The disclosure of Japanese Patent Application No. 2017-235077 filed on Dec. 7, 2017 including the specification, drawings and abstract is incorporated herein by reference in its entirety.
The present disclosure relates to exhaust gas catalysts for an internal combustion engine.
Japanese Patent Application Publication No. 2016-187766 discloses a catalyst for cleaning exhaust gas that is capable of generating heat upon absorption of microwaves. This exhaust gas catalyst includes a ferrite and a catalyst layer coating a surface of the ferrite. The ferrite is a magnetic material having a property of generating heat upon absorption of microwaves and autonomously stopping the heat generation once the temperature of the material reaches the Curie temperature. The catalyst layer is composed of a catalyst metal and a support layer supporting the catalyst metal. The catalyst metal is at least one of platinum (Pt), palladium (Pd), and rhodium (Rh). The support layer is composed of γ-alumina or θ-alumina. When microwaves are applied to the exhaust gas catalyst, the microwaves pass through the catalyst layer and are then absorbed by the ferrite. The heat generation of the ferrite causes an increase in the temperature of the whole exhaust gas catalyst.
Ferrites are generally composed of a multivalent element, and the valence of the element is readily changed due to variation in exhaust gas conditions. Specifically, under high-temperature conditions, magnetic materials undergo a phase change. The occurrence of a phase change of a ferrite means a change in the crystal structure of the ferrite. Under a condition in which an air-fuel ratio is in a range from a stoichiometric air-fuel ratio to a rich air-fuel ratio and a temperature is high, ferrites further undergo a chemical change. The occurrence of a chemical change of a ferrite means a change in the molecular structure of the ferrite. Under the condition in which the air-fuel ratio is in the range from the stoichiometric air-fuel ratio to the rich air-fuel ratio and the temperature is high, therefore, ferrites may undergo an irreversible change in the crystal structure or molecular structure and eventually deteriorate. By contrast, under a condition in which an air-fuel ratio is lean, change in the molecular structure of ferrites is slight. However, ferrites may be poisoned and deteriorated by a sulfur component or phosphorus component contained in the exhaust gas.
In view of such deterioration of ferrites, the surface of the ferrite of the exhaust gas catalyst described above is coated with the catalyst layer (i.e., the support layer). However, γ-alumina and θ-alumina, either of which composes the support layer, have a high specific surface area. The high specific surface area implies the possibility that pores with a volume large enough to allow gas passage are present within these alumina. The presence of pores with such a volume causes exhaust gas around the exhaust gas catalyst to easily pass through the support layer to reach the ferrite. Thus, the occurrence of the above-described deterioration of the ferrite cannot be avoided, with the result that warm-up effect based on the microwave absorption property may be lost relatively early.
The present disclosure has been made in view of the above problems and provides an exhaust gas catalyst that enables warm-up exploiting microwaves and that has high resistance to variation in exhaust gas conditions.
An aspect of the present disclosure relates to an exhaust gas catalyst for an internal combustion engine, the exhaust gas catalyst including: catalyst particles that clean exhaust gas of the internal combustion engine; and magnetic particles that are placed around the catalyst particles and that generate heat upon absorption of microwaves, wherein each of the magnetic particles includes: a core portion composed of a ferromagnetic material capable of generating heat upon absorption of microwaves; and a shell portion coating a surface of the core portion, the shell portion having a property of permitting passage of microwaves, the shell portion being superior to γ-alumina or θ-alumina in a property of blocking gases.
In the above aspect, the shell portion may be composed of at least one material of: i) silicon nitride; ii) aluminum nitride; iii) manganese oxide; iv) α-alumina; and v) silica.
In the above aspect, the shell portion may be composed of at least one material of: i) α-alumina; and ii) silica.
In the above aspect, a BET specific surface area of the shell portion may be less than 180 m2/g.
In the above aspect, a BET specific surface area of the shell portion may be less than 105 m2/g.
In the above aspect, a pore volume of the shell portion may be less than 0.7 cm2/g.
In the above aspect, a pore volume of the shell portion may be less than 0.6 cm2/g.
In the above aspect, the ferromagnetic material may include at least one material of: i) ferromagnetic oxide; ii) a ferromagnetic metal; and iii) a hexagonal ferrite.
In the above aspect, the catalyst particles may include at least one material of: i) γ-alumina; ii) θ-alumina; and iii) zirconia.
According to the present disclosure, magnetic particles each including a core portion composed of a ferromagnetic material and a shell portion coating the core portion are placed around catalyst particles. This shell portion has a property of permitting passage of microwaves. Thus, the temperature of the catalyst particles can be increased by heat generation of the core portion absorbing microwaves. Additionally, the shell portion is composed of silicon nitride, aluminum nitride, manganese oxide, α-alumina, or silica which is superior to γ-alumina or θ-alumina in a property of blocking gases. Thus, gas communication between the core portion and the outside environment can be decreased as compared to when a shell portion is composed of γ-alumina or θ-alumina. That is, entry of gas into the core portion from the outside environment and exit of gas from the core portion to the outside environment can be reduced. This can lead to an increase in the resistance of the magnetic particles to variation in exhaust gas conditions.
