JP6347443B2 - Alumina particles - Google Patents

Description

  The present invention relates to an alumina particle having a novel pore structure, and more particularly to an alumina particle suitably used as a catalyst carrier, particularly as a carrier for an exhaust gas purification catalyst.

  Platinum group metals typified by platinum, palladium, and rhodium have a function as a catalytic active component for exhaust gas purification, and those in which such a platinum group metal is supported on a porous carrier are, for example, automobile exhaust gases. It is used as a catalyst for oxidizing hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx) contained therein (see Patent Document 1).

  By the way, the platinum group metal as described above is a noble metal and is very expensive. Therefore, the platinum group metal must be held on a porous carrier (catalyst carrier) so that its catalytic function is efficiently exhibited. Accordingly, various proposals have been made for porous carriers that are suitably used as catalyst carriers.

For example, Patent Document 1 proposes that at least one selected from the group consisting of alumina, ceria, zirconia, titania, silica, zeolite, and mesoporous silica is used as a catalyst carrier for supporting the platinum group metal. Yes.
Patent Document 2 proposes to use mesoporous silica having uniform mesopores having a regular periodic structure and having Si—O—Zr bonds at a certain ratio as a catalyst carrier.
Further, Patent Document 3 discloses a catalyst carrier having a pore structure having a micropore having a pore diameter in the range of 10 to 100 nm and a macropore having a pore diameter in the range of 300 to 900 nm. Alumina to be used is disclosed, and furthermore, in addition to micropores and macropores, alumina having a super macropore having a pore diameter in the range of 6000 to 9000 nm is also disclosed.

  Each of the various catalyst supports described above exhibits a certain degree of catalytic ability (oxidation effect on HC, CO, NOx, etc.) when a catalytically active component such as platinum is supported thereon, and mainly contains alumina particles. What has to do has the advantage of being inexpensive. On the other hand, according to the studies by the present inventors, there is a problem that the catalytic ability is usually lowered when the gas to be purified is supplied in the mist state as compared with the case where the gas is supplied in the gaseous state. Since the exhaust gas of automobiles or the like has a low volatile fuel component (hydrocarbon) which may be discharged in the form of a mist, it is the view of the present inventors that improvement is necessary.

Based on this view, the inventors of the present invention previously stated in Japanese Patent Application No. 2014-35736 that the pore volume V ₁ of mesopores having a pore diameter of 4 to 50 nm is in the range of 0.05 to 0.80 cm ³ / g. The total pore size of the pores having a pore diameter of 50 to 8000 nm and a pore volume V _{2 in} the range of 0.05 to 0.50 cm ³ / g and a pore diameter of 4 to 8000 nm Alumina particles having a multi-element pore structure characterized by a volume Vt in the range of 0.10 to 1.30 cm ³ / g are proposed. Such alumina particles are preferably used as a catalyst carrier, and in particular, when a catalytically active component such as platinum is supported, it is possible to effectively avoid a decrease in activity when the treatment substance is supplied in a mist form. .
As a result of further research on alumina particles having mesopores and macropores as described above, the present inventors have found that the distribution state of macropores has a great influence on the oxidation action on NOx.

JP 2004-148166 A Japanese Patent Laid-Open No. 2002-241123 JP 2010-179267 A

  Accordingly, an object of the present invention is to have a unique macropore distribution state, and when a catalytically active component such as platinum is supported, it effectively avoids a decrease in activity when the treatment substance is supplied in a mist form. An object of the present invention is to provide alumina particles which can be oxidized and exhibit an excellent oxidizing action on NOx.

According to the present invention, the pore volume V ₁ of a macropore having a pore diameter of 50 to 8000 nm is in the range of 0.04 to 0.50 cm ³ / g, and the cross section of the particle is an electron at a magnification of 1000 times. When micrographs are taken and the electron micrographs are divided by a 50 μm ² lattice, the distribution of the macropores is observed in 60% or more of the lattices.

