Title of Invention	PARTICULATE COMBUSTION CATALYST
Abstract	The particulate combustion catalyst has a carrier, and a catalyst component supported on the carrier and formed of an alloy composed of Ag in an amount of 85 to 20 at. % and at least one noble metal selected from the group consisting of Pd, Pt, and Au in an amount of 15 to 80 at%. The particulate combustion catalyst has high-temperature durability, realizes removal of soot through oxidation at low temperature without employment of an expensive noble metal, and enables oxidation reaction to proceed with the aid of only oxygen and thus realizes removal of soot through oxidation at low temperature regardless of the NOx concentration of exhaust gas. The invention also provides a method for producing the catalyst, a particulate filter coated with the particulate combustion catalyst, a method for producing the particulate filter, an exhaust gas cleaning apparatus having the particulate filter coated with the particulate combustion catalyst.

Title of Invention

PARTICULATE COMBUSTION CATALYST

Abstract

The particulate combustion catalyst has a carrier, and a catalyst component supported on the carrier and formed of an alloy composed of Ag in an amount of 85 to 20 at. % and at least one noble metal selected from the group consisting of Pd, Pt, and Au in an amount of 15 to 80 at%. The particulate combustion catalyst has high-temperature durability, realizes removal of soot through oxidation at low temperature without employment of an expensive noble metal, and enables oxidation reaction to proceed with the aid of only oxygen and thus realizes removal of soot through oxidation at low temperature regardless of the NOx concentration of exhaust gas. The invention also provides a method for producing the catalyst, a particulate filter coated with the particulate combustion catalyst, a method for producing the particulate filter, an exhaust gas cleaning apparatus having the particulate filter coated with the particulate combustion catalyst.

