TWI423923B - A silica-based material, a method for producing the same, and a method for producing a carboxylic acid of a noble metal-supported material and a catalyst - Google Patents

Description

Cerium dioxide-based material, method for producing the same, and precious metal carrier and method for producing carboxylic acid used as catalyst

The present invention relates to a cerium oxide-based material, a method for producing the same, and a method for producing a precious metal carrier and a carboxylic acid used as a catalyst.

The cerium oxide-based material is used in various applications as a material using its characteristics. As an example, a filler for liquid chromatography, a cosmetic base, a catalyst, a catalyst carrier, a flow regulator, and a diluent can be given. One of the methods for satisfying physical properties such as high specific surface area to satisfy the main conditions required for such applications is a method of making the cerium oxide-based material porous, but the mechanical strength of the cerium oxide-based material may change. weak. On the other hand, if the precursor is calcined at a high temperature in order to increase the mechanical strength of the cerium oxide-based material, the specific surface area thereof becomes small. Thus, it is difficult to obtain a cerium oxide-based material that satisfies the physical properties of the mechanical strength and the specific surface area is large, and it is currently impossible to obtain a cerium oxide-based material that satisfies the two main conditions.

Quartz, which is one of the cerium oxide-based materials, is known to be hard and has high mechanical strength. However, in general, quartz is excellent in mechanical strength, but has a low specific surface area (1 m ² /g or less), and is difficult to use for applications requiring a high specific surface area. In order to use as a catalyst carrier, there is a case where the specific surface area of the cerium oxide-based material is increased. However, in this case, the mechanical strength is sacrificed, and there is no example in which the surface area and the mechanical strength are combined.

Patent Document 1 discloses, as a carrier for a catalyst for producing a carboxylic acid ester, cerium oxide-alumina-magnesia, which contains aluminum in the form of Al ₂ O ₃ in an amount of 5 to 40% by weight. The form of MgO contains magnesium in the range of 3 to 30% by weight, and contains cerium in the range of 50 to 92% by weight in the form of SiO ₂ .

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 9-52044

The ceria-alumina-magnesia support disclosed in Patent Document 1 has the characteristics of high mechanical strength, large specific surface area, water resistance higher than that of cerium oxide, and acid resistance higher than that of alumina. However, when the carrier is used as a carrier for a catalyst for producing a carboxylic acid ester, mechanical strength can be satisfied under normal use conditions, but conditions such as mixing of particles with particles and stirring springs, etc., for example, In the reaction under severe conditions in the suspension reaction, there is a problem that cracks or defects occur due to such friction or the like.

Further, according to the study by the inventors of the present invention, it is judged that the reaction is carried out for a long period of time by using the catalyst having the carrier disclosed in Patent Document 1, although the reaction is carried out slowly, but the pore diameter is enlarged. And structural changes in the catalyst particles caused by particle growth. It is considered that the enlargement of the pore diameter is caused by the following reasons: the catalyst particles are locally repeatedly exposed to the acid and the alkali due to the addition of the by-products of the acid component and the alkali component, and the ceria-alumina-magnesia carrier One of the aluminum and aluminum is partially dissolved and precipitated to produce a rearrangement of the ceria-alumina crosslinked structure. Further, it was also judged that the particle growth was carried out by sintering of the noble metal while the pore diameter was enlarged, and as a result, the catalytic activity was lowered.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a cerium oxide-based material, a method for producing the same, and a noble metal carrier containing the cerium oxide-based material, wherein the cerium oxide-based material has a strong mechanical strength. It has a large specific surface area and is excellent in acid resistance and alkalinity.

The inventors of the present invention have considered the improvement of the chemical stability and mechanical strength of the cerium oxide gel, and have focused on the specific structure of the cerium oxide chain (-Si-O-) constituting the cerium oxide gel, These structures and physical properties are subject to intensive research. As a result, it has been unexpectedly found that it contains at least one element selected from the group consisting of iron, cobalt, nickel, and zinc, and a group selected from the group consisting of alkali metal elements, alkaline earth metal elements, and rare earth elements. The cerium oxide-based material of the composite oxide of at least one basic element is excellent in acid resistance and alkalinity, and overcomes the various disadvantages as described above in the conventional cerium oxide-based material, and the above problems can be solved; Thus, the present invention has been completed.

That is, the present invention is as follows.

[1]

A cerium oxide-based material having a total molar amount of 42 to 90 mol% and 3 to 38 mol% with respect to the following cerium, the following aluminum, the following fourth periodic element, and the following basic elements: %, 0.5-20 mol%, and 2~38 mol% of the range: 矽, aluminum, at least one fourth periodic element selected from the group consisting of iron, cobalt, nickel, and zinc, and selected from At least one basic element of the group consisting of an alkali metal element, an alkaline earth metal element, and a rare earth element.

[2]

The cerium oxide-based material according to the above [1], wherein the composition ratio of the fourth periodic element to the aluminum is 0.02 to 2.0 on a molar basis.

[3]

The cerium oxide-based material according to the above [1] or [2], wherein a composition ratio of the fourth periodic element to the basic element is 0.02 to 2.0 on a molar basis.

[4]

The cerium oxide-based material according to any one of the above-mentioned [1], wherein the fourth periodic element is nickel, and the basic element is magnesium, and the bismuth, the aluminum, the nickel, and the magnesium are The total amount of moles is contained in the range of 42 to 90 mol%, and the aluminum is contained in the range of 3 to 38 mol%, and the nickel is contained in the range of 0.5 to 20 mol%. The above-mentioned magnesium is contained in the range of ~38 mol%.

[5]

A method for producing a cerium oxide-based material, comprising: a step of obtaining a composition comprising cerium oxide, an aluminum compound selected from at least one of the group consisting of iron, cobalt, nickel, and zinc a compound of a 4-period element, and a compound selected from the group consisting of at least one basic element consisting of an alkali metal element, an alkaline earth metal element, and a rare earth element; and calcining the above composition or a dried product of the composition to obtain a solid substance And a step of obtaining a cerium oxide-based material having a total amount of erbium-based material relative to the following cerium, the following aluminum, the following fourth periodic element, and the following basic elements: 90% molar, 3~38 mol%, 0.5-20 mol%, 2~38 mol% range: 矽, aluminum, selected from at least the group consisting of iron, cobalt, nickel and zinc A fourth periodic element and at least one basic element selected from the group consisting of an alkali metal element, an alkaline earth metal element, and a rare earth element.

[6]

The method for producing a cerium oxide-based material according to the above [5], which further comprises the step of hydrothermally treating the solid matter.

[7]

A method for producing a cerium oxide-based material, comprising: calcining a compound containing cerium oxide, an aluminum compound, and at least one basic element selected from the group consisting of an alkali metal element, an alkaline earth metal element, and a rare earth element; a step of obtaining a solid matter by the composition or the dried product of the composition; and acidifying the solid matter with a soluble metal salt containing at least one fourth periodic element selected from the group consisting of iron, cobalt, nickel, and zinc a mixture of the aqueous solution is neutralized, and a step of analyzing the element containing the fourth periodic period is analyzed onto the solid matter; a step of hydrothermally treating the solid matter having the fourth periodic element precipitated; and a step of heat-treating the solid matter in the heat treatment step; and obtaining a cerium oxide material having a total amount relative to the following cerium, the following aluminum, the following fourth periodic element, and the following basic elements The amount of ear, in the range of 42-90 mol%, 3~38 mol%, 0.5-20 mol%, 2~38 mol%, respectively: 矽, aluminum, selected from iron, cobalt, nickel and zinc Composed of In the group consisting of at least one element of the fourth period, and selected from the group consisting of alkali metal elements, alkaline earth elements and rare earth metal is at least one kind of basic element.

[8]

A noble metal-supporting material, comprising: the cerium oxide-based material according to any one of the above [1] to [4], and the cerium, lanthanum, palladium, silver supported on the cerium oxide-based material At least one precious metal component of the group consisting of ruthenium, osmium, iridium, platinum, and gold.

[9]

The noble metal carrier according to the above [8], wherein the noble metal component has an average particle diameter of 2 to 10 nm.