In the alumina particles of the present invention,
(1) Mesopores with a pore diameter of 4 to 50 nm have a pore volume V _{2 in} the range of 0.05 to 0.80 cm ³ / g, and the total fineness of pores with a pore diameter of 4 to 8000 nm. Having a multi-pore structure with a pore volume Vt in the range of 0.10 to 1.30 cm ³ / g;
(2) The volume ratio (V ₁ / V ₂ ) between the pore volume V ₁ of the macropores and the pore volume V ₂ of the mesopores is in the range of 0.08 to 0.80,
(3) Silica is dispersed in an amount such that the amount of Si represented by 100 × Si / (Si + Al) is 1.0 to 10.0 mol%,
(4) to be used as a catalyst carrier;
Is preferred.

  According to the present invention, there is also provided an exhaust gas purifying catalyst comprising a platinum group metal supported on the alumina particles.

  In this specification, the expression “mesopore” and “macropore” refers to pores (mesopores) and fine pores having a pore diameter of 4 to 50 nm in consideration of the relative size of the pore diameter. It is used for convenience of explanation as indicating pores (macropores) having a pore diameter of 50 to 8000 nm, and is uniquely used to indicate pores of a certain size among those skilled in the art. It is not an expression that has been made. For example, Patent Document 3 describes the expression “macropore”, but the pore diameter range is different from the macropore range defined in this specification.

The alumina particles of the present invention have macropores having a pore diameter of 50 to 8000 nm, and the pore volume V ₁ is in the range of 0.04 to 0.50 cm ³ / g. A great feature is that the macropores are uniformly distributed in the particles. That is, such macropores are observed in 60% or more of the lattice when the electron micrograph is taken with a magnification of 1000 times and the electron micrograph is divided by a 50 μm ² lattice. Due to the distribution of such macropores throughout the particles, the alumina particles exhibit an excellent oxidizing action on NOx. For example, as shown in Examples described later, NO at 350 ° C. The conversion from NO to NO ₂ is extremely high at about 50%. It is presumed that the macropores are uniformly distributed throughout the particles, so that the nitrogen oxide gas can quickly permeate into the particles and the internal catalyst can be used effectively.

In the present invention, further, the pore diameter is the pore volume _{V 2} of the mesopores of 4~50nm the range of 0.05~0.80cm ³ / g, macropores such mesopores above It is preferable that the multi-pore structure is formed together. When the alumina particles having such a multi-pore structure are loaded with a catalytically active component, even when a treatment substance to be used for the catalytic reaction is supplied in a mist state, the alumina particles have a deep portion through the macropores. A mist-like treatment substance penetrates into the existing mesopores, and the reaction can be stably promoted without deteriorating the catalyst performance.

In the present invention, the present inventors presume that the reason why the deterioration of the catalyst performance can be effectively avoided by using the alumina particles having the multi-element pore structure as a support as described above. Yes.
That is, the mesopores in the alumina particles of the present invention are considered to function as a space for stably holding the catalytically active component, while the macropores are treated substances for the catalytic reaction, and the catalytically active component is supported. It seems to function as an introduction space for stable introduction into a certain area.
When this point is described in detail, the presence of a certain amount of mesopores as described above makes it possible to support the catalytically active component and exert its catalytic ability, but only with such mesopores, When the treatment substance used for the catalytic reaction is supplied in the form of a mist, the catalytic ability is not sufficiently exhibited. This is illustrated by the experimental results of a comparative example described later. Such a decrease in catalytic ability is probably caused by clogging of pores on the outer surface of the carrier due to mist (for example, thermal decomposition product of fuel), and as a result, contact between the catalytically active component and the treatment substance to be subjected to the catalytic reaction is reduced. It seems to be caused by being inhibited. However, when a certain amount of large macropores as described above are present in accordance with the present invention, clogging of the pores due to mist is effectively suppressed, and as a result, the catalytically active component between the catalyst and the treatment substance used for the catalytic reaction is reduced. It is believed that the catalytic ability is stably exhibited without being inhibited.