Full Text	FORM 2 THE PATENT ACT 1970 (39 of 1970) & The Patents Rules, 2003 COMPLETE SPECIFICATION (See Section 10, and rule 13) 1. TITLE OF INVENTION PARTICULATE COMBUSTION CATALYST 2. APPLICANT(S) a) Name : MITSUI MINING & SMELTING CO., LTD. b) Nationality : JAPANESE Company c) Address : 1-11-1, OSAKI, SHINAGAWA-KU, TOKYO 141-8584, JAPAN 3. PREAMBLE TO THE DESCRIPTION The following specification particularly describes the invention and the manner in which it is to be performed : - Technical Field The present invention relates to a particulate combustion catalyst, to a method for producing the catalyst, to a particulate filter, and to an exhaust gas cleaning apparatus. More particularly, the present invention relates to a particulate combustion catalyst which realizes removal (through oxidation) of particulate matter discharged from a diesel internal combustion engine; to a method for producing the catalyst; to a particulate filter coated with the particulate combustion catalyst; and to an exhaust gas cleaning apparatus including the particulate filter coated with the particulate combustion catalyst. Background Art Exhaust gas discharged from diesel engines contains nitrogen oxides (NOx) and particulate matter, and release of such substances into the atmosphere without any treatment is a main cause of air pollution. Therefore, demand has arisen for strict regulation for such substances. There has been proposed, as effective means for removing particulate matter, a flow-through oxidation catalyst for combustion of soluble organic fractions (SOFs), and a diesel exhaust gas trapping system employing a diesel particulate filter (DPF) for trapping soot. However, for regeneration of such a DPF, particulate matter trapped therein must be continuously removed through oxidation. Hitherto, a variety of continuous regeneration systems have been proposed, and examples thereof include a system employing a catalyst including a carrier made of an inorganic oxide (e.g., zirconium oxide, vanadium oxide, or cerium oxide), and an expensive noble metal (e.g., Pt) supported on the carrier (see, for example, Patent Document 1,2, or 3); and a continuous regeneration method involving NO2 (see, for example, Patent Document 4). This continuous regeneration method requires provision, upstream of a DPF, of an oxidation catalyst (e.g., Pt) for oxidizing NO into NO2, and thus involves high cost. In addition, reaction involving NO2 is affected by the ratio of NOx to C, and many restrictions are imposed on the employment of this method. There has been proposed a particulate combustion catalyst which exhibits excellent heat resistance, which realizes removal of soot through oxidation at low temperature without employment of an expensive noble metal, and which enables oxidation reaction to proceed with the aid of only oxygen and thus realizes removal of soot through oxidation at low temperature regardless of the NOx concentration of exhaust gas. The proposed particulate combustion catalyst is composed of a carrier formed of a cerium-zirconium composite oxide having a cerium oxide content of 5 to 50 mass%, and a first catalyst which is supported on the carrier and which is formed of at least one metal selected from Ag and Ru or an oxide of the metal (see Patent Document 5). Prior Art Documents Patent Documents Patent Document 1: Japanese Patent Application Laid-Open (kokai) No. H10-047035 Patent Document 2: Japanese Patent Application Laid-Open (kokai) No. 2003-334443 Patent Document 3: Japanese Patent Application Laid-Open (kokai) No. 2004-058013 Patent Document 4: Japanese Patent No. 3012249 Patent Document 5: Japanese Patent No. 4144898 Summary of the Invention Problems to be Solved by the Invention An object of the present invention is to provide a particulate combustion catalyst which has durability in use at high temperature (hereinafter referred to as high-temperature durability) more excellent than that of the particulate combustion catalyst disclosed in Patent Document 5, which realizes removal of soot through oxidation at low temperature without employment of an expensive noble metal, and which enables oxidation reaction to proceed with the aid of only oxygen and thus realizes removal of soot through oxidation at low temperature regardless of the NOx concentration of exhaust gas. Another object of the present invention is to provide a method for producing the catalyst. Still another object of the present invention is to provide a particulate filter coated with the particulate combustion catalyst. Still another object of the invention is to provide a method for producing the particulate filter. Yet another object of the present invention is to provide an exhaust gas cleaning apparatus comprising the particulate filter coated with the particulate combustion catalyst. Means for Solving the Problems The present inventors have carried out extensive studies in order to attain the aforementioned objects, and have found that the objects can be attained by employing, as a catalyst component of a particulate combustion catalyst, an alloy containing Ag and at least one noble metal selected from the group consisting of Pd, Pt, and Au. The present invention has been accomplished on the basis of this finding. Accordingly, the particulate combustion catalyst of the present invention is characterized by comprising a carrier, and a catalyst component supported on the carrier and formed of an alloy composed of Ag in an amount of 85 to 20 at. % and at least one noble metal selected from the group consisting of Pd, Pt, and Au in an amount of 15 to 80 at.%. The method of the present invention for producing a particulate combustion catalyst is characterized by comprising mixing an aqueous solution containing Ag ions with an aqueous solution containing ions of at least one noble metal selected from the group consisting of Pd, Pt, and Au; adding a powder of a catalyst carrier to the aqueous solution mixture with stirring, to thereby form a slurry; exsiccating the slurry and drying; and firing the dried product in air at a firing temperature of 700 to 1,000°C for a period of time of [50 - 0.047x (firing temperature)(°C)] (hour) or longer. The present invention also provides a particulate filter characterized by being coated with any of the aforementioned particulate combustion catalysts. The present invention also provides an exhaust gas cleaning apparatus characterized by comprising a particulate filter coated with any of the aforementioned particulate combustion catalysts. The method of the present invention for producing a particulate filter is characterized by comprising mixing and pulverizing a carrier with a binder component and water, to thereby form a slurry; coating a filter substrate with the slurry; firing the filter substrate, to thereby form a wash-coating layer; impregnating the wash-coating layer with a mixture of an aqueous solution containing Ag ions and an aqueous solution containing ions of at least one noble metal selected from the group consisting of Pd, Ft, and Au, as catalyst components; drying the filter substrate; and firing the dried product in air at a firing temperature of 700 to 1,000°C for a period of time of [50 - 0.047x(firing temperature)(°C)] (hour) or longer. Effects of the Invention The particulate combustion catalyst of the present invention has excellent high-temperature durability, which realizes removal of soot through oxidation at low temperature, and which enables oxidation reaction to proceed with the aid of only oxygen and thus realizes removal of soot through oxidation at low temperature regardless of the NOx concentration of exhaust gas. Brief Description of the Drawings [Fig. 1] A graph showing the relationship between the Pd content of the particulate combustion catalyst and combustion initiation temperature (Tig). [Fig. 2] A graph showing the relationship between the Pd content and XRD peak shift of the particulate combustion catalyst after thermal treatment at various temperature. [Fig. 3] A chart showing a change in diffraction peak (peak shift). Modes for Carrying Out the Invention The particulate combustion catalyst of the present invention employs, as a catalyst component, an alloy composed of Ag and at least one noble metal selected from the group consisting of Pd, Pt, and Au, preferably an alloy composed of Ag and Pd and/or Pt, in order to lower the combustion initiation temperature. However, when the alloy contains at least one noble metal selected from the group consisting of Pd, Pt, and Au in an amount or amounts less than 20 at.