[10]

A method for producing a carboxylic acid ester by reacting an aldehyde with an alcohol in the presence of a noble metal support of the above [8] or [9] and oxygen.

[11]

The method for producing a carboxylic acid ester according to the above [10], wherein the aldehyde is at least one selected from the group consisting of acrolein, methacrolein, and a mixture thereof.

[12]

The method for producing a carboxylic acid ester according to the above [10], wherein the aldehyde is at least one selected from the group consisting of acrolein, methacrolein, and a mixture thereof, and the alcohol is methanol.

[13]

A method for producing a carboxylic acid, which is obtained by oxidizing an aldehyde in the presence of a noble metal carrier of the above [8] or [9] to produce a carboxylic acid.

[14]

The method for producing a carboxylic acid according to the above [13], wherein the aldehyde is at least one selected from the group consisting of acrolein, methacrolein, and a mixture thereof.

According to the present invention, it is possible to provide a cerium oxide-based material and a noble metal carrier containing the cerium oxide-based material, which has strong mechanical strength, large specific surface area, and acid resistance and alkali resistance. Excellent sex.

Hereinafter, the form for carrying out the present invention (hereinafter simply referred to as "this embodiment") will be described in detail. The present invention is not limited to the embodiments described below, and various modifications can be made without departing from the spirit and scope of the invention.

The total amount of moles of the cerium oxide-based material of the present embodiment with respect to the following cerium, the following aluminum, the following fourth periodic element, and the basic element are respectively 42 to 90 mol%, 3 to 38 mol%. %, 0.5-20 mol%, and 2~38 mol% of the range: 矽, aluminum, at least one fourth periodic element selected from the group consisting of iron, cobalt, nickel, and zinc, and selected from At least one basic element of the group consisting of an alkali metal element, an alkaline earth metal element, and a rare earth element.

The cerium oxide-based material of the present embodiment contains at least one fourth periodic element containing cerium and aluminum selected from the group consisting of iron (Fe), cobalt (Co), nickel (Ni), and zinc (Zn). And a composite oxide of at least one basic element selected from the group consisting of an alkali metal element, an alkaline earth metal element, and a rare earth element, that is, a so-called cerium oxide composite material.

Hereinafter, the characteristics of the cerium oxide-based material of the present embodiment will be described. In the present embodiment, the reason why the acid resistance, alkalinity, and mechanical strength of the cerium oxide-based material can be greatly improved can be estimated as follows.

It is considered that the cerium oxide-based material of the present embodiment is newly formed by coexisting aluminum (Al) in a cerium oxide having an uncrosslinked cerium oxide (Si-O) chain such as a cerium oxide gel. The cross-linking structure of the Si-O-Al-O-Si bond caused by the Al of the Si-O chain (hereinafter also referred to as "cerium oxide-alumina cross-linking structure") does not lose the Si-O chain. In the case of the stability of an acidic substance, a crosslinked structure is formed by Al. It is considered that the Si-O bond can be strengthened by this, and the hydrolysis stability (hereinafter referred to simply as "water resistance") is remarkably improved. It is also considered that when the ceria-alumina crosslinked structure is formed, the Si-O uncrosslinked chain is reduced and the mechanical strength is also increased as compared with the case of the ceria alone. That is, it is inferred that the amount of formation of the ceria-alumina crosslinked structure is related to the improvement of the mechanical strength and water resistance of the obtained ceria-based material.

With the formation of the ceria-alumina crosslinked structure, since the valence of Si (tetravalent) and Al (trivalent) is different, the electric charge becomes unstable. Therefore, in the cerium oxide-based material of the present embodiment, in addition to cerium and aluminum, at least one basic element selected from the group consisting of an alkali metal element, an alkaline earth metal element, and a rare earth element is coexistent. Thereby, the neutral element of 1 to 3 valence is neutralized to promote the stabilization of the charge. Further, it is estimated that the balance of electric charges is further obtained by the three-component system, and thus the stability of the structure is further improved. As one of the bases, cerium oxide-alumina exhibits acidity, whereas cerium oxide-alumina-magnesia generally exhibits neutrality.

Further, the cerium oxide-based material of the present embodiment contains at least one fourth periodic element selected from the group consisting of iron, cobalt, nickel, and zinc in addition to the above-described three component elements, and does not include the fourth cycle. Compared with the elements, the acid resistance and alkalinity are improved. Therefore, even under the pH swing condition which is repeatedly exposed to an acid or a base, the structural stability is high, and the enlargement of the pore diameter and the decrease of the specific surface area can be suppressed.

According to the study by the inventors of the present invention, it has been found that when ceria-alumina or ceria-alumina-magnesia is repeatedly exposed to an acid or a base, although it is carried out slowly, it causes Structural changes in the bismuth dioxide-based material. The reason for this phenomenon is that the cerium oxide-based materials are partially repeatedly exposed to an acid and a base, and a part of cerium oxide and aluminum in the cerium oxide-based material is partially dissolved and precipitated to produce cerium oxide-alumina. The re-arrangement of the joint structure increases the pore diameter of the cerium oxide-based material. Further, when it is determined that the metal carrier carrying the noble metal is supported on the above-mentioned ceria-based material, the expansion of the pores caused by the pH fluctuation causes the sintering of the supported noble metal. The specific surface area of the noble metal decreases, so the catalytic activity decreases.

On the other hand, in the cerium oxide-based material of the present embodiment, it is considered that the fourth periodic element reacts with aluminum and/or a basic element which is a constituent element of the cerium oxide-based material to form a A composite oxide of 4 periodic elements. As a result of the formation of such a compound on the stabilization of the ceria-alumina crosslinked structure, the acid resistance and alkalinity of the ceria-based material are improved, and the structural change is greatly improved.

Here, the "composite oxide" in the present specification means an oxide containing two or more kinds of metals. In other words, the "composite oxide" is an oxide of a compound which forms two or more kinds of metal oxides, and includes a complex oxide in which an oxyacid-containing ion is not present as a structural unit (for example, a perovskite-type oxide of nickel) Challenging spinel oxide). However, the concept of a complex oxide is a composite of all two or more metals. The oxide of two or more kinds of metal oxides to form a solid solution is also in the category of "composite oxide".

For example, a nickel dioxide is selected as the fourth periodic element, magnesium is selected as the basic element, and a cerium oxide-based material containing a composite oxide of cerium-aluminum-nickel-magnesium is used, and a double crystal type high-resolution fluorescent X is used. When the chemical state of nickel is analyzed by the ray analysis method (HRXRF), the nickel in the cerium oxide-based material of the present embodiment does not exist in the form of nickel oxide as a single compound. The nickel is present in the form of a nickel-containing oxidized compound formed by combining nickel oxide with aluminum oxide and/or magnesium oxide, or a composite oxide containing nickel such as a solid solution or a mixture thereof.

The double crystal type high-resolution fluorescent X-ray analysis method (HRXRF) has an extremely high energy resolution, and can analyze the chemical state of an element according to the energy position (chemical shift) or shape of the obtained spectrum. In particular, in the Kα spectrum of the 3d transition metal element, the chemical state of the element can be analyzed in detail due to changes in chemical shift or spectral shape due to changes in valence or electronic state. In the cerium oxide-based material of the present embodiment, the NiKα spectrum is different from that in the case of nickel oxide, and the chemical state of nickel different from the nickel oxide as a single compound is confirmed.

It is presumed that in the cerium oxide-based material of the present embodiment, nickel is a solid solution of a spinel compound such as nickel oxide and aluminum oxide, that is, nickel aluminate (NiAl ₂ O ₄ ) or nickel oxide and magnesium oxide ( The form of NiO‧MgO) exists. It is considered that the above-mentioned fourth periodic element other than nickel is also formed in the ceria-alumina crosslinked structure by forming a spinel compound of its oxide and alumina or a solid solution with an alkali metal oxide. It plays a role in stabilizing and improves chemical stability.

