the electrically heated catalyst devices 200 shown in FIGS. 10 to 12 can achieve the same effects as the electrically heated catalyst device 200 shown in FIG.
- the metal wire 31b may not be provided at the center portion in the carrier axial direction of the surface electrode 31 to which the wiring 32 is connected. That is, the metal wire 31b may be provided by being divided at both ends in the carrier axis direction of the surface electrode 31 via the center portion of the surface electrode 31 in the carrier axis direction.
- the metal wire 31c extending in the carrier circumferential direction is provided. May be. Such a configuration can be said to be similar to the metal mesh 31a according to the first embodiment.
- the metal wire 31b may not be provided at the center in the carrier axial direction of the surface electrode 31 to which the wiring 32 is connected. That is, the metal wire 31b may be provided by being divided at both ends in the carrier axis direction of the surface electrode 31 via the center portion of the surface electrode 31 in the carrier axis direction. Further, the metal wire 31b may be provided obliquely with an inclination from the carrier axis direction. In the example of FIG. 12, four metal wires 31 b are provided radially from the central portion of the surface electrode 31 in the carrier axis direction toward the four corners of the surface electrode 31.
- FIG. 13 is a plan view seen from directly above the surface electrode 31 of the electrically heated catalyst device 300 according to the third embodiment.
- FIG. 14A is a plan view of a punched metal plate 31d of the electrically heated catalyst device 300 according to the third embodiment.
- the metal electrode extending member extending in the carrier axial direction is provided inside the surface electrode 31 as in the first embodiment.
- a punched metal plate 31d is embedded instead of the metal mesh 31a.
- a single stamped metal plate 31 d is embedded over substantially the entire surface of the surface electrode 31 formation region.
- a number of circular punching holes are arranged in the punching metal plate 31d.
- the punched metal plate 31d is preferably made of a heat-resistant (oxidation-resistant) alloy such as, for example, a stainless steel alloy, a Ni-base alloy, or a Co-base alloy, like the metal mesh 31a according to the first embodiment.
- the punched metal plate 31d may be divided into a plurality of sheets.
- the punched metal plate 31d extending in the carrier axial direction is the surface electrode. Since it is embedded in 31, the spread of current in the direction of the carrier axis is maintained via the punched metal plate 31d. Therefore, heat is not concentrated in the vicinity of the central portion in the carrier axial direction to which the wiring 32 is connected, and thermal stress cracking due to this concentrated heating can be avoided.
- the punched metal plate 31d is embedded in the surface electrode 31, no friction is generated between the punched metal plate and the mat even under a thermal cycle load. There is no fear that the metal plate 31d is disconnected.
- the surface electrode 31 is formed by thermal spraying from above the punched metal plate 31d, a cavity (not shown) is formed immediately below the punched metal plate 31d. That is, the punched metal plate 31 d is not joined to the carrier 20.
- a cavity non-joined part
- the surface electrode 31 since the cavity is formed along the shape of the punched metal plate 31d, the surface electrode 31 has a pseudo segment structure, and thermal stress can be effectively suppressed.
- the joint between the punched metal plate 31d and the surface electrode 31 can ensure electrical conductivity.
- the non-joined portion between the punched metal plate 31d and the surface electrode 31 can relieve the thermal stress between the surface electrode 31 and the stamped metal plate 31d. Therefore, when the surface of the punched metal plate 31d is shot blasted, a part of the stamped metal plate 31d may not be subjected to shot blasting by using a mask or the like. Thereby, the balance between the conductivity and the relaxation of thermal stress can be optimized. Since other configurations are the same as those of the first embodiment, description thereof is omitted.
- FIGS. 14B and 14C are plan views of the punched metal plate 31d of the electrically heated catalyst device 300 according to the modification of the third embodiment. Even if any of the punched metal plates 31d shown in FIGS. 14B and 14C is used, the same effects as those of the electrically heated catalyst device 300 shown in FIG. 13 can be obtained.
- the shape of the punched hole may be rectangular. Further, like the punched metal plate 31d shown in FIG. 14C, the shape of the punched hole may be a diamond shape. Note that the shape of the punched hole is not particularly limited, and may be any shape.