% or in excess of 85 at.%, the combustion initiation temperature is not sufficiently lowered. Thus, the catalyst component is an alloy composed of 85 to 20 at.% (preferably 80 to 30 at.%) of Ag and 15 to 80 at.% (preferably 20 to 70 at.%) of at least one noble metal selected from the group consisting of Pd, Pt, and Au. In order to reduce the amount of expensive noble metal so as to reduce production cost, the alloy is preferably composed of 80 to 65 at.% of Ag and 20 to 35 at.% of noble metal. Notably, when Pd is used as a noble metal, the effect of firing particulates at low temperature is most fully attained. The particulate combustion catalyst of the present invention preferably contains an alloy serving as the catalyst component in an amount of 0.5 to 30 parts by mass with respect to 100 parts by mass of the carrier, more preferably 0.5 to 15 parts by mass (mass%). When the amount of alloy with respect to that of the carrier is less than 0.5 mass%, the catalytic effect is not sufficiently attained, whereas when the amount is in excess of 30 mass%, the catalytic activity (per unit mass) of the supported alloy tends to decreases. In addition to the aforementioned alloys, the particulate combustion catalyst of the present invention may employ, in combination, a catalyst formed of elemental Ag, Pt, Pd, or Au. The particulate combustion catalyst of the present invention may employ any of the carriers which are generally employed as carriers of particulate combustion catalysts containing Ag as a catalyst component. However, preferably employed is a carrier which attains high-speed transfer of oxygen therefrom and combustion of particulates at high efficiency. Examples of such carries include CeCh-ZrCh and ZrO2. Of these, Ce02 -ZrO2 is more preferably used. When a Ce02-Zr02 carrier is used in the particulate combustion catalyst of the present invention, the CeO2 content of the composite oxide is preferably 5 to 50 mass%. When the CeO2 content is in excess of 50 mass%, the specific surface area of the carrier decreases at high temperature (e.g., 700°C or higher), in some cases, eventually causing thermal deterioration of the catalyst, whereas when Ce02 content is less than 5 mass%, the catalyst may be thermally deteriorated in some cases. The carrier of the particulate combustion catalyst of the present invention is preferably formed of a Ce02 -ZrO2 -based composite oxide containing at least one metal selected from among Nd, La, Fe, Y, Pr, Ba, Ca, Mg, Sn, and Sr. By virtue of the presence of these metallic elements, the carrier formed of the CeO2 -Z1O2 -based composite oxide exhibits improved thermal stability and improved oxidation performance at low temperature. In order to fully attain these effects, the amount of oxide containing at least one metal selected from among Nd, La, Fe, Y, Pr, Ba, Ca, Mg, Sn, and Sr must be 1 mass% or more. However, when the amount of metal oxide is in excess of 35 mass%, the relative amounts of CeC»2 and Zr02 decrease, and the performance of the carrier formed of the CeCh -ZrCh -based composite oxide is likely to be impaired. Therefore, the carrier employed in the catalyst is preferably a CeO2 -Zr02 -based composite oxide having an amount of oxide containing at least one metal selected from among Nd, La, Fe, Y, Pr, Ba, Ca, Mg, Sn, and Sr (the total amount in the case where a plurality of metal oxides are present) of 1 to 35 mass% and a CeCh content of 5 to 50 mass %. One embodiment of the method of the present invention for producing a particulate combustion catalyst is as follows. Firstly, an aqueous solution containing Ag ions (e.g., aqueous silver nitrate solution) and an aqueous solution containing ions of at least one noble metal selected from the group consisting of Pd, Pt, and Au (e.g., aqueous palladium nitrate solution, dinitrodiamine-Pt nitrate solution, or aqueous platinum chloride solution) were mixed at such a ratio that the amount of Ag is adjusted to 85 to 20 at.% and the amount of at least one noble metal selected from the group consisting of Pd, Pt, and Au is adjusted to 15 to 80 at.%. To the aqueous solution mixture, the aforementioned carrier powder is added in such an amount that the total metal amount of the catalyst component(s) with respect to 100 parts by mass of the carrier is adjusted to 0.5 to 30 parts by mass, and the mixture is stirred, to thereby form a slurry. The slurry is exsiccated and further dried at a specific temperature (e.g., 120°C). The dried product is fired in air at 700 to 1,000°C, preferably 800 to 950°C for a period of time of [50 - 0.047x (firing temperature)(°C)] (hour) or longer. Through the procedure, alloying of Ag with at least one noble metal selected from the group consisting of Pd, Pt, and Au is completed. The firing time is [50 - 0.047x (firing temperature)(°C)] (hour) or longer, and preferably 10 to 30 hours, more preferably 15 to 25 hours. The firing time [50 - 0.047x(firing temperature) (°C)] (hour) or longer, defined in the present invention, has been derived from a large number of times of experiments. In the particulate combustion catalyst of the present invention employing the aforementioned alloy serving as a catalyst component, the XRD peak of the catalyst is preferably shifted by 0.45° or more from the XRD peak of a particulate combustion catalyst employing Ag as a sole catalyst component. The shift of the XRD peak of the particulate combustion catalyst [shift of the peak attributed to Ag(lll)] is an index for the degree of formation of solid solution in the alloy or the degree of alloying. As is clear from the description hereinbelow, the shift varies depending on the alloy composition and the thermal treatment temperature (firing temperature). In consideration that the particulate filter of the present invention is produced by causing the particulate combustion catalyst of the present invention to be held on a base, preferably, the surface of the carrier is provided with a binder component such as SiO2, Ti02, Zr02, or AI2O3. When such a binder component is provided on the surface of the carrier, adhesion between the base and the carrier is enhanced, and the catalyst exhibits improved durability and heat resistance. The particulate filter of the present invention may assume any known form of particulate filter, but preferably has a three-dimensional structure. Specific examples of filters having a three-dimensional structure include a wall-through filter, a flow-through honeycomb filter, a wire mesh filter, a ceramic fiber filter, a metallic porous filter, a particle-charged filter, and a foam filter. Examples of the material of the base include ceramic materials such as cordierite and SiC; Fe-Cr-Al alloys; and stainless steel alloys. The exhaust gas cleaning apparatus of the present invention, which includes therein the aforementioned particulate filter of the present invention, will be readily appreciated by those skilled in the art. Next will be described a method for producing the particulate filter of the present invention. A cerium zirconium composite oxide serving as a carrier is mixed with a binder component (e.g., S1O2 or alumina sol) and water, and the resultant mixture is finely milled by means of a milling apparatus (e.g., a ball mill). A particulate filter substrate (e.g., a wire mesh filter) is coated with the thus-obtained slurry. In general, the slurry-coated filter is fired at a temperature of about 500°C to about 700°C The thus-formed wash-coating layer is impregnated with, for example, an aqueous solution mixture of, for example, aqueous silver nitrate solution and aqueous palladium nitrate solution, and then drying and firing are carried out. Firing is performed under the same firing condition as employed in the aforementioned particulate combustion catalyst production method. The total catalyst coating amount is preferably about 10 to about 100 g/L (for a wall-flow DPF) or about 50 to about 150 g/L (for a wire mesh DPF). When the total catalyst coating amount is excessively small, sufficient performance fails to be attained, whereas when the total catalyst coating amount is excessively large, back pressure to exhaust gas increases. Examples The present invention will next be described in detail with reference to Examples and Comparative Examples. In each of the Examples and Comparative Examples, a parenthesized numerical value following each of the oxides forming a composite oxide (i.e., carrier) represents the amount (mass%) of