The specific surface area of the cerium oxide-based material of the present embodiment is not particularly limited, and when it is used as a carrier, it is preferably 20 to 500 m ² /g, more preferably 50 to 400 m ² /g, and further Good is 50~350 m ² /g. When a cerium oxide-based material is used as a carrier, from the viewpoint of the ease of carrying a supporting component such as a noble metal, when the carrier is used as a catalyst, the catalytic activity is considered. In particular, the specific surface area of the cerium oxide-based material is preferably 20 m ² /g or more. Moreover, the specific surface area of the ceria-based material is preferably 500 m ² /g or less from the viewpoint of mechanical strength and water resistance.

When a cerium oxide-based material is used as the catalyst carrier, the pore diameter is preferably from 3 to 50 nm, more preferably from 3 to 30 nm, and still more preferably from 3 to 10 nm. When the catalyst is used in the liquid phase reaction, the pore diameter is preferably 3 nm from the viewpoint of not limiting the diffusion rate of the reaction substrate without excessively increasing the diffusion resistance in the pores and maintaining the reaction activity highly. the above. On the other hand, from the viewpoint of the difficulty of cracking of the catalyst and the ease of peeling of the supporting component such as a noble metal, it is preferably 50 nm or less.

The pore volume of the cerium oxide-based material is preferably in the range of 0.1 to 1.0 mL/g, more preferably in the range of 0.1 to 0.5 mL/g, from the viewpoint of strength and supporting characteristics. The pores in the cerium oxide-based material are required to carry the supporting component. In view of mechanical strength and water resistance, the ceria-based material of the present embodiment preferably has a specific surface area, a pore diameter, and a pore volume in the above range. Here, the specific surface area, the pore diameter, and the pore volume of the cerium oxide-based material are measured by the method described later.

a cerium oxide-based material containing a composite oxide containing cerium, aluminum, the fourth periodic element, and the basic element, and a total amount of cerium, aluminum, a fourth periodic element, and an alkaline element, 42~ 90% of the range contains 矽, containing aluminum in the range of 3 to 38% by mole, containing the fourth periodic element in the range of 0.5 to 20% by mole, and containing in the range of 2 to 38% by mole. Alkaline element. If the amount of lanthanum, aluminum, the fourth periodic element, and the basic element is within the above range, yttrium, aluminum, the fourth periodic element, the basic element, and the oxygen atom form a specific stable bonding structure with each other, and the bonding structure is easy to It is formed in a state in which it is uniformly dispersed in the cerium oxide-based material. Preferably, it contains yttrium in the range of 70 to 90 mol%, aluminum in the range of 5 to 30 mol%, and the fourth periodic element in the range of 0.75 to 15 mol%, in 2 to 30 mo The range of the ear% contains an alkaline element, more preferably contains yttrium in the range of 75 to 90% by mole, and contains aluminum in the range of 5 to 15% by mole, and contains in the range of 1 to 10% by mole. The element of the fourth cycle contains an alkaline element in the range of 2 to 15 mol%. In particular, when the composition ratio of the elements of the fourth periodic period is 0.75 mol% or more and the components are uniformly dispersed in the entire material, it is possible to obtain a portion in which the fourth periodic element is not present in the structure, even if A cerium oxide-based material which exhibits resistance (high acid resistance and high alkalinity) in the case of repeated exposure to an acid and/or a base. From the viewpoint of obtaining a cerium oxide-based material having a high mechanical strength and a large specific surface area, the element of the fourth periodic period is preferably 10 mol% or less, and the basic element is 30 mol% or less. The composition ratio of bismuth to aluminum is set within a preferred range from the viewpoints of acid resistance, alkalinity, and water resistance of the cerium oxide-based material. The composition of bismuth relative to aluminum is better (矽/aluminum) = 2~4. When (矽/aluminum) is less than the above range, there is a tendency for acid resistance and alkalinity to decrease. If (矽/aluminum) is larger than the above range, the water resistance tends to decrease.

Examples of the alkali metal element of the basic element include lithium (Li), sodium (Na), potassium (K), ruthenium (Rb), and cesium (Cs). Examples of the alkaline earth metal element include ruthenium. (Be), magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba). Examples of the rare earth element include lanthanum (La), cerium (Ce), and praseodymium (Pr).

In the present embodiment, the composition ratio of the fourth periodic element to aluminum or an alkaline element is present in a preferred range. The composition ratio of the fourth period element to aluminum (the fourth period element/aluminum) is preferably 0.02 to 2.0, more preferably 0.05 to 1.75, still more preferably 0.1 to 1.2, on a molar basis. Further, the composition ratio of the fourth periodic element to the basic element (the fourth periodic element/alkaline element) is preferably 0.02 to 2.0, more preferably 0.05 to 1.75, still more preferably 0.1 to 1.2, on a molar basis. When the composition ratio of the element of the fourth cycle to the aluminum or the basic element is within the above range, the effect of improving the structure of the aluminum and the structure change of the cerium oxide-based material tends to increase. The reason is considered to be that, in this range, the fourth periodic element, aluminum, and basic element form a specific composite oxide to form a stable bonded structure. That is, in the cerium oxide-based material, if the ratio of the fourth periodic element to the basic element or aluminum is too low, a preferred structure is locally formed, but the entire thickness of the cerium oxide-based material is not present. A preferred structure is formed. On the other hand, when the composition ratio is satisfied, in particular, (the fourth periodic element/aluminum) = 0.05 to 1.75, and the (fourth periodic element/alkaline element) = 0.05 to 1.75, the preferred structure can be The degree of stabilization of the material as a whole exists.

In the case where the element is nickel and the basic element is magnesium in the fourth cycle, the cerium oxide-based material containing a composite oxide of cerium, aluminum, nickel, and magnesium is resistant to acidity and alkali, mechanical strength, and water resistance. From the viewpoint of the total amount of lanthanum, aluminum, nickel and magnesium, it is preferably contained in the range of 42 to 90 mol%, and aluminum in the range of 3 to 38 mol%, at 0.5. Nickel is contained in the range of ~20 mol%, and magnesium is contained in the range of 2 to 38 mol%. More preferably, it contains yttrium in the range of 70 to 90% by mole, aluminum in the range of 5 to 30% by mole, and nickel in the range of 0.75 to 15% by mole, and 2 to 30% by mole. The range contains magnesium, and further preferably contains yttrium in the range of 75 to 90% by mole, aluminum in the range of 5 to 15% by mole, and nickel in the range of 1 to 10% by mole. Magnesium is contained in the range of ~15% by mole. If the elemental composition of cerium, aluminum, nickel and magnesium is within the above range, cerium, aluminum, nickel and magnesium tend to form a specific stable bonding structure. In particular, in the case of a better composition ratio, even if it is assumed that the above-mentioned stable bonded structure is uniformly dispersed in the cerium oxide-based material, it is expected to be sufficiently present for contributing to the stabilization of the entire cerium oxide-based material. Density formation. As a result, the cerium oxide-based material tends to exhibit acid resistance, alkalinity, and mechanical strength which are excellent in resistance to repeated use.

The solid form of the cerium oxide-based material of the present embodiment is not particularly limited as long as the specific physical properties are obtained.

The dispersion state of the fourth periodic element in the ceria-based material of the present embodiment is not particularly limited, and from the viewpoint of stabilizing the structure of the entire ceria-based material, it is preferred that there is no distribution in the entire material. Disperse evenly. Specifically, it is preferable to observe the cross section of the ceria material by electron probe microanalysis (EPMA), and it is preferable that the elements of the fourth cycle are present at substantially the same concentration in all the observed portions. In such a dispersed state, there is a tendency that a specific stable bonding structure formed by ruthenium, aluminum, a fourth periodic element, and an alkaline element exists to contribute to the stabilization of the entire material, and even if it is repeated for a long time. It also maintains acid and alkali resistance. Here, the term "substantially the same concentration" means a state in which the distribution range of the measured values is within 10%.

