EXHAUST GAS CATALYST FOR INTERNAL COMBUSTION ENGINES
20190176140 ยท 2019-06-13
Assignee
Inventors
- Hiroshi OTSUKI (Gotemba-shi, JP)
- Shinji IKEDA (Mishima-shi, JP)
- Keishi Takada (Mishima-shi, JP)
- Tetsuya Sakuma (Mishima-shi, JP)
- Norio ISHIKAWA (Toyota-shi, JP)
Cpc classification
B01J35/33
PERFORMING OPERATIONS; TRANSPORTING
F01N2510/06
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F01N3/2828
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F01N2240/05
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
Y02T10/12
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
F01N2330/06
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
B01J2231/005
PERFORMING OPERATIONS; TRANSPORTING
F01N3/202
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
International classification
B01J37/34
PERFORMING OPERATIONS; TRANSPORTING
B01J23/46
PERFORMING OPERATIONS; TRANSPORTING
Abstract
An exhaust gas catalyst includes: catalyst particles that clean exhaust gas; and magnetic particles that are placed around the catalyst particles and that generate heat upon absorption of microwaves. 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 -alumina or -alumina in a property of blocking gases.
Claims
1. An exhaust gas catalyst for an internal combustion engine, comprising: 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 -alumina or -alumina in a property of blocking gases.
2. The exhaust gas catalyst according to claim 1, wherein the shell portion is composed of at least one material of: i) silicon nitride; ii) aluminum nitride; iii) manganese oxide; iv) -alumina; and v) silica.
3. The exhaust gas catalyst according to claim 1, wherein the shell portion is composed of at least one material of: i) -alumina; and ii) silica.
4. The exhaust gas catalyst according to claim 1, wherein a BET specific surface area of the shell portion is less than 180 m.sup.2/g.
5. The exhaust gas catalyst according to claim 1, wherein a BET specific surface area of the shell portion is less than 105 m.sup.2/g.
6. The exhaust gas catalyst according to claim 1, wherein a pore volume of the shell portion is less than 0.7 cm.sup.2/g.
7. The exhaust gas catalyst according to claim 1, wherein a pore volume of the shell portion is less than 0.6 cm.sup.2/g.
8. The exhaust gas catalyst according to claim 1, wherein the ferromagnetic material includes at least one material of: i) ferromagnetic oxide; ii) a ferromagnetic metal; and iii) a hexagonal ferrite.
9. The exhaust gas catalyst according to claim 1, wherein the catalyst particles include at least one material of: i) -alumina; ii) -alumina; and iii) zirconia.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] 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:
[0018]
[0019]
[0020]
[0021]
[0022]
[0023]
[0024]
[0025]
[0026]
[0027]
[0028]
[0029]
DETAILED DESCRIPTION OF EMBODIMENTS
[0030] 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.
1. Outline of Exhaust Gas Control System
[0031]
[0032] 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.
[0033] 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.
2. Description of Exhaust Gas Catalyst According to Present Disclosure
2.1 Description of Configuration of Exhaust Gas Catalyst
[0034]
[0035] 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 -alumina or -alumina) or zirconia (ZrO.sub.2). 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 (CeO.sub.2), while under rich conditions, ceria (CeO.sub.2) is partially reduced as a result of part of oxygen being released (2CeO.sub.2.fwdarw.Ce.sub.2O.sub.3+O.sub.2). 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.
[0036] 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.
[0037] 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, -Fe.sub.2O.sub.3, Fe.sub.3O.sub.4, FeO.sub.x (1x1.5), CoFeO.sub.x (1x1.5), CoFe.sub.3O.sub.4, or CrO.sub.2. The ferromagnetic metal is, for example, Fe, FeCo alloy, FePt, Fe.sub.3Pt, CoPt, Fe.sub.4N, or Fe.sub.5C.sub.2. 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.
[0038] The coating material composing the shell portion 26b is, for example, a ceramic such as silicon nitride (Si.sub.3N.sub.4), aluminum nitride (AlN), manganese oxide (Mn.sub.3O.sub.4), or -alumina or silica (SiO.sub.2). 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 -alumina or -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 -alumina or -alumina. These ceramics and silica have heat resistance and heat conductivity in addition to the above property. -alumina and silica have high producibility and high poisoning resistance in addition to the above properties. It can therefore be considered that -alumina and silica are particularly preferred as the coating material composing the shell portion 26b.
[0039] 2.2 Advantage and Disadvantage of Ferromagnetic Materials
[0040] 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.
[0041] 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.
[0042] 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
[0043] As indicated by an arrow in the center of
[0044] 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
[0045] Under the condition in which the air-fuel ratio is lean, iron(II, III) oxide (Fe.sub.3O.sub.4) is not subjected to any reducing action. Thus, under the condition in which the air-fuel ratio is lean, iron(II, III) oxide (Fe.sub.3O.sub.4) 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 (Fe.sub.3O.sub.4). Under such a condition in which the air-fuel ratio is lean, however, iron(II, III) oxide (Fe.sub.3O.sub.4) 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.
[0046] Materials subject to influence on the above-described properties as a ferromagnetic material are not limited to iron(II, III) oxide (Fe.sub.3O.sub.4) or ferrites containing iron(II, III) oxide (Fe.sub.3O.sub.4) as a main component. For example, chromium(IV) oxide (CrO.sub.2), which has the properties as a ferromagnetic material like iron(II, III) oxide (Fe.sub.3O.sub.4), can lose the properties as a ferromagnetic material by undergoing a phase change into chromium(III) oxide (Cr.sub.2O.sub.3). 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 (CrO.sub.2) is reduced and converted to chromium(III) oxide (Cr.sub.2O.sub.3). Thus, the ferromagnetic oxides and ferromagnetic metals as mentioned above have the same disadvantage as iron(II, III) oxide (Fe.sub.3O.sub.4) described with reference to
2.3 Effects Provided by Configuration of Exhaust Gas Catalyst According to Present Disclosure
[0047] 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 -alumina or -alumina in the property of blocking gases.
[0048] 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.
[0049] 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.
3. Specific Methods for Obtaining Exhaust Gas Catalyst According to Present Disclosure
3.1 First Method
[0050]
[0051]
[0052] In the method illustrated in
[0053] 3.2 Second Method
[0054]
[0055] In the method illustrated in
[0056] 3.3 Third Method
[0057]
[0058]
[0059] In the method illustrated in
[0060] 3.4 Fourth Method
[0061]
[0062] In the method illustrated in
[0063] 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.