the constitutive oxide with respect to the entirety of the composite oxide. Examples 1 to 5, and Comparative Examples 1 to 4 To a catalyst component solution having a metal element content of 5 mass% (with respect to the mass of carrier), water (30 g), and the mixture was stirred to thereby form an aqueous solution. The employed catalyst component solutions are as follows: aqueous silver nitrate solution (Comparative Example 1), solution mixture of aqueous silver nitrate solution and aqueous palladium nitrate solution (Ag : Pd = 95 : 5 (atomic)) (Comparative Example 2), solution mixture of aqueous silver nitrate solution and aqueous palladium nitrate solution (Ag : Pd = 90 : 10 (atomic)) (Comparative Example 3), solution mixture of aqueous silver nitrate solution and aqueous palladium nitrate solution (Ag : Pd = 80 : 20 (atomic)) (Example 1), solution mixture of aqueous silver nitrate solution and aqueous palladium nitrate solution (Ag : Pd = 70 : 30 (atomic)) (Example 2), solution mixture of aqueous silver nitrate solution and aqueous palladium nitrate solution (Ag : Pd = 50 : 50 (atomic)) (Example 3), solution mixture of aqueous silver nitrate solution and aqueous palladium nitrate solution (Ag : Pd = 30 : 70 (atomic)) (Example 4), solution mixture of aqueous silver nitrate solution and aqueous palladium nitrate solution (Comparative Example 4), and solution mixture of aqueous silver nitrate solution and dinitrodiamine-Pt nitrate solution (Ag : Pd = 80 : 20 (atomic)) (Example 5). To each of the thus-prepared solutions, a powder of a composite oxide (Ce02(21) + ZrCh (72) + La2O3 (2) + Nd2O3 (5)) (5.0 g) was added, and the mixture was stirred for 30 minutes, to thereby form a slurry. The thus-formed slurry was exsiccated to dryness and further dried at 120°C for 3 hours. Subsequently, the dried product was fired in air at 800°C for 20 hours. Thus thus-yielded particulate combustion catalyst was found to have a catalyst metal content of 5 mass% with respect to the mass of carrier. The Tig (combustion initiation temperature) of each particulate combustion catalyst powder produced in Examples 1 to 4 and Comparative Examples 1 to 4 was measured through the following method. Each particulate combustion catalyst powder {20 mg) produced in Examples 1 to 4 and Comparative Examples 1 to 4 and carbon (2 mg) (Printex-V (toner carbon), product of Degussa) were mixed for 15 seconds by means of a mortar agate. The mixture was fixed at a center portion of a quartz-made reaction tube by use of quartz wool. While a circulation gas having the below-described composition was caused to flow through the quartz reaction tube at the below-described flow rate, the temperature of the reaction tube was elevated at the below-described temperature elevation rate by means of an electric furnace, and CO and CO2 concentrations were measured at the outlet of the reaction tube by means of an infrared analyzer. The temperature as measured at the inlet of the catalyst-containing reaction tube when CO2+CO concentration reached 30 ppm (i.e., electric furnace control temperature) was regarded as Tig. Fig. 1 shows the combustion initiation temperatures of the particulate combustion catalyst powders. Gas composition: O2:10%, N2: balance Flow rate: 400 cc/min Temperature elevation rate: 10 degrees (°C)/min As is clear from the graph of Fig. 1, an alloy composed of 85 to 20 at.% of Ag and 15 to 80 at.% of at least one noble metal selected from the group consisting of Pd, Pt, and Au is preferably employed as a catalyst component. More preferably, an alloy composed of 80 to 30 at.% of Ag and 20 to 70 at.% of at least one noble metal selected from the group consisting of Pd, Pt, and Au is preferably employed as a catalyst component. The procedure of producing particulate combustion catalyst powders of Example 1, Comparative Example 1, and Example 5 was repeated, except that the firing temperature was changed to 800°C, 900°C, and 1,000°C, to thereby form catalyst powders. In a similar manner, the combustion initiation temperature (Tig) of each catalyst powder was measured. The combustion initiation temperatures of the particulate combustion catalyst powders are shown in Table 1. [Table 1] Table 1 (Tig temp.) Firing temp. 800°C 900°C 1,000°C Ag Ag-20 at.% Pd Ag-20 at.% Pt 294°C 265°C 298°C 284°C 323°C 293°C 306°C As is clear from Table 1, when an alloy of Ag 80 at.% and Pd 20 at.% or an alloy of Ag 80 at.% and Pt 20 at.% was employed as a catalyst component, high-temperature durability of the catalyst is more effectively improved, as compared with the case where Ag is employed as a sole catalyst component. The particulate combustion catalysts having a Pd content of 5 at.%, 10 at.%, or 20 at.% and treated at 800°C; the particulate combustion catalysts having a Pd content of 20 at.% and treated at 900°C; and the particulate combustion catalysts having a Pd content of 20 at.% and treated at 1,000°C were analyzed in terms of shift of XRD peak [the peak attributed to Ag(lll)] (the degree of formation of solid solution in the alloy or the degree of alloying). Fig. 2 shows the peak shifts of the respective particulate combustion catalyst powders. The mode of shifting the peak is shown in Fig. 3. Preferably/ alloying is performed such that the XRD peak of the catalyst component of the aforementioned alloy is increased by about 0.45° or more from that of the catalyst component employing Ag as a sole catalyst component. As is clear from the graph of Fig. 2, the peak shift increases as the Pd content increases and as the thermal treatment temperature is elevated, indicating that solid solution formation or alloying is promoted. WE CLAIM: 1. A particulate combustion catalyst, characterized by comprising a carrier, and a catalyst component supported on the carrier and formed of an alloy composed of Ag in an amount of 85 to 20 at.% and at least one noble metal selected from the group consisting of Pd, Pt, and Au in an amount of 15 to 80 at.%. 2. A particulate combustion catalyst according to claim 1, wherein the catalyst component is formed of an alloy composed of Ag in an amount of 80 to 30 at.% and at least one noble metal selected from the group consisting of Pd, Pt, and Au in an amount of 20 to 70 at.%. 3. A particulate combustion catalyst according to claim 1 or 2, wherein the catalyst component is formed of an alloy composed of Ag and at least one noble metal selected from the group consisting of Pt and Pd. 4. A particulate combustion catalyst according to claim 1, 2, or 3, wherein the XRD peak of the catalyst employing the alloy as a catalyst component is shifted by 0.45° or more from the XRD peak of a particulate combustion catalyst employing Ag as a sole catalyst component. 5. A particulate combustion catalyst according to claim 1, 2, 3, or 4, wherein the carrier is formed of a Ce02 -Zr02 -based material. 6. A method for producing a particulate combustion catalyst as recited in any one of claims 1 to 5, characterized in that the method comprises mixing an aqueous solution containing Ag ions with an aqueous solution containing ions of at least one noble metal selected from the group consisting of Pd, Pt, and Au; adding a powder of a catalyst carrier to the aqueous solution mixture with stirring, to thereby form a slurry; exsiccating the slurry and drying; and firing the dried product in air at a firing temperature of 700 to 1,000°C for a period of time of [50 - 0.047x(firing temperature)(°C)] (hour) or longer. 7. A particulate filter characterized by being coated with a particulate combustion catalyst as recited in any one of claims 1 to 5. 8. A method for producing a particulate filter as recited in claim 7, characterized in that the method comprises mixing and pulverizing a carrier with a binder component and water, to thereby form a slurry; coating a filter substrate with the slurry; firing the filter substrate, to thereby form a wash-coating layer; impregnating the wash-coating layer with a mixture of an aqueous solution containing Ag ions and an aqueous solution containing ions of at least one noble metal selected from the group consisting of Pd, Pt, and Au, as catalyst components; drying the filter substrate; and firing the dried product in air at a firing temperature of 700 to 1,000°C for a period of time of [50 - 0.047x(firing temperature)(°C)] (hour) or longer. 9. An exhaust gas cleaning apparatus characterized by comprising a particulate filter coated with a particulate combustion catalyst as recited in any one of claims 1 to 5.