The substantial thickness or particle diameter of the cerium oxide-based material may be various sizes ranging from μm to cm, and the shape is also not particularly limited. Specific examples of the shape of the cerium oxide-based material include a spherical shape, an elliptical shape, a cylindrical shape, a tablet form, a hollow cylindrical shape, a plate shape, a rod shape, a sheet shape, and a honeycomb shape. When it is used as a catalyst or a catalyst carrier, the shape of the cerium oxide-based material of the present embodiment can be appropriately changed depending on the reaction form to be used. For example, in the case of using a ceria-based material in a fixed-bed reaction, it is preferably a hollow cylindrical or honeycomb having a small pressure loss, and is generally spherical in the liquid slurry suspension condition. In particular, when the cerium oxide-based material is used as a carrier for the catalyst used in the fluid bed reaction, the shape thereof is preferably spherical particles, and the average particle diameter of the particle diameter is preferably from 1 to 200 μm. More preferably, it is 10 to 200 μm, and further preferably 30 to 150 μm. By using the cerium oxide-based material as such particles, the excellent effects of the present invention can be exhibited more effectively and surely. The average particle diameter of the cerium oxide-based material is measured by the method described later.

The cerium oxide-based material containing a composite oxide containing cerium, aluminum, the above-mentioned fourth periodic element, and the above basic element has a water resistance higher than that of cerium oxide and has higher acid resistance than alumina. Further, the cerium oxide-based material has excellent physical properties such as mechanical strength higher than that of cerium oxide. Moreover, the cerium oxide-based material has extremely high chemical stability as compared with cerium oxide-alumina or cerium oxide-alumina-magnesia, for example, it can suppress pH swing conditions which are repeatedly exposed to acid and alkali. In the next step, a structural change such as an increase in pore diameter or a decrease in specific surface area caused by dissolution or precipitation of one of bismuth and aluminum is partially caused.

Next, a method for producing the cerium oxide-based material of the present embodiment having the above composition will be described.

The method for producing a cerium oxide-based material containing a composite oxide containing cerium, aluminum, the fourth periodic element, and the basic element is not particularly limited, and includes, for example, the following steps: (1) to (1) below a method of obtaining a composition comprising a compound of cerium oxide, an aluminum compound, a compound of a fourth periodic element, and a basic element, by a method of 6); a step of drying the composition as needed to obtain a dried product; and drying the composition The step of calcining the material or the above composition under the conditions described below.

(1) A commercially available ceria-alumina composition is reacted with a compound of a fourth cycle element and a compound of a basic element.

(2) A ceria-alumina gel is formed in advance, and a compound of the fourth periodic element and a compound of a basic element are added to the gel to cause a reaction.

(3) The cerium oxide sol is reacted with an aluminum compound, a compound of the fourth periodic element, and a compound of a basic element.

(4) The cerium oxide sol is reacted with a water-insoluble aluminum compound, a compound which is insoluble in the fourth periodic element of water, and a compound which is insoluble in water.

(5) The cerium oxide gel is reacted with an aqueous solution of a water-soluble aluminum compound, a compound of a water-soluble fourth periodic element, and a compound of a water-soluble basic element.

(6) The ceria gel is subjected to a solid phase reaction with a compound of an aluminum compound, a compound of a fourth cycle element, and a compound of a basic element.

Hereinafter, a method of preparing the ceria-based material using the methods (1) to (6) above will be described in detail.

In the method of the above (1), a compound containing a fourth periodic element and a compound containing a basic element are mixed in a commercially available ceria-alumina composition to obtain a slurry. The slurry is dried and further calcined under the conditions described below, whereby a cerium oxide-based material can be prepared. The compound containing a fourth periodic element and the compound containing a basic element are preferably water-soluble compounds typified by chlorides, carbonates, nitrates, and acetates. However, a water-insoluble compound such as a hydroxide or an oxide can also be used.

In the methods (2) to (6) above, for example, a cerium oxide sol, a water glass or a cerium oxide gel can be used as the source of cerium oxide. The cerium oxide gel may be any one having an uncrosslinked Si site which reacts with Al, and the length of the Si-O chain is not particularly limited. The aluminum compound is preferably a water-soluble compound represented by sodium aluminate, aluminum chloride hexahydrate, aluminum perchlorate hexahydrate, aluminum sulfate, aluminum nitrate nonahydrate, and aluminum diacetate. However, it may be a water-insoluble compound such as aluminum hydroxide or aluminum oxide, and if it is a cerium oxide sol or a compound which reacts with uncrosslinked Si in a cerium oxide gel, it can be used for a cerium oxide-based material. preparation. Examples of the compound containing the fourth periodic element or the basic element include oxides, hydroxides, chlorides, carbonates, sulfates, nitrates, and acetates of the elements.

In the case of the method using the cerium oxide-alumina gel (2), sulfuric acid is added to the water glass to prepare a cerium oxide hydrogel having a pH of 8 to 10.5, and a pH of 2 is added thereto. Or a 2 or less Al ₂ (SO ₄ ) ₃ solution, and further add sodium aluminate having a pH of 5 to 5.5 to prepare a ceria-alumina hydrogel. Next, the water contained in the hydrogel is adjusted to 10 to 40% by spray drying or the like, and a compound of the fourth periodic element and a basic element are added thereto to obtain a composition. Further, after the composition is dried, it is calcined under the conditions described below, whereby a cerium oxide-based material can be obtained.

In the case of the method of (3) and (4) using a cerium oxide sol as a starting material, a compound of an aluminum compound, a compound of a fourth periodic element, and a compound of a basic element are mixed in a cerium oxide sol to obtain a second a mixture of a cerium oxide sol, an aluminum compound, a compound of a fourth periodic element and a compound of a basic element, that is, a mixture sol, and secondly, the mixture is dried to obtain a gel, which is condensed under the conditions of temperature, time and atmosphere described later. The glue is calcined.

Alternatively, an alkaline aqueous solution is added to the mixture sol to coprecipitate the cerium oxide, the aluminum compound, the compound of the fourth periodic element, and the basic element, and the coprecipitate is dried and then calcined under the conditions described below. Further, a cerium oxide-based material having a desired particle diameter can also be obtained by a step of granulating the gel by directly drying the sol of the mixture by using a spray dryer or drying the sol of the mixture.

Particularly in the case of the method of (4), the cerium oxide sol is reacted with a water-insoluble aluminum compound, a compound which is insoluble in the fourth periodic element of water, and a compound which is insoluble in water. In the case of the above, the aluminum compound, the compound of the fourth periodic element, and the compound of the basic element may be separately pulverized to a specific particle diameter or may be pre-crushed. After mixing and reacting the water-insoluble aluminum compound, the compound insoluble in the fourth-cycle element of water, and the compound insoluble in water with the cerium oxide sol, the reactant is dried, and further under the conditions described later Calcination is carried out. Further, the aluminum compound, the compound of the fourth periodic element, and the compound of the basic element may not be pre-pulverized or pre-calcined, and the calcined ceria-alumina-fourth periodic element-alkaline element may be used. The composition is comminuted to a specific particle size.

In the case of the method of (5) using a cerium oxide gel as a starting material, a cerium oxide gel and a water-soluble aluminum compound, a water-soluble fourth periodic element compound, and a water-soluble basic element are used. The aqueous solution of the compound is reacted. At this time, the ceria gel may be preliminarily pulverized to a specific particle size or pre-crushed. In the case of the method of (5), a mixture of an aqueous solution of a cerium oxide gel and a water-soluble aluminum compound, an aqueous solution of a water-soluble fourth periodic element, and a water-soluble basic element compound is obtained. After the slurry, the slurry is dried and further calcined for 1 to 48 hours under the conditions described below. Alternatively, the composition of the calcined ceria-alumina-fourth cycle element-alkaline element may be pulverized to a specific particle size without pre-pulverizing or pre-grinding the ceria gel.