The figure which shows the experimental method of fuel mist oxidation activity. The SEM image of the alumina obtained in Example 1 (1000 times magnification). The SEM image of the alumina obtained in Example 2 (1000 times magnification). The SEM image of the alumina obtained in Comparative Example 3 (magnification 1000 times). The SEM image of the alumina obtained in Comparative Example 4 (magnification 1000 times).

<Alumina particles>
The alumina particles of the present invention are not particularly limited as long as they have a multi-pore structure described later, and may have a crystal structure such as γ, θ, δ, η, and κ. In particular, γ-alumina is preferable in that a stable multi-pore structure can be easily formed.

The alumina particles, the size of the macropores of pore diameters 50～8000Nm, pore volume _{V 1} is 0.04~0.50cm ³ / g, preferably a 0.04~0.30cm ³ / g In particular, such macropores are obtained by taking a cross-section of particles with an electron micrograph at a magnification of 1000 times, and when the electron micrograph is divided by a 50 μm ² lattice, 60% or more of the lattice, Especially observed at 75-100%. Due to the distribution of such macropores throughout the particles, the alumina particles exhibit an excellent oxidizing action on NOx. Even if macropores exist in the particles, if they are distributed unevenly, it is difficult for the nitrogen oxide gas to penetrate evenly into the particles. When such macropores are not provided, the purification action of alumina particles for NOx is reduced (see Comparative Example 1 described later).

More preferably, the alumina particles of the present invention have mesopores having a pore diameter of 4 to 50 nm together with such macropores, and the total pore volume Vt of pores having a pore diameter of 4 to 8000 nm is It has a multi-pore structure in the range of 0.10 to 1.30 cm ³ / g, particularly 0.15 to 0.90 cm ³ / g. That is, when the total volume Vt is in the above range, the mesopores and macropores as described above can be formed in a certain amount, and in particular, the ratio of the macropores occupying all the pores increases, A decrease in catalyst performance when supplied in the form of a mist can be effectively avoided. In the case of having such a multi-element pore structure, it seems that the change of the pore structure due to the thermal contraction of the particles can be effectively suppressed.

Furthermore, in the present invention, on the condition that the total pore volume Vt of pores having a pore diameter of 4 to 8000 nm is within the above range, the pore volume V ₂ of mesopores having a pore diameter of 4 to 50 nm. preferably but is 0.05~0.80cm ³ / g, it is particularly preferably from 0.10~0.60cm ³ / g. By pore volume V ₂ of the mesopores is in the above range, it is possible to carry a sufficient amount of catalytically active components, it is possible to obtain a satisfactory catalyst performance.

When the alumina particles of the present invention have the above-described multi-pore structure, in such alumina particles, the volume ratio (V ₁ / V ₂ ) between the pore volume V ₁ of the macropores and the pore volume V ₂ of the mesopores. Is preferably adjusted in the range of 0.08 to 0.80, particularly 0.08 to 0.60. That is, in order to improve the catalyst performance when the catalytic active component is supported on the alumina particles, the mesopore volume (V ₂ ) should be increased. The pore volume (V ₁ ) may be increased, but the total pore volume (Vt) is limited. Therefore, if one pore volume is increased, the other pore volume is decreased. Therefore, it is preferable to adjust the pore volume ratio (V ₁ / V ₂ ) within the above range in terms of ensuring a good balance between excellent catalyst performance and mist catalyst performance.

In the present invention, the various pore volumes Vt, V ₁ and V ₂ described above can be measured by mercury porosimetry.

In addition, when the alumina particles of the present invention have the above-described multi-pore structure, the alumina particles have a high specific surface area in relation to the pore volumes Vt, V ₁ and V ₂ being in the above-described range. For example, the BET specific surface area is in the range of 100 to 400 m ² / g.