Full Text

FORM 2
THE PATENT ACT 1970
(39 of 1970)
&
The Patents Rules, 2003 COMPLETE SPECIFICATION
(See Section 10, and rule 13)
1. TITLE OF INVENTION PARTICULATE COMBUSTION CATALYST
2. APPLICANT(S)

a) Name : MITSUI MINING & SMELTING CO., LTD.
b) Nationality : JAPANESE Company
c) Address : 1-11-1, OSAKI,
SHINAGAWA-KU, TOKYO 141-8584, JAPAN
3. PREAMBLE TO THE DESCRIPTION
The following specification particularly describes the invention and the manner in which it is to be performed : -

Technical Field
The present invention relates to a particulate combustion catalyst, to a method for producing the catalyst, to a particulate filter, and to an exhaust gas cleaning apparatus. More particularly, the present invention relates to a particulate combustion catalyst which realizes removal (through oxidation) of particulate matter discharged from a diesel internal combustion engine; to a method for producing the catalyst; to a particulate filter coated with the particulate combustion catalyst; and to an exhaust gas cleaning apparatus including the particulate filter coated with the particulate combustion catalyst.
Background Art
Exhaust gas discharged from diesel engines contains nitrogen oxides (NOx) and particulate matter, and release of such substances into the atmosphere without any treatment is a main cause of air pollution. Therefore, demand has arisen for strict regulation for such substances. There has been proposed, as effective means for removing particulate matter, a flow-through oxidation catalyst for combustion of soluble organic fractions (SOFs), and a diesel exhaust gas trapping system employing a diesel particulate filter (DPF) for trapping soot. However, for regeneration of such a DPF, particulate matter trapped therein must be continuously removed through oxidation.
Hitherto, a variety of continuous regeneration systems have been proposed, and examples thereof include a system employing a catalyst including a carrier made of an inorganic oxide (e.g., zirconium oxide, vanadium oxide, or cerium oxide), and an expensive noble metal (e.g., Pt) supported on the carrier (see, for example, Patent

Document 1,2, or 3); and a continuous regeneration method involving NO2 (see, for example, Patent Document 4). This continuous regeneration method requires provision, upstream of a DPF, of an oxidation catalyst (e.g., Pt) for oxidizing NO into NO2, and thus involves high cost. In addition, reaction involving NO2 is affected by the ratio of NOx to C, and many restrictions are imposed on the employment of this method.
There has been proposed a particulate combustion catalyst which exhibits excellent heat resistance, which realizes removal of soot through oxidation at low temperature without employment of an expensive noble metal, and which enables oxidation reaction to proceed with the aid of only oxygen and thus realizes removal of soot through oxidation at low temperature regardless of the NOx concentration of exhaust gas. The proposed particulate combustion catalyst is composed of a carrier formed of a cerium-zirconium composite oxide having a cerium oxide content of 5 to 50 mass%, and a first catalyst which is supported on the carrier and which is formed of at least one metal selected from Ag and Ru or an oxide of the metal (see Patent Document 5).
Prior Art Documents Patent Documents
Patent Document 1: Japanese Patent Application Laid-Open (kokai) No.
H10-047035 Patent Document 2: Japanese Patent Application Laid-Open (kokai) No.
2003-334443 Patent Document 3: Japanese Patent Application Laid-Open (kokai) No.
2004-058013

Patent Document 4: Japanese Patent No. 3012249 Patent Document 5: Japanese Patent No. 4144898
Summary of the Invention
Problems to be Solved by the Invention
An object of the present invention is to provide a particulate combustion catalyst which has durability in use at high temperature (hereinafter referred to as high-temperature durability) more excellent than that of the particulate combustion catalyst disclosed in Patent Document 5, which realizes removal of soot through oxidation at low temperature without employment of an expensive noble metal, and which enables oxidation reaction to proceed with the aid of only oxygen and thus realizes removal of soot through oxidation at low temperature regardless of the NOx concentration of exhaust gas. Another object of the present invention is to provide a method for producing the catalyst. Still another object of the present invention is to provide a particulate filter coated with the particulate combustion catalyst. Still another object of the invention is to provide a method for producing the particulate filter. Yet another object of the present invention is to provide an exhaust gas cleaning apparatus comprising the particulate filter coated with the particulate combustion catalyst.
Means for Solving the Problems
The present inventors have carried out extensive studies in order to attain the aforementioned objects, and have found that the objects can be attained by employing, as a catalyst component of a particulate combustion catalyst, an alloy containing Ag and at least one noble metal selected from the group consisting of Pd,

Pt, and Au. The present invention has been accomplished on the basis of this finding.
Accordingly, the particulate combustion catalyst of the present invention is characterized by comprising a carrier, and a catalyst component supported on the carrier and formed of an alloy composed of Ag in an amount of 85 to 20 at. % and at least one noble metal selected from the group consisting of Pd, Pt, and Au in an amount of 15 to 80 at.%.
The method of the present invention for producing a particulate combustion catalyst is characterized by comprising mixing an aqueous solution containing Ag ions with an aqueous solution containing ions of at least one noble metal selected from the group consisting of Pd, Pt, and Au; adding a powder of a catalyst carrier to the aqueous solution mixture with stirring, to thereby form a slurry; exsiccating the slurry and drying; and firing the dried product in air at a firing temperature of 700 to 1,000°C for a period of time of [50 - 0.047x (firing temperature)(°C)] (hour) or longer.
The present invention also provides a particulate filter characterized by being coated with any of the aforementioned particulate combustion catalysts. The present invention also provides an exhaust gas cleaning apparatus characterized by comprising a particulate filter coated with any of the aforementioned particulate combustion catalysts.
The method of the present invention for producing a particulate filter is characterized by comprising mixing and pulverizing a carrier with a binder component and water, to thereby form a slurry; coating a filter substrate with the slurry; firing the filter substrate, to thereby form a wash-coating layer; impregnating