The method of (6) using the cerium oxide gel as a starting material is a solid phase reaction of a cerium oxide gel with an aluminum compound, a compound of a fourth periodic element, and a compound of a basic element to obtain a composition. The reactants. In this case, Al is reacted with uncrosslinked Si in a solid phase state. The cerium oxide gel, the aluminum compound, the compound of the fourth periodic element, and the compound of the basic element may be previously pulverized to a specific particle diameter, or may be subjected to preliminary coarse pulverization. In this case, each substance may be separately pulverized or may be mixed and pulverized. The reactant obtained by the solid phase reaction is dried as needed, and then calcined. The calcination is preferably carried out under the conditions of temperature, time and atmosphere described later. The cerium oxide gel, the aluminum compound, the compound of the fourth periodic element, and the compound of the basic element may not be pre-pulverized or pre-crushed, and the reactant obtained by the reaction may be pulverized to a desired particle size. .

As a method for preparing a composition of a compound containing a cerium oxide, an aluminum compound, a compound of a fourth periodic element, and a basic element, it is also possible to use a component which adsorbs the above-mentioned basic element to contain cerium, aluminum, and the fourth cycle. A method of a composite oxide of an element of a cerium oxide-based material. In this case, for example, a method of adding a cerium oxide-based material to a liquid in which a compound having a basic element is dissolved, a method of immersing such as drying, or a basic element having a pore volume fraction may be used. A method of impregnation of a compound into the above-mentioned ceria-based material and drying it.

A method of adsorbing a component containing a fourth periodic element to a ceria-based material containing a composite oxide containing cerium, aluminum, and a basic element may also be used. In this case, for example, a method of using a immersion method such as adding the above-mentioned cerium oxide-based material to a liquid in which a compound containing a fourth periodic element is dissolved and drying treatment, or using a portion containing a pore volume fraction may be used. A method in which a compound of a 4-period element is infiltrated into the above-mentioned ceria-based material and subjected to a drying treatment. However, the method of adsorbing the component containing the basic element or the component containing the fourth periodic element must be followed by high concentration of the component containing the basic element or the component containing the fourth periodic element in the ceria-based material, and The liquid drying treatment is carried out under mild conditions.

In order to control the properties of the slurry and finely adjust the properties of the pore structure of the product and the physical properties obtained, an inorganic substance or an organic substance may be added to the slurry containing the various raw materials obtained as described above. Specific examples of the inorganic material include mineral acids such as nitric acid, hydrochloric acid, and sulfuric acid; alkali metals such as Li, Na, K, Rb, and Cs; metal salts such as alkaline earth metals such as Mg, Ca, Sr, and Ba; and ammonia or A water-soluble compound such as ammonium nitrate, or a clay mineral which is dispersed in water to form a suspension. Further, specific examples of the organic substance include polymers such as polyethylene glycol, methyl cellulose, polyvinyl alcohol, polyacrylic acid, and polypropylene decylamine.

There are various effects obtained by adding an inorganic substance and an organic substance, and it is mainly a case where a ceria-based material is formed into a spherical shape, and a pore diameter and a pore volume are controlled. More specifically, in terms of obtaining a spherical cerium oxide-based material, the liquid quality of the mixed slurry becomes an important factor. By adding an inorganic substance or an organic substance, the viscosity of the slurry or the concentration of the solid content component is adjusted, and the liquid state of the spherical cerium oxide-based material can be more easily obtained. Further, in order to control the pore diameter and the pore volume, the optimum organic compound which can be removed by the calcination and washing operation after the formation of the ceria-based material in the molding stage is selected.

Next, a composition such as a slurry, a gel, or a reactant containing the above various raw materials and additives is dried. The drying method is not particularly limited, and from the viewpoint of controlling the particle size of the ceria-based material, spray drying is preferred. In this case, as a method of droplet-forming the mixed slurry, a method using a known spray device such as a rotary disk method, a two-fluid nozzle method, or a pressurized nozzle method can be mentioned.

The sprayed liquid (slurry) must be used in a state of being sufficiently mixed. In the case where the mixing state is poor, the durability is lowered due to the uneven distribution of the composition, which affects the performance of the cerium oxide-based material. In particular, when the raw materials are blended, there is a case where the viscosity of the slurry rises and a part of the gelation (condensation of the colloid) occurs, and there is a possibility that uneven particles are formed. Therefore, in addition to the consideration of slowly mixing the raw materials under stirring, there is also a method of preparing a mixed slurry while controlling the mixture to a quasi-stable region of, for example, a cerium oxide sol having a pH of 2 by adding an acid or a base. The better case.

The sprayed liquid preferably has a specific range of viscosity and solids component concentration. When the viscosity or the solid content concentration is less than a specific range, there is a tendency that the porous body obtained by spray drying does not become a spherical ball, and a large spherical hollow body is scattered. Moreover, when these are higher than the specific range, there is a case where the dispersibility of the porous bodies is adversely affected, and the droplets are not stably formed due to the properties. Therefore, as long as the viscosity of the liquid to be sprayed can be sprayed, the temperature at the time of spraying is preferably in the range of 5 to 10,000 cp. Further, from the viewpoint of the shape, it is preferable that the viscosity is higher in the range which can be sprayed, and the viscosity is more preferably in the range of 10 to 1000 cp from the viewpoint of balance of workability. . Further, from the viewpoint of shape or particle diameter, the solid content concentration is preferably in the range of 10 to 50% by mass. Further, as a target of the spray drying conditions, it is preferred that the hot air temperature at the inlet of the drying tower of the spray dryer is 200 to 280 ° C, and the outlet temperature of the drying tower is in the range of 110 to 140 ° C.

Next, the solid matter is obtained by calcining the composition obtained by the method further dried by the above methods (1) to (5) or the method obtained by the method of (6). The calcination temperature is generally in the range of 200 to 800 °C. When the composition is calcined at 800 ° C or lower, the specific surface area of the ceria-based material can be increased. When the composition is calcined at 200 ° C or higher, the dehydration or condensation reaction between the gels becomes more sufficient, and the film can be further suppressed. The pore volume is greatly increased. When the calcination temperature is in the range of 300 to 600 ° C, it is preferable from the viewpoint of balance of physical properties and workability. However, in the case where the composition contains a nitrate, it is preferred to carry out calcination at a temperature higher than the decomposition temperature of the nitrate. The physical properties of the ceria-based material such as porous material can be changed by the calcination temperature or the temperature increase rate, and a suitable calcination temperature and temperature rise condition can be selected depending on the target physical properties. In other words, by setting the calcination temperature to an appropriate condition, the durability of the composite oxide is maintained to be good, and the decrease in pore volume can be suppressed. Moreover, as a temperature raising condition, it is preferable to gradually heat up by a temperature rise etc. Thereby, it is possible to prevent the gasification or combustion of inorganic substances and organic substances from becoming severe, and it is easy to be exposed to a high temperature state set above or to cause cracks, and as a result, pulverization is caused.

The calcination atmosphere is not particularly limited, and it is generally calcined in air or nitrogen. Further, the calcination time can be determined depending on the specific surface area of the calcined cerium oxide-based material, and is usually from 1 to 48 hours. The physical properties of the ceria-based material such as porous material may be changed by the calcination conditions, and each calcination condition may be selected depending on the target physical properties.

The solid matter obtained by the step of calcination as described above may be used as the ceria-based material of the present embodiment, and it is preferred to further hydrothermally treat the solid matter. By the hydrothermal treatment step, a uniform pore structure having a pore diameter of a majority of pores existing in a narrow range of 3 to 5 nm and a cerium oxide-based material having a large specific surface area and mechanical strength are unexpectedly obtained. .

The term "hydrothermal treatment" as used herein refers to an operation in which the solid matter is immersed in water or a solution containing water and heated, and kept for a fixed period of time. The inventors of the present invention have estimated that sufficient water is present in the pores of the solid matter, and the water is used as a medium to cause the substance to move, and the pores are reconstituted. Therefore, from the viewpoint of promoting rapid material movement, the temperature of the hydrothermal treatment is preferably 60 ° C or higher, more preferably 70 ° C or higher, further preferably 80 ° C or higher, and particularly preferably 90 ° C or higher. The temperature of the hydrothermal treatment may be a higher temperature of 100 ° C or more, in which case it is necessary to pressurize the apparatus so as not to excessively evaporate the moisture. Further, even if the temperature of the hydrothermal treatment is less than 60 ° C, the cerium oxide-based material of the present embodiment can be obtained, but the treatment time tends to be long. Further, as described above, the hydrothermal treatment at a temperature equal to or higher than the boiling point of the solution under pressure has an advantage of exhibiting an effect in a short period of time. However, from the viewpoint of easiness of handling, it is generally preferred to carry out hydrothermal treatment at a higher temperature in the range below the boiling point. The time of the hydrothermal treatment varies depending on the type of the constituent metal of the solid, the amount of the metal, the composition ratio of the metal, the treatment temperature, and the like, and is preferably in the range of 1 minute to 5 hours, more preferably in the range of 5 minutes to 3 hours. Further preferably, it is in the range of 5 minutes to 1 hour.