- metal fibers having a diameter of 0.01 to 0.15 mm may be embedded in the surface electrode.
Abstract
Description
EHCの表面電極は円筒状の担体の軸方向に延設されている。また、表面電極の担体軸方向中央部に金属配線が接続され、電流が供給される。この電流が表面電極において担体軸方向に広がることにより、一対の表面電極間において担体全体が通電加熱される。
通電加熱を繰り返すと、上述の熱応力により、表面電極に担体円周方向のクラックが発生し、担体軸方向への電流の広がりが阻害される結果、表面電極と金属配線との接続部近傍(担体の軸方向中央部)が集中的に加熱されるという問題があった。
触媒が担持されたセラミックスからなる担体と、
前記担体の外周面において、互いに対向しつつ前記担体の軸方向に延設された一対の表面電極と、
前記表面電極へ外部から電力を供給する配線と、を備え、前記表面電極を介して前記担体を通電加熱する通電加熱式触媒装置であって、
前記担体の軸方向に延設された金属製の展伸部材が、前記表面電極に埋設されている、ものである。
表面電極に担体円周方向のクラックが発生しても、担体軸方向への電流の広がりが保持される通電加熱式触媒装置を提供することができる。
また、前記表面電極が、溶射により形成されることが好ましい。
さらに、前記担体と前記展伸部材との間に、空洞が形成されていることが好ましい。これにより、熱応力が緩和される。
さらに、800℃以上での使用環境に耐えるため、展伸部材が、ステンレス系合金、Ni基系合金、Co基系合金のいずれかからなることが好ましい。
前記セラミックスは、SiCを含むことが好ましい。
また、前記表面電極が、Ni-Cr合金(但し、Cr含有量は20~60質量%)又はMCrAlY合金(但し、MはFe、Co、Niのうち少なくとも一種)からなることが好ましい。
触媒が担持されたセラミックスからなる担体の表面に形成された表面電極を介して前記担体を通電加熱する通電加熱式触媒装置の製造方法であって、
前記担体の外周面に、互いに対向させて前記担体の軸方向に延設された一対の前記表面電極を形成する工程と、
前記表面電極へ外部から電力を供給する配線を接続する工程と、を備え、
前記表面電極を形成する工程において、
前記担体の軸方向に延設された金属製の展伸部材を前記表面電極に埋設する、ものである。
また、前記表面電極を形成する工程では、前記担体上に載置された前記展伸部材の上から溶射する溶射工程を備えることが好ましい。
さらに、前記担体と前記展伸部材との間に、空洞が形成されることが好ましい。
前記粗面化工程では、前記表面電極と接合する接合部については粗面化し、前記表面電極と接合しない非接合部については粗面化しないことが好ましい。
まず、図1~4を参照して、実施の形態1に係る通電加熱式触媒装置について説明する。図1は、実施の形態1に係る通電加熱式触媒装置100の斜視図である。図2は、実施の形態1に係る通電加熱式触媒装置100の表面電極31の真上から見た平面図である。図3は、図2におけるIII-III切断線による断面図であって、固定層33が形成された部位での断面図である。図4は、図2におけるIV-IV切断線による断面図である。
次に、図8、9を参照して、実施の形態2に係る通電加熱式触媒装置について説明する。図8は、実施の形態2に係る通電加熱式触媒装置200の表面電極31の真上から見た平面図である。図9は、図8におけるIX-IX切断線による断面図である。実施の形態2に係る通電加熱式触媒装置200では、図8に示すように、表面電極31の内部には、担体軸方向に延設された金属製の展伸部材として、実施の形態1に係る金属メッシュ31aに代えて、金属線31bが埋設されている。また、図9に示された断面図からも、表面電極31の内部に断面矩形状の金属線31bが埋設されていることが分かる。もちろん金属線31bの断面形状は円形その他の形状であってもよい。
その他の構成は実施の形態1と同様であるため、説明を省略する。
次に、図13、14Aを参照して、実施の形態3に係る通電加熱式触媒装置について説明する。図13は、実施の形態3に係る通電加熱式触媒装置300の表面電極31の真上から見た平面図である。図14Aは、実施の形態3に係る通電加熱式触媒装置300の打抜金属(パンチングメタル)板31dの平面図である。実施の形態3に係る通電加熱式触媒装置300では、図13に示すように、表面電極31の内部には、担体軸方向に延設された金属製の展伸部材として、実施の形態1に係る金属メッシュ31aに代えて、打抜金属板31dが埋設されている。
その他の構成は実施の形態1と同様であるため、説明を省略する。
31 表面電極
31a 金属メッシュ
31b、31c 金属線
31d 打抜金属板
32 配線
33 固定層
35 空洞
100、200、300 通電加熱式触媒装置
Claims (15)
- 触媒が担持されたセラミックスからなる担体と、