the wash-coating layer with a mixture of an aqueous solution containing Ag ions and an aqueous solution containing ions of at least one noble metal selected from the group consisting of Pd, Ft, and Au, as catalyst components; drying the filter substrate; and firing the dried product in air at a firing temperature of 700 to 1,000°C for a period of time of [50 - 0.047x(firing temperature)(°C)] (hour) or longer.
Effects of the Invention
The particulate combustion catalyst of the present invention has excellent high-temperature durability, which realizes removal of soot through oxidation at low temperature, and which enables oxidation reaction to proceed with the aid of only oxygen and thus realizes removal of soot through oxidation at low temperature regardless of the NOx concentration of exhaust gas.
Brief Description of the Drawings
[Fig. 1] A graph showing the relationship between the Pd content of the particulate combustion catalyst and combustion initiation temperature (Tig).
[Fig. 2] A graph showing the relationship between the Pd content and XRD peak shift of the particulate combustion catalyst after thermal treatment at various temperature.
[Fig. 3] A chart showing a change in diffraction peak (peak shift).

Modes for Carrying Out the Invention
The particulate combustion catalyst of the present invention employs, as a catalyst component, an alloy composed of Ag and at least one noble metal selected from the group consisting of Pd, Pt, and Au, preferably an alloy composed of Ag and Pd and/or Pt, in order to lower the combustion initiation temperature. However, when the alloy contains at least one noble metal selected from the group consisting of Pd, Pt, and Au in an amount or amounts less than 20 at.% or in excess of 85 at.%, the combustion initiation temperature is not sufficiently lowered. Thus, the catalyst component is an alloy composed of 85 to 20 at.% (preferably 80 to 30 at.%) of Ag and 15 to 80 at.% (preferably 20 to 70 at.%) of at least one noble metal selected from the group consisting of Pd, Pt, and Au. In order to reduce the amount of expensive noble metal so as to reduce production cost, the alloy is preferably composed of 80 to 65 at.% of Ag and 20 to 35 at.% of noble metal. Notably, when Pd is used as a noble metal, the effect of firing particulates at low temperature is most fully attained.
The particulate combustion catalyst of the present invention preferably contains an alloy serving as the catalyst component in an amount of 0.5 to 30 parts by mass with respect to 100 parts by mass of the carrier, more preferably 0.5 to 15 parts by mass (mass%). When the amount of alloy with respect to that of the carrier is less than 0.5 mass%, the catalytic effect is not sufficiently attained, whereas when the amount is in excess of 30 mass%, the catalytic activity (per unit mass) of the supported alloy tends to decreases. In addition to the aforementioned alloys, the particulate combustion catalyst of the present invention may employ, in combination, a catalyst formed of elemental Ag, Pt, Pd, or Au.

The particulate combustion catalyst of the present invention may employ any of the carriers which are generally employed as carriers of particulate combustion catalysts containing Ag as a catalyst component. However, preferably employed is a carrier which attains high-speed transfer of oxygen therefrom and combustion of particulates at high efficiency. Examples of such carries include CeCh-ZrCh and ZrO2. Of these, Ce02 -ZrO2 is more preferably used.
When a Ce02-Zr02 carrier is used in the particulate combustion catalyst of the present invention, the CeO2 content of the composite oxide is preferably 5 to 50 mass%. When the CeO2 content is in excess of 50 mass%, the specific surface area of the carrier decreases at high temperature (e.g., 700°C or higher), in some cases, eventually causing thermal deterioration of the catalyst, whereas when Ce02 content is less than 5 mass%, the catalyst may be thermally deteriorated in some cases.
The carrier of the particulate combustion catalyst of the present invention is preferably formed of a Ce02 -ZrO2 -based composite oxide containing at least one metal selected from among Nd, La, Fe, Y, Pr, Ba, Ca, Mg, Sn, and Sr. By virtue of the presence of these metallic elements, the carrier formed of the CeO2 -Z1O2 -based composite oxide exhibits improved thermal stability and improved oxidation performance at low temperature. In order to fully attain these effects, the amount of oxide containing at least one metal selected from among Nd, La, Fe, Y, Pr, Ba, Ca, Mg, Sn, and Sr must be 1 mass% or more. However, when the amount of metal oxide is in excess of 35 mass%, the relative amounts of CeC»2 and Zr02 decrease, and the performance of the carrier formed of the CeCh -ZrCh -based composite oxide is likely to be impaired. Therefore, the carrier employed in the catalyst is preferably a CeO2 -Zr02 -based composite oxide having an amount of oxide containing at least

one metal selected from among Nd, La, Fe, Y, Pr, Ba, Ca, Mg, Sn, and Sr (the total amount in the case where a plurality of metal oxides are present) of 1 to 35 mass% and a CeCh content of 5 to 50 mass %.
One embodiment of the method of the present invention for producing a particulate combustion catalyst is as follows. Firstly, an aqueous solution containing Ag ions (e.g., aqueous silver nitrate solution) and an aqueous solution containing ions of at least one noble metal selected from the group consisting of Pd, Pt, and Au (e.g., aqueous palladium nitrate solution, dinitrodiamine-Pt nitrate solution, or aqueous platinum chloride solution) were mixed at such a ratio that the amount of Ag is adjusted to 85 to 20 at.% and the amount of at least one noble metal selected from the group consisting of Pd, Pt, and Au is adjusted to 15 to 80 at.%. To the aqueous solution mixture, the aforementioned carrier powder is added in such an amount that the total metal amount of the catalyst component(s) with respect to 100 parts by mass of the carrier is adjusted to 0.5 to 30 parts by mass, and the mixture is stirred, to thereby form a slurry. The slurry is exsiccated and further dried at a specific temperature (e.g., 120°C). The dried product is fired in air at 700 to 1,000°C, preferably 800 to 950°C for a period of time of [50 - 0.047x (firing temperature)(°C)] (hour) or longer. Through the procedure, alloying of Ag with at least one noble metal selected from the group consisting of Pd, Pt, and Au is completed. The firing time is [50 - 0.047x (firing temperature)(°C)] (hour) or longer, and preferably 10 to 30 hours, more preferably 15 to 25 hours. The firing time [50 - 0.047x(firing temperature) (°C)] (hour) or longer, defined in the present invention, has been derived from a large number of times of experiments.
In the particulate combustion catalyst of the present invention employing the aforementioned alloy serving as a catalyst component, the XRD peak of the catalyst