The reason why the pore distribution is narrowed by the hydrothermal treatment is not certain, and the detailed research is not very thorough, and the present inventors have now estimated the reason as follows. That is, by subjecting the composition containing the above-mentioned cerium oxide to molding, drying, calcining, or the like, the crosslinking reaction between the particles in the composition is carried out, thereby forming a pore distribution having a thickness of 2 to 10 nm. Structure (solid). In the drying step or the calcination step, the dehydration reaction and the crosslinking reaction between the gels are carried out by heating under a gas atmosphere, and the reactions are solid phase reactions, so that the obtained cerium oxide-based material does not have to be uniform. Fine pore distribution. Further, it is presumed that the hydrolyzate is further subjected to a hydrothermal treatment to cause a reaction caused by hydrolysis and recrosslinking reaction of the solid matter, thereby causing rearrangement of the structure. Further, considering that the obtained pore volume is close to the void ratio obtained by the closest packing of the particles, the hydrothermal reaction is hydrothermally stabilized to change to a thermodynamically stable filling structure, and as a result, it is presumed that it is obtained in the pore diameter. A cerium oxide-based material having a pore distribution in a narrow range of 3 to 5 nm.

Next, another preferred manufacturing method of the cerium oxide-based material of the present embodiment will be described. The manufacturing method includes: drying a composition containing a cerium oxide, an aluminum compound, and a compound selected from the group consisting of an alkali metal element, an alkaline earth metal element, and a rare earth element, or drying the composition a step of calcining to obtain a solid matter (first step); and an acidic aqueous solution of the solid matter and a soluble metal salt containing at least one fourth periodic element selected from the group consisting of iron, cobalt, nickel, and zinc a step of neutralizing the fourth periodic element to the solid matter by the neutralization (second step); a step of hydrothermally treating the solid matter having the fourth periodic element deposited (third step); The solid matter of the hydrothermal treatment step is subjected to a heat treatment step (fourth step).

In the first step, a slurry containing a compound of cerium oxide, an aluminum compound, and the above basic element is further blended and dried, followed by calcination to obtain a solid matter. The slurry may be blended in the same manner as in the above embodiment except for the compound containing no element of the fourth cycle. Further, the calcination temperature may be the same as the calcination temperature in the above embodiment.

Next, in the second step, by neutralizing the mixture of the solid matter obtained in the first step and the acidic aqueous solution containing the fourth periodic element, the component containing the fourth periodic element is analyzed to the solid matter. on. At this time, the solid matter mixed with the acidic aqueous solution may be in a state of being dispersed in a water slurry in water. At this stage, the ions of the fourth periodic element in the aqueous solution are neutralized with the alkali, and the element containing the fourth periodic element is analyzed and immobilized in the solid state, for example, in the state of the hydroxide of the fourth periodic element. On the object.

Examples of the base to be used for the neutralization in the second step include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and ammonia. Further, the solid material or the aqueous slurry containing the solid material may contain an alkali metal element (Li, Na, K, Rb, Cs) and an alkaline earth metal element (Be, Mg, Ca, Sr, Ba). And a component of one or two or more kinds of basic elements of the group consisting of rare earth elements (La, Ce, and Pr). Examples of the component containing such a basic element include potassium hydroxide, barium hydroxide, magnesium oxide, cerium oxide, cerium oxide, and cerium oxide.

In the second step, for example, while stirring and stirring the acidic aqueous solution containing the soluble metal salt of the fourth periodic element and the solid matter, the mixture is neutralized with a base, and the fourth periodic element is analyzed by precipitation to the solid matter. . When the formation of the fourth periodic element is carried out, the concentration of the acidic aqueous solution containing the fourth periodic element, the pH of the alkali, the aqueous solution, and the temperature may be appropriately selected.

The concentration of the fourth periodic element in the acidic aqueous solution (in the case of containing two or more kinds of the fourth periodic element, the concentration of each fourth periodic element) is preferably in the range of 0.0001 to 1.0 mol/L, more preferably 0.001 to 0.5. The range of mol/L is further preferably in the range of 0.005 to 0.2 mol/L.

When neutralizing with a base, the amount of the alkali may be adjusted so that the pH of the aqueous solution is in the range of preferably 5 to 10, more preferably 6 to 8. The temperature of the aqueous solution is preferably from 0 to 100 ° C, more preferably from 30 to 90 ° C, still more preferably from 60 to 90 ° C.

The time required for the analysis of the element containing the fourth cycle element varies depending on the conditions of the content of the alumina, the fourth cycle element, and the basic element, or the temperature, and is preferably in the range of 1 minute to 5 hours. It is in the range of 5 minutes to 3 hours, and more preferably in the range of 5 minutes to 1 hour.

Next, in the third step, the solid matter in which the component containing the fourth periodic element is precipitated is subjected to a hydrothermal treatment to obtain a mixture. The hydrolyzate and the re-crosslinking reaction of the cerium oxide gel are carried out by hydrothermal treatment of the solid matter, and the structure is rearranged, and the compound of the fourth periodic element is compounded.

The hydrothermal treatment may be the same as in the above embodiment, or the hydrothermal treatment may be carried out by directly heating the intermediate liquid used in the second step. The hydrothermal treatment is preferably carried out at a temperature range of 60 ° C or higher for 1 to 48 hours. That is, it is also possible to carry out hydrothermal treatment at a lower temperature of less than 60 ° C, but there is a tendency that the treatment time becomes long. The hydrothermal treatment is preferably carried out at 60 to 90 ° C from the viewpoints of workability, treatment time, and the like.

Further, the solid matter contained in the mixture obtained in the third step is washed with water and dried as necessary, and then subjected to heat treatment in the fourth step. Thus, the cerium oxide-based material of the present embodiment can be obtained.

The heat treatment temperature of the solid matter in the fourth step is preferably from 40 to 900 ° C, more preferably from 80 to 800 ° C, still more preferably from 200 to 700 ° C, and particularly preferably from 300 to 600 ° C.

The atmosphere of the heat treatment may be in air (or in the atmosphere) or in an oxidizing atmosphere (oxygen, ozone, nitrogen oxides, carbon dioxide, hydrogen peroxide, hypochlorous acid, inorganic ‧ organic peroxide, etc.), and an inert gas In the atmosphere (helium, argon, nitrogen, etc.). The heat treatment time may be appropriately selected depending on the heat treatment temperature and the amount of the solid matter.

The cerium oxide-based material of the present embodiment can be preferably used for a pigment, a filler, an abrasive, a cosmetic base, a carrier for a pesticide, a catalyst carrier, an adsorbent, a film constituent material, and the like.

Specific examples will be described below for each use. First, the pigment is required to be a fine powder which is insoluble in water, oil, an organic solvent, etc., and has high mechanical strength. The spherical particles containing the cerium oxide-based material of the present embodiment have high mechanical strength and are excellent in water resistance, oil resistance, and organic solvent resistance, and thus can be preferably used as a pigment. Further, as the pigment, generally smaller particles are used, and the average particle diameter is preferably 10 μm or less, more preferably 5 μm or less.