Features, advantages, and technical and industrial significance of exemplary embodiments of the disclosure will be described below with reference to the accompanying drawings, in which like numerals denote like elements, and wherein:
Hereinafter, embodiments of the present disclosure will be described with reference to the drawings. The same or equivalent components are denoted by the same reference signs in the figures, and the description of the components may be simplified or omitted.
An antenna 20 of a microwave oscillator 18 is provided upstream of the honeycomb substrate 16. The microwave oscillator 18 is configured to generate microwaves. The microwave oscillator 18 is, for example, a semiconductor oscillator. The microwave oscillator 18 may be configured with a magnetron, klystron, gyrotron, or the like. The antenna 20 is configured to emit microwaves toward the honeycomb substrate 16. The antenna 20 is, for example, a planar antenna, parabola antenna, or horn antenna. The frequency of the microwaves to be emitted is, for example, 2.45 GHz, 5.8 GHz, 24 GHz, or 915 MHz. The intensity of the microwaves to be emitted is not particularly limited.
The microwave oscillator 18 is driven in response to a predetermined control signal, for example, during cold start of the engine 10. Once the microwave oscillator 18 is driven, microwaves emitted from the antenna 20 are applied to (incident on) the honeycomb substrate 16. The exhaust gas catalyst supported on the rib 16a absorbs the microwaves to generate heat and become hot. The exhaust gas catalyst is activated once the temperature of the catalyst reaches a predetermined temperature range. Consequently, it becomes possible to clean exhaust gas passing through the honeycomb substrate 16.
The catalyst particles 24 are formed by supporting a noble metal such as platinum (Pt), palladium (Pd), or rhodium (Rh) on a porous ceramic. The porous ceramic is, for example, alumina (in particular γ-alumina or θ-alumina) or zirconia (ZrO2). In the catalyst particles 24, cerium (Ce) may be further supported as an additive. Under a condition in which an air-fuel ratio is lean, cerium (Ce) is chemically combined with oxygen present in exhaust gas to form ceria (CeO2), while under rich conditions, ceria (CeO2) is partially reduced as a result of part of oxygen being released (2CeO2→Ce2O3+½O2). Due to the characteristics of cerium (Ce), the catalyst particles 24 adsorb oxygen from exhaust gas and store the oxygen under the condition in which the air-fuel ratio is lean. Under rich conditions, the catalyst particles 24 release the stored oxygen.
The feature of the exhaust gas catalyst 22 lies in the structure of the magnetic particles 26. Specifically, the magnetic particles 26 have a core-shell structure.
The ferromagnetic material composing the core portion 26a is a ferromagnetic oxide, a ferromagnetic metal, or a hexagonal ferrite. The ferromagnetic material may contain any one of these substances or may contain two or more of these substances. The ferromagnetic oxide is, for example, γ-Fe2O3, Fe3O4, FeOx (1≤x≤1.5), Co—FeOx (1≤x≤1.5), Co—Fe3O4, or CrO2. The ferromagnetic metal is, for example, Fe, Fe—Co alloy, Fe—Pt, Fe3—Pt, Co—Pt, Fe4N, or Fe5C2. The outer surface of the ferromagnetic metal may include an oxide layer. The hexagonal ferrite is barium ferrite, strontium ferrite, lead ferrite, calcium ferrite, or a material resulting from substitution of any of these ferrites with Co or the like. More specific examples of the hexagonal ferrite include magnetoplumbite-type barium ferrite and strontium ferrite and magnetoplumbite-type barium ferrite and strontium ferrite partially containing a spinel phase.
The coating material composing the shell portion 26b is, for example, a ceramic such as silicon nitride (Si3N4), aluminum nitride (AlN), manganese oxide (Mn3O4), or α-alumina or silica (SiO2). The coating material may contain any one of these substances or may contain two or more of these substances. These ceramics and silica have a property of permitting passage of microwaves and are superior to γ-alumina or θ-alumina in a property of blocking gases (gas barrier property). Thus, these ceramics and silica have a property of permitting passage of microwaves while blocking passage of gases such as exhaust gas to a greater extent than γ-alumina or θ-alumina. These ceramics and silica have heat resistance and heat conductivity in addition to the above property. α-alumina and silica have high producibility and high poisoning resistance in addition to the above properties. It can therefore be considered that α-alumina and silica are particularly preferred as the coating material composing the shell portion 26b.
2.2 Advantage and Disadvantage of Ferromagnetic Materials
Typical substances having the property of generating heat upon absorption of microwaves include dielectric materials and magnetic materials. Some dielectric materials have high durability. However, in the 2.45 GHz band which is the ISM band for microwaves, the wavelength of microwaves is around 12 cm, and there exist loops and nodes in microwave electric fields. Thus, it is difficult to cause a microwave electric field to act uniformly on a dielectric material. Additionally, dielectric materials have a property of becoming able to absorb microwaves to a greater extent with an increase in temperature. The use of a dielectric material is therefore likely to result in localization of the heat generating site, leading to uneven heating.