is preferably shifted by 0.45° or more from the XRD peak of a particulate combustion catalyst employing Ag as a sole catalyst component. The shift of the XRD peak of the particulate combustion catalyst [shift of the peak attributed to Ag(lll)] is an index for the degree of formation of solid solution in the alloy or the degree of alloying. As is clear from the description hereinbelow, the shift varies depending on the alloy composition and the thermal treatment temperature (firing temperature).
In consideration that the particulate filter of the present invention is produced by causing the particulate combustion catalyst of the present invention to be held on a base, preferably, the surface of the carrier is provided with a binder component such as SiO2, Ti02, Zr02, or AI2O3. When such a binder component is provided on the surface of the carrier, adhesion between the base and the carrier is enhanced, and the catalyst exhibits improved durability and heat resistance.
The particulate filter of the present invention may assume any known form of particulate filter, but preferably has a three-dimensional structure. Specific examples of filters having a three-dimensional structure include a wall-through filter, a flow-through honeycomb filter, a wire mesh filter, a ceramic fiber filter, a metallic porous filter, a particle-charged filter, and a foam filter. Examples of the material of the base include ceramic materials such as cordierite and SiC; Fe-Cr-Al alloys; and stainless steel alloys.
The exhaust gas cleaning apparatus of the present invention, which includes therein the aforementioned particulate filter of the present invention, will be readily appreciated by those skilled in the art.

Next will be described a method for producing the particulate filter of the present invention.
A cerium zirconium composite oxide serving as a carrier is mixed with a binder component (e.g., S1O2 or alumina sol) and water, and the resultant mixture is finely milled by means of a milling apparatus (e.g., a ball mill). A particulate filter substrate (e.g., a wire mesh filter) is coated with the thus-obtained slurry. In general, the slurry-coated filter is fired at a temperature of about 500°C to about 700°C The thus-formed wash-coating layer is impregnated with, for example, an aqueous solution mixture of, for example, aqueous silver nitrate solution and aqueous palladium nitrate solution, and then drying and firing are carried out. Firing is performed under the same firing condition as employed in the aforementioned particulate combustion catalyst production method. The total catalyst coating amount is preferably about 10 to about 100 g/L (for a wall-flow DPF) or about 50 to about 150 g/L (for a wire mesh DPF). When the total catalyst coating amount is excessively small, sufficient performance fails to be attained, whereas when the total catalyst coating amount is excessively large, back pressure to exhaust gas increases.
Examples
The present invention will next be described in detail with reference to Examples and Comparative Examples. In each of the Examples and Comparative Examples, a parenthesized numerical value following each of the oxides forming a composite oxide (i.e., carrier) represents the amount (mass%) of the constitutive oxide with respect to the entirety of the composite oxide.

Examples 1 to 5, and Comparative Examples 1 to 4
To a catalyst component solution having a metal element content of 5 mass% (with respect to the mass of carrier), water (30 g), and the mixture was stirred to thereby form an aqueous solution. The employed catalyst component solutions are as follows: aqueous silver nitrate solution (Comparative Example 1), solution mixture of aqueous silver nitrate solution and aqueous palladium nitrate solution (Ag : Pd = 95 : 5 (atomic)) (Comparative Example 2), solution mixture of aqueous silver nitrate solution and aqueous palladium nitrate solution (Ag : Pd = 90 : 10 (atomic)) (Comparative Example 3), solution mixture of aqueous silver nitrate solution and aqueous palladium nitrate solution (Ag : Pd = 80 : 20 (atomic)) (Example 1), solution mixture of aqueous silver nitrate solution and aqueous palladium nitrate solution (Ag : Pd = 70 : 30 (atomic)) (Example 2), solution mixture of aqueous silver nitrate solution and aqueous palladium nitrate solution (Ag : Pd = 50 : 50 (atomic)) (Example 3), solution mixture of aqueous silver nitrate solution and aqueous palladium nitrate solution (Ag : Pd = 30 : 70 (atomic)) (Example 4), solution mixture of aqueous silver nitrate solution and aqueous palladium nitrate solution (Comparative Example 4), and solution mixture of aqueous silver nitrate solution and dinitrodiamine-Pt nitrate solution (Ag : Pd = 80 : 20 (atomic)) (Example 5). To each of the thus-prepared solutions, a powder of a composite oxide (Ce02(21) + ZrCh (72) + La2O3 (2) + Nd2O3 (5)) (5.0 g) was added, and the mixture was stirred for 30 minutes, to thereby form a slurry. The thus-formed slurry was exsiccated to dryness and further dried at 120°C for 3 hours. Subsequently, the dried product was fired in air at 800°C for 20 hours. Thus thus-yielded particulate combustion catalyst was found to have a catalyst metal content of 5 mass% with respect to the mass of carrier.

The Tig (combustion initiation temperature) of each particulate combustion catalyst powder produced in Examples 1 to 4 and Comparative Examples 1 to 4 was measured through the following method.
Each particulate combustion catalyst powder {20 mg) produced in Examples 1 to 4 and Comparative Examples 1 to 4 and carbon (2 mg) (Printex-V (toner carbon), product of Degussa) were mixed for 15 seconds by means of a mortar agate. The mixture was fixed at a center portion of a quartz-made reaction tube by use of quartz wool. While a circulation gas having the below-described composition was caused to flow through the quartz reaction tube at the below-described flow rate, the temperature of the reaction tube was elevated at the below-described temperature elevation rate by means of an electric furnace, and CO and CO2 concentrations were measured at the outlet of the reaction tube by means of an infrared analyzer. The temperature as measured at the inlet of the catalyst-containing reaction tube when CO2+CO concentration reached 30 ppm (i.e., electric furnace control temperature) was regarded as Tig. Fig. 1 shows the combustion initiation temperatures of the particulate combustion catalyst powders.
Gas composition: O2:10%, N2: balance
Flow rate: 400 cc/min
Temperature elevation rate: 10 degrees (°C)/min
As is clear from the graph of Fig. 1, an alloy composed of 85 to 20 at.% of Ag and 15 to 80 at.% of at least one noble metal selected from the group consisting of Pd, Pt,

and Au is preferably employed as a catalyst component. More preferably, an alloy composed of 80 to 30 at.% of Ag and 20 to 70 at.% of at least one noble metal selected from the group consisting of Pd, Pt, and Au is preferably employed as a catalyst component.