前記担体の外周面において、互いに対向しつつ前記担体の軸方向に延設された一対の表面電極と、
前記表面電極へ外部から電力を供給する配線と、を備え、前記表面電極を介して前記担体を通電加熱する通電加熱式触媒装置であって、
前記担体の軸方向に延設された金属製の展伸部材が、前記表面電極に埋設されている、通電加熱式触媒装置。 - 前記展伸部材が、メッシュ、線、打抜板のいずれかであることを特徴とする請求項1に記載の通電加熱式触媒装置。
- 前記表面電極が、溶射により形成されることを特徴とする請求項1又は2に記載の通電加熱式触媒装置。
- 前記担体と前記展伸部材との間に、空洞が形成されていることを特徴とする請求項3に記載の通電加熱式触媒装置。
- 前記展伸部材は、
前記表面電極と接合された接合部と、
前記表面電極と接合されていない非接合部と、を備えることを特徴とする請求項3又は4に記載の通電加熱式触媒装置。 - 前記展伸部材が、ステンレス系合金、Ni基系合金、Co基系合金のいずれかからなることを特徴とする請求項1~5のいずれか一項に記載の通電加熱式触媒装置。
- 前記表面電極において前記配線が接続された接続領域が、前記担体の軸方向の中央部に位置することを特徴とする請求項1~6のいずれか一項に記載の通電加熱式触媒装置。
- 前記セラミックスが、SiCを含むことを特徴とする請求項1~7のいずれか一項に記載の通電加熱式触媒装置。
- 前記表面電極が、Ni-Cr合金(但し、Cr含有量は20~60質量%)又はMCrAlY合金(但し、MはFe、Co、Niのうち少なくとも一種)からなることを特徴とする請求項1~8のいずれか一項に記載の通電加熱式触媒装置。
- 触媒が担持されたセラミックスからなる担体の表面に形成された表面電極を介して前記担体を通電加熱する通電加熱式触媒装置の製造方法であって、
前記担体の外周面に、互いに対向させて前記担体の軸方向に延設された一対の前記表面電極を形成する工程と、
前記表面電極へ外部から電力を供給する配線を接続する工程と、を備え、
前記表面電極を形成する工程において、
前記担体の軸方向に延設された金属製の展伸部材を前記表面電極に埋設する、通電加熱式触媒装置の製造方法。 - 前記展伸部材を、メッシュ、線、打抜板のいずれかとすることを特徴とする請求項10に記載の通電加熱式触媒装置の製造方法。
- 前記表面電極を形成する工程において、
前記担体上に載置された前記展伸部材の上から溶射する溶射工程を備えることを特徴とする請求項10又は11に記載の通電加熱式触媒装置の製造方法。 - 前記担体と前記展伸部材との間に、空洞が形成されることを特徴とする請求項12に記載の通電加熱式触媒装置の製造方法。
- 前記表面電極を形成する工程において、
前記溶射工程の前に、前記担体上に載置された前記展伸部材の表面を粗面化する粗面化工程を備えることを特徴とする請求項12又は13に記載の通電加熱式触媒装置の製造方法。 - 前記粗面化工程において、
前記表面電極と接合する接合部については粗面化し、前記表面電極と接合しない非接合部については粗面化しないことを特徴とする請求項14に記載の通電加熱式触媒装置の製造方法。
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US14/356,261 US9295944B2 (en) | 2011-12-27 | 2011-12-27 | Electrically heated catalyst device and its manufacturing method |
CN201180076048.5A CN104023846B (zh) | 2011-12-27 | 2011-12-27 | 通电加热式催化装置及其制造方法 |
EP11879086.4A EP2799136B1 (en) | 2011-12-27 | 2011-12-27 | Electrically heated catalyst device and its manufacturing method |
JP2013551034A JP5786961B2 (ja) | 2011-12-27 | 2011-12-27 | 通電加熱式触媒装置及びその製造方法 |
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2011
- 2011-12-27 US US14/356,261 patent/US9295944B2/en not_active Expired - Fee Related
- 2011-12-27 WO PCT/JP2011/007328 patent/WO2013098889A1/ja active Application Filing
- 2011-12-27 JP JP2013551034A patent/JP5786961B2/ja not_active Expired - Fee Related