Furthermore, it is preferable that a minute amount of fine silica is dispersed in the alumina particles of the present invention. For example, the amount of Si represented by 100 × Si / (Si + Al) is 1.0 to 10.0 mol%. In particular, it is preferable that silica is dispersed in an amount of 1.5 to 8.0 mol%.
The alumina particles in which such a small amount of silica is dispersed have extremely high heat resistance and durability of catalytic activity when used as an exhaust gas purifying catalyst by supporting a catalytically active component such as platinum. That is, particularly when the alumina particles of the present invention have a multi-pore structure, such alumina particles cause pore shrinkage when exposed to high temperatures (eg, 700 ° C. or higher), but a minute amount of silica is dispersed. As a result, the thermal contraction of the pores is effectively suppressed, and as a result, the catalytically active component is stably held in the pores, and the catalytic activity is not impaired even by heat treatment at a high temperature and can be maintained stably. it can.

  When the Si content (mol%) is larger than the above range, the amount of dispersed silica is large. As a result, the loading of the catalytically active component in the pores is hindered, and the catalytic activity itself is reduced. It will decline. Further, when the Si content (mol%) is smaller than the above range, the amount of silica dispersed is small, so that the heat shrinkage of the alumina pores cannot be sufficiently suppressed, and the heat resistance durability of the catalytic activity is reduced. It becomes difficult to increase.

<Manufacture of alumina particles>
The alumina particles of the present invention are produced by using an aqueous solution of an aluminum salt such as aluminum sulfate as a raw material, mixing the raw material liquid and an alkali, and gelling, washing with water, drying and firing. It is necessary to carry out in the presence of a modifier.

  As the alkali to be mixed with the aluminum salt aqueous solution, caustic soda, caustic potash, ammonium hydroxide or the like is used, and the alkali is used in such an amount that the pH of the mixed liquid with the raw material liquid is in the alkaline range.

Further, organic resin particles are used as the pore adjusting agent. That is, since gelation is performed in the presence of such organic resin particles, an alumina hydrogel is formed so as to include the organic resin particles, and further, the organic resin particles are decomposed and removed by subsequent firing. The alumina particles having the above-mentioned multi-pore structure can be obtained.
Therefore, it is necessary that such organic resin particles maintain the form of the particles until the temperature is raised to a certain high temperature in the firing process. For this reason, the alkali resin has a high alkali resistance and a melting point. Or a thing with a comparatively high softening point (for example, 100 degreeC or more) is used. For example, resin particles such as polymethyl methacrylate (PMMA) and polystyrene can be suitably used. These resins are modified by copolymerization, and heat resistance and alkali resistance are improved by introducing a crosslinked structure. Good.

Such organic resin particles contribute particularly to the formation of macropores, and are preferably fine. For example, the volume-based median diameter (D ₅₀ ) measured by a laser diffraction scattering method is 0.1 to 0.1. The fine particles are preferably in the range of 10 μm. That is, if the particle size is excessively large, it becomes difficult not only to uniformly disperse the organic resin particles in the gel, but also gelation in a state including the particles becomes difficult, and pore adjustment is effective. There is a risk that it will not be possible to perform it automatically. When the particle size is excessively small, not only handling is difficult, but aggregation and the like are likely to occur, and pore adjustment may be difficult. Furthermore, in order to disperse the macropores uniformly in the particles, the above particle size distribution needs to be extremely broad. For example, when the median diameter (D ₅₀ ) is in the above range and 0 to 10 μm is divided every 2 μm in the particle size distribution graph, the number of particles having a particle size in each range is 0 of the total number. By using organic resin particles that are 0.5% or more (number%), macropores can be uniformly distributed throughout the particles. When organic resin particles having a sharp particle size distribution are used, macropores are not uniformly distributed and tend to be concentrated locally. Examples of the organic resin particles having a broad distribution as described above include GANZPEARL GM-0401S manufactured by Aika Industry.