Magnetic materials have a property of ceasing to exhibit magnetism at a temperature equal to or higher than the Curie temperature. Thus, once the temperature of a magnetic material increases beyond the Curie temperature, the magnetic material becomes insensitive to the action of microwaves.
Furthermore, when a magnetic material is designed to have a Curie temperature within the activation temperature range mentioned above, not only the temperature of the magnetic material but also the temperature of a substance placed around the magnetic material can be increased to the Curie temperature. As previously stated, however, ferrites can deteriorate due to variation in exhaust gas conditions. This deterioration will be described with reference to
As indicated by an arrow in the center of
If a phase change into iron(II) oxide (FeO) occurs alone and then the temperature of the atmosphere surrounding iron(II) oxide (FeO) decreases, a phase change may occur in a direction opposite to the direction of the arrow shown in
Under the condition in which the air-fuel ratio is lean, iron(II, III) oxide (Fe3O4) is not subjected to any reducing action. Thus, under the condition in which the air-fuel ratio is lean, iron(II, III) oxide (Fe3O4) undergoes only a phase change, so that a subsequent decrease in the temperature of the surrounding atmosphere can cause a phase change of iron(II) oxide (FeO) into iron(II, III) oxide (Fe3O4). Under such a condition in which the air-fuel ratio is lean, however, iron(II, III) oxide (Fe3O4) may be poisoned by a sulfur component or phosphorus component contained in the exhaust gas. The poisoning will result in the loss of the properties as a ferromagnetic material.
Materials subject to influence on the above-described properties as a ferromagnetic material are not limited to iron(II, III) oxide (Fe3O4) or ferrites containing iron(II, III) oxide (Fe3O4) as a main component. For example, chromium(IV) oxide (CrO2), which has the properties as a ferromagnetic material like iron(II, III) oxide (Fe3O4), can lose the properties as a ferromagnetic material by undergoing a phase change into chromium(III) oxide (Cr2O3). Additionally, under the condition in which the air-fuel ratio is in the range from the stoichiometric air-fuel ratio to the rich air-fuel ratio and the temperature is high, chromium(IV) oxide (CrO2) is reduced and converted to chromium(III) oxide (Cr2O3). Thus, the ferromagnetic oxides and ferromagnetic metals as mentioned above have the same disadvantage as iron(II, III) oxide (Fe3O4) described with reference to
In the exhaust gas catalyst according to the present disclosure, the shell portion 26b is provided on a surface of a ferromagnetic material powder composing the core portion 26a. The coating material composing the shell portion 26b is superior to γ-alumina or θ-alumina in the property of blocking gases.
Having a small BET specific surface area and a small pore volume means being superior in the property of blocking gases. Being a coating material superior in the property of blocking gases means that the coating material, when used for the shell portion 26b, exhibits a high ability to inhibit gas communication between the core portion 26a and the outside environment. Thus, even under the condition in which the air-fuel ratio is in the range from the stoichiometric air-fuel ratio to the rich air-fuel ratio and the temperature is high, the influence of reducing components present in the exhaust gas can be diminished. Consequently, it is possible to decrease the extent to which the ferromagnetic material in the core portion 26a is subjected to a reducing action. In addition, under the condition in which the air-fuel ratio is lean, the influence of poisoning components present in the exhaust gas can be diminished.
Furthermore, even when the temperature of the atmosphere surrounding the magnetic particles 26 increases to induce a phase change which entails release of oxygen from the crystal structure composing the core portion 26a, the released oxygen can be retained inside the shell portion 26b. Thus, after a decrease in the temperature of the atmosphere surrounding the magnetic particles 26, the core portion 26a can incorporate the released oxygen into the crystal structure to regain the properties as a ferromagnetic material. For these reasons, the configuration of the exhaust gas catalyst according to the present disclosure can achieve an increased resistance of the magnetic particles 26 to variation in exhaust gas conditions. Consequently, the warm-up effect based on the microwave absorption property of the magnetic particles 26 can last for a long period of time.
In the method illustrated in
3.2 Second Method
In the method illustrated in
3.3 Third Method
In the method illustrated in
3.4 Fourth Method
In the method illustrated in
Although numerical values indicating the number, numerical quantity, amount, or range may be presented for the elements of the foregoing embodiment, the present disclosure is not limited to the presented numerical values unless otherwise explicitly stated or unless it is clear that the numerical values should be employed in principle. The structures etc. described for the foregoing embodiment are not necessarily essential for the disclosure unless otherwise explicitly stated or unless it is clear that such structures etc. should be employed in principle.
Number | Date | Country | Kind |
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2017-235077 | Dec 2017 | JP | national |