- 2011-12-27 CN CN201180076048.5A patent/CN104023846B/zh not_active Expired - Fee Related
- 2011-12-27 EP EP11879086.4A patent/EP2799136B1/en not_active Not-in-force
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US9181838B2 (en) | 2014-04-07 | 2015-11-10 | Ford Global Technologies, Llc | Temperature maintenance and regulation of vehicle exhaust catalyst systems with phase change materials |
US9566552B2 (en) | 2014-04-07 | 2017-02-14 | Ford Global Technologies, Llc | Temperature maintenance and regulation of vehicle exhaust catalyst systems with phase change materials |
US10265657B2 (en) | 2014-04-07 | 2019-04-23 | Ford Global Technologies, Llc | Temperature maintenance and regulation of vehicle exhaust catalyst systems with phase change materials |
CN104975915A (zh) * | 2014-04-11 | 2015-10-14 | 丰田自动车株式会社 | 电加热催化剂装置及其制造方法 |
US9815024B2 (en) | 2014-04-11 | 2017-11-14 | Toyota Jidosha Kabushiki Kaisha | Electrically heated catalyst device and its manufacturing method |
CN108884737A (zh) * | 2015-11-16 | 2018-11-23 | 日本碍子株式会社 | 蜂窝型加热装置及其使用方法 |
JPWO2017086019A1 (ja) * | 2015-11-16 | 2018-08-30 | 日本碍子株式会社 | ハニカム型加熱装置及びその使用方法 |
WO2017086019A1 (ja) * | 2015-11-16 | 2017-05-26 | 日本碍子株式会社 | ハニカム型加熱装置及びその使用方法 |
US10287942B2 (en) | 2015-11-16 | 2019-05-14 | Ngk Insulators, Ltd. | Honeycomb type heating device and method for using the same |
CN108884737B (zh) * | 2015-11-16 | 2020-08-04 | 日本碍子株式会社 | 蜂窝型加热装置及其使用方法 |
JP2019171345A (ja) * | 2018-03-29 | 2019-10-10 | 日本碍子株式会社 | 電気加熱型触媒用担体 |
US10570794B2 (en) | 2018-06-01 | 2020-02-25 | Toyota Jidosha Kabushiki Kaisha | Electrically heated catalyst device |
JP2021030163A (ja) * | 2019-08-26 | 2021-03-01 | トヨタ自動車株式会社 | 電気加熱式触媒装置 |
JP7331553B2 (ja) | 2019-08-26 | 2023-08-23 | トヨタ自動車株式会社 | 電気加熱式触媒装置 |
Also Published As
Publication number | Publication date |
---|---|
EP2799136A4 (en) | 2015-04-29 |
JP5786961B2 (ja) | 2015-09-30 |
CN104023846A (zh) | 2014-09-03 |
CN104023846B (zh) | 2016-06-22 |
US20140301908A1 (en) | 2014-10-09 |
US9295944B2 (en) | 2016-03-29 |
EP2799136A1 (en) | 2014-11-05 |
JPWO2013098889A1 (ja) | 2015-04-30 |
EP2799136B1 (en) | 2016-06-29 |
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