In the present invention, the larger the amount of the organic resin particles used, the greater the proportion of macropore volume (V ₁ ) occupying the total pore volume Vt. Therefore, in order to obtain alumina particles of the above-mentioned multi-pore structure, such organic resin particles, Al quantity (Al 2 O ₃₎ 5~40 weight per ₁₀₀ parts by weight as oxides contained in an aqueous solution of aluminum sulfate It is better to use in parts quantity.

  The above-mentioned gelation by mixing an aqueous solution (raw material solution) of an aluminum salt such as aluminum sulfate and an alkali is performed by mixing the raw material solution and organic resin particles into an alkaline solution heated to a temperature of 45.0 to 80.0 ° C. (The pH of the mixed solution is alkaline as described above), and after gel formation, washing with water is performed, whereby an alumina hydrogel is obtained.

The alumina hydrogel obtained above is dried, moisture is removed to obtain a xerogel encapsulating organic resin particles, and this is fired to obtain alumina particles having a target multi-pore structure. That is, by firing, the organic resin particles contained in the xerogel are decomposed and removed, and alumina particles having macropores together with mesopores of a predetermined size are obtained.
The firing temperature is about 600 to 900 ° C. If this temperature is high enough to form α-alumina, the pore shrinkage is large, which may be inappropriate for supporting the catalytically active component. If the temperature is too low, the organic resin particles may not be decomposed and removed.

In addition, the alumina particles produced by the above-described method have low heat resistance. For example, when held in a high temperature atmosphere of 600 ° C. or higher, the pores shrink due to thermal shrinkage, resulting in a decrease in catalyst performance. There is. In order to prevent such inconvenience, acidic silica sol is preferably allowed to coexist during gelation by mixing the raw material liquid with an alkali liquid.
That is, the above-described hydrogel is produced in the presence of acidic silica sol, and further dried and calcined to disperse by-produced silica fine particles in alumina particles, and these silica fine particles are kept at a high temperature. As a result, it is possible to effectively suppress pore shrinkage and maintain a stable multi-pore structure. As a result, it is possible to effectively avoid performance degradation due to pore shrinkage.

  Such an acidic silica sol has a Si amount relative to Al in the raw material liquid, that is, a molar ratio of 100 × Si / (Si + Al) is 1.0 to 10.0 mol%, particularly 1.5 to 8.0 mol%. Used in an amount that is within the range. Use of a larger amount of Si than the above range may change the multi-pore structure of the resulting alumina particles, and if the amount used is small, the effect of suppressing pore shrinkage at high temperatures is ineffective. It will be enough.

  In addition, when gelatinizing in the presence of acidic silica sol and producing the target alumina particle, it is preferable to perform either drying or baking in the presence of moisture. Although it has not been clarified theoretically, the thermal contraction of silica particles during firing is suppressed by interposing moisture during the thermal history, and fluctuations in pores due to the presence of silica particles are suppressed. Seem.

Drying in the presence of moisture can be performed by so-called steam drying. For example, it is preferable to perform drying while spraying steam at 60 ° C. or higher, particularly 100 to 200 ° C. or suppressing exhaust in the dryer and retaining moisture from the hydrogel for a long time.
Further, firing in the presence of moisture can be performed by steam firing. This steam firing is performed by heating to a predetermined firing temperature in a container that can be fired while retaining moisture generated from the xerogel itself for a long time.

  When an acidic silica sol is used, it is desirable to perform either drying or firing in the presence of moisture as described above, but it is most preferable to perform both steam drying and steam firing. That is, by adopting such means, the shrinkage of particles (particularly silica particles) can be more effectively suppressed, and fluctuations in pores due to the introduction of silica particles can be avoided more reliably.

  The silica-dispersed alumina thus obtained is porous and has a structure in which a minute amount of fine silica particles are uniformly dispersed therein, thereby suppressing pore shrinkage due to heat treatment at high temperature. In addition, fluctuations in the pores during firing accompanying an increase in the Si content are effectively suppressed, and excellent characteristics as a catalyst carrier are exhibited.