The procedure of producing particulate combustion catalyst powders of Example 1, Comparative Example 1, and Example 5 was repeated, except that the firing temperature was changed to 800°C, 900°C, and 1,000°C, to thereby form catalyst powders. In a similar manner, the combustion initiation temperature (Tig) of each catalyst powder was measured. The combustion initiation temperatures of the particulate combustion catalyst powders are shown in Table 1.
[Table 1]
Table 1 (Tig temp.)

Firing temp. 800°C 900°C 1,000°C
Ag Ag-20 at.% Pd Ag-20 at.% Pt 294°C 265°C 298°C 284°C 323°C 293°C 306°C
As is clear from Table 1, when an alloy of Ag 80 at.% and Pd 20 at.% or an alloy of Ag 80 at.% and Pt 20 at.% was employed as a catalyst component, high-temperature durability of the catalyst is more effectively improved, as compared with the case where Ag is employed as a sole catalyst component.

The particulate combustion catalysts having a Pd content of 5 at.%, 10 at.%, or 20 at.% and treated at 800°C; the particulate combustion catalysts having a Pd content of 20 at.% and treated at 900°C; and the particulate combustion catalysts having a Pd content of 20 at.% and treated at 1,000°C were analyzed in terms of shift of XRD peak [the peak attributed to Ag(lll)] (the degree of formation of solid solution in the alloy or the degree of alloying). Fig. 2 shows the peak shifts of the respective particulate combustion catalyst powders. The mode of shifting the peak is shown in Fig. 3. Preferably/ alloying is performed such that the XRD peak of the catalyst component of the aforementioned alloy is increased by about 0.45° or more from that of the catalyst component employing Ag as a sole catalyst component.
As is clear from the graph of Fig. 2, the peak shift increases as the Pd content increases and as the thermal treatment temperature is elevated, indicating that solid solution formation or alloying is promoted.

WE CLAIM:
1. A particulate combustion catalyst, characterized by comprising a carrier, and a catalyst component supported on the carrier and formed of an alloy composed of Ag in an amount of 85 to 20 at.% and at least one noble metal selected from the group consisting of Pd, Pt, and Au in an amount of 15 to 80 at.%.
2. A particulate combustion catalyst according to claim 1, wherein the catalyst component is formed of an alloy composed of Ag in an amount of 80 to 30 at.% and at least one noble metal selected from the group consisting of Pd, Pt, and Au in an amount of 20 to 70 at.%.
3. A particulate combustion catalyst according to claim 1 or 2, wherein the catalyst component is formed of an alloy composed of Ag and at least one noble metal selected from the group consisting of Pt and Pd.
4. A particulate combustion catalyst according to claim 1, 2, or 3, wherein the XRD peak of the catalyst employing the alloy as a catalyst component is shifted by 0.45° or more from the XRD peak of a particulate combustion catalyst employing Ag as a sole catalyst component.
5. A particulate combustion catalyst according to claim 1, 2, 3, or 4, wherein the carrier is formed of a Ce02 -Zr02 -based material.
6. A method for producing a particulate combustion catalyst as recited in any one of claims 1 to 5, characterized in that the method comprises

mixing an aqueous solution containing Ag ions with an aqueous solution
containing ions of at least one noble metal selected from the group consisting
of Pd, Pt, and Au;
adding a powder of a catalyst carrier to the aqueous solution mixture with
stirring, to thereby form a slurry;
exsiccating the slurry and drying; and
firing the dried product in air at a firing temperature of 700 to 1,000°C for a
period of time of [50 - 0.047x(firing temperature)(°C)] (hour) or longer.
7. A particulate filter characterized by being coated with a particulate combustion catalyst as recited in any one of claims 1 to 5.
8. A method for producing a particulate filter as recited in claim 7, characterized in that the method comprises
mixing and pulverizing a carrier with a binder component and water, to
thereby form a slurry;
coating a filter substrate with the slurry;
firing the filter substrate, to thereby form a wash-coating layer;
impregnating the wash-coating layer with a mixture of an aqueous solution
containing Ag ions and an aqueous solution containing ions of at least one
noble metal selected from the group consisting of Pd, Pt, and Au, as catalyst
components;
drying the filter substrate; and
firing the dried product in air at a firing temperature of 700 to 1,000°C for a
period of time of [50 - 0.047x(firing temperature)(°C)] (hour) or longer.

9. An exhaust gas cleaning apparatus characterized by comprising a particulate filter coated with a particulate combustion catalyst as recited in any one of claims 1 to 5.

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Patent Number

279595

Indian Patent Application Number

73/MUMNP/2012

PG Journal Number

05/2017

Publication Date

03-Feb-2017

Grant Date

27-Jan-2017

Date of Filing

09-Jan-2012

Name of Patentee

MITSUI MINING & SMELTING CO., LTD.

Applicant Address

1-11-1, OSAKI, SHINAGAWA-KU, TOKYO 141-8584, JAPAN

Inventors:

#	Inventor's Name	Inventor's Address
1	ASANUMA TAKAHITO	C/O CORPORATE R&D CENTER, MITSUI MINING & SMELTING CO., LTD. 1333-2, HARAICHI, AGEO-SHI, SAITAMA 362-0021, JAPAN
2	AOKI AKIRA	C/O CORPORATE R&D CENTER, MITSUI MINING & SMELTING CO., LTD. 1333-2, HARAICHI, AGEO-SHI, SAITAMA 362-0021, JAPAN

PCT International Classification Number

B01J 23/66

PCT International Application Number

PCT/JP2010/060358

PCT International Filing date

2010-06-18

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	2009-160197	2009-07-06	Japan