Previously, the bulk density of the synthetic cerium oxide filler used as a filler was as small as 0.04 to 0.2 g/cm ³ , which was inconvenient to transport and handle. The cerium oxide-based material of the present embodiment can also have a bulk density of 0.9 to 1.2 g/cm ³ , so that the disadvantages of the conventional synthetic cerium oxide filler can be solved. Further, since the cerium oxide-based material has a high mechanical strength, it can be used as a reinforcing agent for increasing the strength of the polymer. Further, the cerium oxide-based material can also be used as a matting agent or a viscosity adjusting material for a prepolymer of a vinyl chloride paste, an epoxy resin or a polyester resin.

The wear resistance of the cerium oxide-based material of the present embodiment measured by the method described later is preferably 1.0% by mass/15 hours or less, and can also be used as an abrasive. As an abrasive, it is important to have the geometric properties of shape and bulk density. The cerium oxide-based material of the present embodiment has a higher mechanical strength than quartz sand, pumice, diatomaceous earth or the like, and has a high bulk density in a spherical shape, and therefore is excellent as an abrasive. In addition, it is necessary to make the particle diameters uniform according to the object to be polished. However, since the mechanical strength is strong, even if classification is performed, it is less likely to cause breakage, and the spherical particles having a particle size corresponding to the polishing target can be obtained. The average particle diameter of the abrasive may be in various ranges depending on the object to be polished, and is generally preferably from 1 to 300 μm, and the optimum particle size is used depending on the application. The cerium oxide-based material of the present embodiment can also be used as an abrasive for the following aspects: glass, wood grinding, or rust removal, decontamination, processing of bone, metal, wood, ivory, etc., art crafts, plastics , polishing of soft metals, etc.

As a cosmetic base, it is desired to have high stability to the human body and good usability. Since the cerium oxide-based material of the present embodiment is excellent in water resistance, oil resistance, and organic solvent resistance, it has high stability to the human body, and when it is spherical, it can impart a smooth feeling and has high usability. Can be used as a cosmetic base.

The particles used as the carrier for the agricultural chemical preferably have a uniform particle size distribution, and it is preferred to remove particles of 10 μm or less by treatment such as classification. When the particles of 10 μm or less are removed, the physical properties of the powder, such as powdering property, dispersibility, scattering property, and stability over time, are remarkably improved.

The cerium oxide-based material of the present embodiment can control the pore diameter in the range of 3 to 5 nm, and can be effectively used as an ink absorbing material for paper for an inkjet printer because the pore distribution is narrow. Further, since the cerium oxide-based material of the present embodiment has a small pore volume and a high bulk density, the disadvantages of the conventional synthetic cerium oxide filler can be eliminated, and the mechanical strength is also high, so that it can be used as A reinforcing agent that enhances the strength of the polymer. Further, the cerium oxide-based material of the present embodiment can also be used as a matting agent or a prepolymer viscosity adjusting material of a vinyl chloride paste, an epoxy resin or a polyester resin.

The cerium oxide-based material can also carry various metal ions and can be used as a catalyst carrier. When it is used as a catalyst carrier, the catalyst active component is supported on the cerium oxide-based material, and the catalytically active component is appropriately selected depending on the reaction to be targeted. The metal component supported as the active component is preferably at least one noble metal component selected from the group consisting of ruthenium, rhodium, palladium, silver, rhodium, iridium, iridium, platinum, and gold. Among the precious metal components, at least one selected from the group consisting of ruthenium, palladium, platinum, and gold is more preferable. These noble metal components may be used alone or in combination of two or more. The chemical state of the precious metal component may be a metal monomer, an oxide, a hydroxide, a composite compound containing two or more noble metal elements, or a mixture thereof, and the preferred chemical state is metal monomer or metal oxidation. Things.

The noble metal particles are preferably supported on the carrier in a state of being highly dispersed. Specifically, the noble metal particles are preferably supported in a state in which the particles do not overlap each other in the lamination direction of the carrier, and more preferably in the form of fine particles (that is, a state in which the particles are not in contact with each other) or a film (ie, particles). They are in contact with each other but are dispersed and supported in a state in which they do not overlap with the direction of lamination of the carrier. The average particle diameter of the noble metal particles is preferably 2 to 10 nm, more preferably 2 to 8 nm, and still more preferably 2 to 6 nm.

When the average particle diameter of the noble metal particles is within the above range, there is a tendency that a specific active species structure is formed and the reactivity is improved. Here, the "average particle diameter" in the present embodiment means the number average particle diameter measured by a transmission electron microscope (TEM). Specifically, in the image observed by the transmission electron microscope, the portion of the black contrast is a composite particle, and the diameters of the respective particles in the image are measured, and the number is averaged and calculated.

The precious metal carrier may contain a second component element in addition to the precious metal component. The second component element is at least one metal selected from the group consisting of elements of Groups 4 to 16 of the fourth cycle, the fifth cycle, and the sixth cycle of the periodic table. Specific examples of the second component element include titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, zirconium, hafnium, molybdenum, cadmium, indium, tin, antimony, bismuth, antimony, and Tungsten, antimony, mercury, antimony, lead, antimony, etc. Further, an alkali metal, an alkaline earth metal, and a rare earth metal may be contained as the second component element.

These metal elements may be used alone or in combination of two or more. The chemical state of the metal elements may be any one of a metal monomer, an oxide, a hydroxide, a complex containing two or more metal elements, or a mixture thereof, and the preferred chemical state is a metal monomer or Metal oxide.

The amount of each precious metal component supported is not particularly limited. When the at least one precious metal component selected from the group consisting of ruthenium, osmium, palladium, silver, rhodium, iridium, iridium, platinum, and gold is supported, the amount of each supported component is preferably 0.1% by mass based on 100% by mass of the carrier. ~20% by mass, more preferably 1% to 10% by mass. The precious metal component may be a monomer of a noble metal or a compound of a noble metal element (for example, an oxide or a hydroxide).

Each of the supporting amounts of at least one metal element selected from the group consisting of elements of Groups 4 to 16 of the fourth, fifth, and sixth cycles of the periodic table and/or a compound of the metal element With respect to the mass of the unit precious metal support, the total amount is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, and when the alkali metal, the alkaline earth metal or the rare earth metal is supported, the supporting amount is The total amount of the precious metal carrier is preferably 0.5 to 30% by mass, and more preferably 1 to 15% by mass.

The specific surface area of the noble metal carrier of the present embodiment is preferably in the range of 20 to 500 m ² /g, preferably in the range of 20 to 500 m ² /g, from the viewpoint of the improvement of the reactivity and the ease of separation of the active ingredient. It is in the range of 50 to 400 m ² /g, and more preferably in the range of 100 to 350 m ² /g.

The pore structure of the noble metal carrier of the present embodiment is one of extremely important physical properties, from the viewpoint of the supporting characteristics of the precious metal component, the long-term stability including peeling, and the reaction property when used as a catalyst. The pore diameter is a physical property value that is an index for expressing these characteristics. When the pore diameter is less than 3 nm, the peeling property of the noble metal-supporting component tends to be good, and when it is used as a catalyst for a liquid phase reaction or the like, the diffusion resistance in the pores of the reaction substrate increases. It is easy to limit the rate of diffusion process and the tendency to decrease in reactivity. Therefore, the pore diameter is preferably 3 nm or more. On the other hand, the pore diameter is preferably 50 nm or less from the viewpoint of the ease of cracking of the carrier and the ease of peeling of the supported noble metal particles. Therefore, the pore diameter of the noble metal carrier is preferably from 3 nm to 50 nm, more preferably from 3 nm to 30 nm, and further preferably from 3 nm to 10 nm. The pore volume is preferably in the range of 0.1 to 1.0 mL/g, more preferably in the range of 0.1 to 0.5 mL/g, and further preferably 0.1 to 0.3 mL/g, from the viewpoint of the supporting characteristics and the reaction characteristics. range. The noble metal carrier of the present embodiment preferably has a pore diameter and a pore volume satisfying the above range.

The method of supporting the noble metal component in the ceria-based material is not particularly limited as long as the above-described support is obtained, and a method of preparing a metal carrier generally used, for example, an impregnation method (adsorption method, filling) can be applied. Hole method, evaporation dry solid method, spray method), precipitation method (coprecipitation method, deposition method, kneading method), ion exchange method, vapor phase evaporation method, and the like. The metal component other than the noble metal may be added during the preparation of the precious metal carrier. However, when the noble metal carrier is used as a catalyst, it may be added to the reaction system using the catalyst.