<Catalyst>
Alumina particles having the above characteristics are extremely inexpensive, and are formed into various forms such as cylindrical, granular, and tablet by known methods such as extrusion molding and granulation molding, and platinum or the like is formed thereon. The catalyst active component is supported and applied suitably for use as a catalyst.
In particular, since a decrease in catalytic activity when a processing substance is supplied in a mist state is effectively avoided, it is extremely suitable as a catalyst for purifying automobile exhaust gas carrying a platinum group metal, and HC, CO, NOx can be oxidized.
Furthermore, the alumina particles of the present invention in which a small amount of silica is dispersed have excellent heat resistance and durability, and even when held at a high temperature by aging or the like, pore shrinkage is effectively suppressed. Therefore, excellent catalyst performance can be exhibited.

Typical platinum group metals used as exhaust gas purifying catalysts are platinum, palladium, rhodium, iridium and ruthenium, all of which are extremely expensive noble metals. For this reason, the exhaust gas catalyst using the inexpensive alumina particles of the present invention as a carrier can effectively avoid a decrease in catalytic activity even by high temperature treatment such as aging, and can maintain the catalyst performance over a long period of time. Suitable for significant cost reduction.
In addition, the above-described alumina particles may be used in addition to expensive platinum group catalysts, as well as other metals having a function as catalysts such as hydrorefining catalysts, hydrodesulfurization catalysts, hydrodenitrogenation catalysts, such as copper and vanadium. Manganese, chromium, molybdenum, tungsten, iron, cobalt, nickel, osmium, molybdenum-cobalt, molybdenum-nickel, tungsten-nickel, molybdenum-cobalt-nickel, tungsten-cobalt-nickel or molybdenum-tungsten-cobalt-nickel, etc. It can also be used as a carrier to be supported, and can also be used as various catalysts.

  As a method for supporting the catalytically active component, an impregnation method in which the above-mentioned molded article (support) of alumina particles is immersed in a solution of a soluble salt of the catalytically active component and the metal component is introduced into the support, or an alumina particle is produced. At this time, a known method such as a coprecipitation method for simultaneously precipitating the metal components can be employed, but it is preferable to use an impregnation method that is easy in operation and convenient for maintaining the stabilization of the catalyst characteristics. For example, the support of alumina particles may be immersed in an impregnation solution at room temperature or above and kept under conditions where the desired component is sufficiently impregnated in the support. The amount and temperature of the impregnation solution can be appropriately adjusted so that a desired amount of the catalytically active component is supported. Further, the amount of the carrier immersed in the impregnation solution can be determined according to the desired loading amount of the catalytically active component.

  In order to carry two or more types of catalytically active components, a one-component impregnation method in which two or more types of catalytically active components are mixed in advance and simultaneously impregnated from the mixed solution can be adopted. It is also possible to employ a two-component impregnation method in which the above active ingredient solutions are separately prepared and impregnated sequentially.

The present invention will be described in detail by the following experimental examples.
Various measurement methods used in the following experiments are as follows.

(1) Chemical analysis;
Si and Al are measured according to JIS. M.M. Measured according to 8853.

(2) specific surface area;
Measurement was performed by a nitrogen adsorption method using TriStarII 3020 manufactured by Micromeritics. The specific surface area was analyzed by the BET method from the adsorption side nitrogen adsorption isotherm having a specific pressure of 0.05 to 0.20.

(3) Median diameter (D ₅₀ )
Measurement by laser diffraction / scattering method was performed using a Mastersizer 2000 manufactured by Malvern. Ethanol was used as the dispersion medium, and the particle refractive index 1.49, the dispersion medium refractive index 1.36, and the light scattering model were analyzed by Mie theory.

(4) pore volume, pore distribution, macropore diameter peak top;
Measurement was performed by mercury porosimetry using an AutoPore IV 9500 manufactured by Micromeritics. The pore volume V ₂ of mesopores having a pore diameter of 4 to 50 nm is 5,000 to 60000 psia, and the pore volume V ₁ of macropores having a pore diameter of 50 to 8000 nm is 27.5 to 5000 psia. Thus, the total pore volume Vt of pores having a pore diameter of 4 to 8000 nm was determined from the press-fit amount of 27.5 to 60000 psia. The pore distribution was expressed as a differential pore volume, and the pore diameter showing the maximum differential pore volume value in the range of the pore diameter of 50 to 8000 nm was defined as the macropore diameter peak top.

(5) Macropore distribution An electron microscope image of the cross section of the particle was taken at a magnification of 1000 and analyzed using image processing software ImageJ. The width of the 10 μm scale bar described in the electron microscope image was measured and converted into pixels, and a 50 μm ² grid was overwritten on the electron microscope image. The number of lattices in which the four sides of a 50 μm ² lattice are not in contact with the outer surface of the particle is measured, and a lattice having at least some macropores in the 50 μm ² lattice using an electron microscope image in which the number is at least 80 or more The number was measured and obtained as a percentage of the number of macropore lattices / the total number of lattices.

(6) catalyst preparation;
It is impregnated with platinum and palladium dinitrodiammine nitric acid solution to 0.9 wt% Pt + 0.1 wt% Pd with respect to alumina, reduced at 400 ° C in hydrogen, treated in air at 500 ° C for 1 hour, A sample subjected to aging treatment at 750 ° C. for 50 hours in air was used as a sample for evaluating catalyst performance.

(7) HC, NO oxidation activity evaluation;
It was carried out by a normal pressure fixed bed flow reaction method. A sample exhaust gas of NO200 ppm + C ₁₀ H ₂₂ (decane) 180 ppm + C ₁₁ H ₁₀ (α-methylnaphthalene) 18 ppm + 10% H ₂ O + 5% O ₂ (N ₂ diluted) as 400 m · min ⁻¹ was passed through 400 mg · min ⁻¹ and stepped from 500 ° C. The temperature at which the HC was converted to 50% and the conversion rate from NO to NO _{2 at} 350 ° C. were determined.

(8) Evaluation of fuel mist oxidation activity;
This was carried out by a fixed bed flow type reactor shown in FIG. 0.1 g of granular catalyst was installed in the center of a quartz reactor having an inner diameter of 10 mm. Quartz wool was installed only at the bottom of the bottom so that the fuel mist could reach the catalyst layer directly, and the upper part from the electric furnace was covered with aluminum foil to keep it warm in order to prevent fuel condensation on the inner wall of the reactor. A thermocouple (K type) was inserted into the central part of the catalyst lower quartz wool, and the reaction temperature was continuously monitored. Light oil (JIS No. 2) as fuel was pressurized and flow rate controlled by a liquid mass flow controller (manufactured by GL Science, test was fueled at 2 μL · min ⁻¹ ), and then introduced into a two-fluid spray nozzle for ICP (manufactured by Fujiwara Seisakusho). . The fuel mist was added directly to the reaction tube by simultaneously introducing 0.1 L · min ⁻¹ of air as the atomizing gas. Furthermore, air 0.9L * min < ^-1 > was added and diluted from the circumference | surroundings of the spraying part. As a result, a fuel of 5000 ppmC + 5% O ₂ (N ₂ dilution) was allowed to flow through the catalyst layer at 1 L · min ⁻¹ , and the temperature was continuously decreased from 500 ° C. (3 ° C. · min ⁻¹ ). In order to always maintain the same test conditions, the distance from the nozzle tip to the heater and the upper part of the catalyst layer was kept at 40 mm and 90 mm, respectively. A U-shaped tube containing glass wool cooled to 0 ° C. was provided at the rear stage of the reaction tube. After capturing and separating unreacted fuel mist, the gas component was further introduced into the analyzer at the rear stage. Gas analysis NDIR-COx meter (Shimadzu, CGT7000) was used to monitor the CO and CO ₂ concentration. The catalytic activity was compared at a temperature (T50) at which the complete oxidation rate to CO ₂ was 50% (Table 2).

<Pore modifier>
The organic resin fine particles used for the pore adjuster were as follows.
Pore adjuster 1: GANZPEARL GM-0401S (median diameter 3.1 μm) manufactured by Aika Industry
Pore modifier 2: Chemisnow MX-300 (median diameter 3.0 μm) manufactured by Soken Chemical
In addition, when 0 to 10 μm is divided every 2 μm in the particle size distribution graph, the number (number%) of particles having a particle size in each range is as shown in Table 1 below.

<Example 1>
Aluminum sulfate (Al ₂ O ₃ 11.3%, SO ₃ 14.5%, SG 1.25) was used as a raw material for the alumina source. To 300 g of aluminum sulfate, 10.2 g of pore adjusting agent 1 (GANZPEARL GM-0401S) as a pore adjusting agent was added and mixed by stirring, and 600 mL of water and 73.2 g of 49% caustic soda were mixed and heated to 60 ° C. It was poured into a container and washed with ion-exchanged water heated to 60 ° C. until the washing liquid became 10 μS / cm or less to obtain an organic resin particle-added alumina hydrogel. This gel was put into a 300 mL beaker and the upper part was covered with aluminum foil to make a hydrothermal atmosphere and dried at 150 ° C. for 24 hours to obtain a xerogel. The obtained xerogel was put in a 155 mL crucible, covered with a hydrothermal atmosphere, and calcined at 750 ° C. for 2 hours to obtain macropore-added alumina.

<Comparative Example 1>
A sample was obtained in the same manner as in Example 1 except that the pore adjusting agent was changed to 10.2 g of the pore adjusting agent 2 (Chemisnow MX-300).

<Comparative example 2>
Alumina was obtained in the same manner as in Example 1 except that the pore modifier was not added and drying and firing were not performed in a hydrothermal atmosphere.

<Example 2>
Sodium silicate (SiO ₂ 22.5%, Na ₂ O 7.2%, SG 1.30) and 45% sulfuric acid were supplied using an apparatus capable of instantaneous contact with both, and this solution was supplied at the same magnification. Except that 30 g of acidic silica sol prepared by adding water was added to 300 g of aluminum sulfate, the same operation as in Example 1 was performed to obtain macropore-added silica-dispersed alumina.

<Comparative Example 3>
A sample was obtained in the same manner as in Example 2 except that the pore adjusting agent was changed to 10.2 g of the pore adjusting agent 2 (Chemisnow MX-300).

<Comparative Example 4>
A silica-dispersed alumina was obtained in the same manner as in Example 2 except that the pore modifier was not added.

  The physical properties of each sample obtained in Examples and Comparative Examples were measured and the catalyst performance was evaluated. The results are shown in Table 2.

Claims (6)

There pore diameter is the pore volume _{V 1} of the macropores 50~8000nm the range of 0.04~0.50cm ³ / g, and was determined by taking an electron microphotograph at a magnification 1,000 times the particle cross section, Alumina particles characterized in that distribution of the macropores is observed in 60% or more of the lattice when the electron micrograph is divided by a lattice of 50 μm ² . Mesopores having a pore diameter of 4 to 50 nm have a pore volume V _{2 in} the range of 0.05 to 0.80 cm ³ / g and a total pore volume Vt of pores having a pore diameter of 4 to 8000 nm. The alumina particles according to claim 1, having a multi-pore structure in the range of 0.10 to 1.30 cm ³ / g. Alumina particles according to claim 2 volume ratio of the pore volume _{V 2} of the pore volume _{V 1} and mesopores of the macropores _(V 1 / _{V 2)} is in the range of from 0.08 to 0.80.   The alumina particles according to any one of claims 1 to 3, wherein silica is dispersed in such an amount that the amount of Si represented by 100 x Si / (Si + Al) is 1.0 to 10.0 mol%.   The alumina particles according to any one of claims 1 to 4, which are used as a catalyst carrier.   An exhaust gas purifying catalyst comprising a platinum group metal supported on the alumina particles according to claim 5.