When the second component element is contained in addition to the precious metal component, the second component element may be contained in the noble metal carrier during the production or reaction of the noble metal carrier, or the second component element may be contained in the carrier in advance. . Further, the structure of the second component element to be used in the noble metal carrier is not particularly limited, and may be formed into an alloy or an intermetallic compound with the noble metal particles, or may be carried on the carrier separately from the noble metal particles. The alkali metal compound or the alkaline earth metal compound may be preliminarily coexisted in the preparation of the noble metal support, or may be added during the preparation of the noble metal support or in the reaction system. As the metal raw material used in the preparation of the catalyst, a compound such as an inorganic compound or an organometallic compound of the above metal is used, and a metal halide, a metal oxide, a metal hydroxide, a metal nitrate, a metal sulfate or a metal is preferable. Acetate, metal phosphate, metal carbonyl compound, ethyl acetonide metal salt, metal porphyrin, metal phthalocyanine.

[Preparation method of precious metal carrier containing element of second component other than precious metal component]

The preparation method of the case where the element of the second component is contained in the precious metal carrier other than the noble metal component is described by taking the precipitation method as an example. For example, in the first step, the acidic component of the soluble metal salt containing the second component and the noble metal is neutralized, and the second component and the noble metal are analyzed to the ceria-based material to obtain a noble metal carrier. Before the drive. At this stage, the second component and the noble metal ion and the base are neutralized by the neutralization reaction in the aqueous solution, and the second component and the precious metal component (for example, hydroxide) are precipitated and immobilized on the ceria-based material. Next, as a second step, if necessary, the noble metal carrier precursor obtained in the above first step is washed with water and dried, and then a noble metal carrier can be obtained by heat treatment.

Examples of the soluble metal salt containing the second component element used in the preparation of the noble metal carrier include nitrate, acetate and chloride of the second component element. Further, examples of the soluble metal salt containing a noble metal component include palladium chloride and palladium acetate when palladium is used as the noble metal, and ruthenium chloride and lanthanum nitrate in the case of ruthenium. In the case of the case, there may be mentioned gold chloride, sodium chloride, potassium dicyanophosphate, diethylamine gold trichloride and gold cyanide. In the case of silver, silver chloride and silver nitrate may be mentioned. .

As the base used in the preparation of the noble metal carrier, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia or the like is used. Further, the carrier may also contain a single metal (Li, Na, K, Rb, Cs), an alkaline earth metal (Be, Mg, Ca, Sr, Ba) and a rare earth metal (La, Ce, Pr) alone or A plurality of basic metal components.

In the first step, the acidic aqueous solution containing the soluble metal salt of the second component element and the noble metal is mixed with the ceria-based material, and neutralized with a base to precipitate a second component element and a precious metal component. On the cerium oxide system. When the second component element and the noble metal are analyzed, the concentration of the aqueous solution containing the second component element and the precious metal component, the pH of the alkali, the aqueous solution, and the temperature may be appropriately selected.

The concentration of the aqueous solution containing the second component element and the noble metal is usually in the range of 0.0001 to 1.0 mol/L, preferably in the range of 0.001 to 0.5 mol/L, more preferably in the range of 0.005 to 0.2 mol/L. The ratio of the second component element to the noble metal in the aqueous solution is preferably in the range of 0.1 to 10, more preferably 0.2 to 5.0, still more preferably 0.5 to 3.0, in terms of the atomic ratio of the second component element to the noble metal.

The pH of the aqueous solution may be adjusted by the above-mentioned alkali so as to be in the range of usually 5 to 10, preferably 6 to 8. The temperature of the aqueous solution is usually in the range of 0 to 100 ° C, preferably 30 to 90 ° C, more preferably 60 to 90 ° C.

The time when the second component element and the noble metal are analyzed is not particularly limited, and is usually 1 minute to 5 hours depending on the type of the cerium oxide-based material, the loading amount and ratio of the second component element and the noble metal, and the like. Preferably, it is 5 minutes to 3 hours, more preferably 5 minutes to 1 hour.

The heat treatment temperature of the noble metal carrier precursor in the second step is usually 40 to 900 ° C, preferably 80 to 800 ° C, more preferably 200 to 700 ° C, and still more preferably 300 to 600 ° C.

The atmosphere of heat treatment is in air (or in the atmosphere), in an oxidizing atmosphere (oxygen, ozone, nitrogen oxides, carbon dioxide, hydrogen peroxide, hypochlorous acid, inorganic, organic peroxide, etc.) or an inert gas atmosphere ( Helium, argon, nitrogen, etc.). The heat treatment time may be appropriately selected depending on the heat treatment temperature and the amount of the precursor of the noble metal carrier.

After the second step described above, it is also possible to carry out a reduction treatment in a reducing atmosphere (hydrogen, helium, fumarin, formic acid, etc.). The temperature and time of the reduction treatment may be appropriately selected depending on the type of the reducing agent, the type of the precious metal, and the amount of the precious metal carrier.

After the above heat treatment or reduction treatment, it may also be used in air (or in the atmosphere) or in an oxidizing atmosphere (oxygen, ozone, nitrogen oxides, carbon dioxide, hydrogen peroxide, hypochlorous acid, inorganic ‧ organic peroxides, etc.) Oxidation treatment is carried out. The temperature and time at this time are appropriately selected depending on the type of the oxidizing agent, the type of the precious metal, and the amount of the precious metal carrier.

[Manufacturing method of a compound using a noble metal carrier as a catalyst]

The noble metal carrier of the present embodiment can be widely used as a catalyst for chemical synthesis. The noble metal carrier can be used, for example, for oxidation of an alkoxide, oxidation of an alcohol, oxidation of an aldehyde, oxidation of a carbonyl group, oxidation of an alkene, epoxidation of an alkene, oxidative addition of an alkene, oxidative esterification of an aldehyde with an alcohol, Oxidative esterification of alcohols, oxidative esterification of diols and alcohols, hydrogenation of alkenes, hydrogenation of alkynes, hydrogenation of phenols, selective hydrogenation of α,β-unsaturated ketones, nitro, olefins, carbonyls, aromatics A hydrogenation reaction, an amination, a direct hydrogen peroxide synthesis using hydrogen and oxygen, a oxidation of carbon monoxide, a water gas shift reaction, or the like, or a reduction catalyst or photocatalyst for NOx.

Hereinafter, a method of producing a carboxylic acid ester by an oxidative esterification reaction using an aldehyde and an alcohol in the presence of oxygen using the noble metal carrier of the present embodiment as a catalyst will be described as an example.

Examples of the aldehyde used as a raw material include C1-C10 aliphatic saturated aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, isobutyraldehyde, and glyoxal; and C3-C10 such as acrolein, methacrolein, and crotonaldehyde. An aliphatic α,β-unsaturated aldehyde; a C6-C20 aromatic aldehyde such as benzoic aldehyde, tolualdehyde, benzaldehyde or phthalaldehyde; and a derivative of the aldehyde. These aldehydes may be used singly or in combination of two or more. However, if the aldehyde is at least one selected from the group consisting of acrolein, methacrolein, and a mixture thereof, the noble metal carrier of the present embodiment can be more effectively used as a catalyst. Preferably.

Examples of the alcohol include a C1-C10 aliphatic saturated alcohol such as methanol, ethanol, isopropanol, butanol, 2-ethylhexanol or octanol; and a C5-C10 alicyclic group such as cyclopentanol or cyclohexanol. Alcohol; C2-C10 diol such as ethylene glycol, propylene glycol or butylene glycol; C3-C10 aliphatic unsaturated alcohol such as allyl alcohol or methyl allyl alcohol; C6-C20 aromatic alcohol such as benzyl alcohol; A hydroxy oxetane such as a 3-hydroxymethyloxetane. These alcohols may be used singly or in combination of two or more. Among them, when the alcohol is methanol, the noble metal carrier of the present embodiment can be more effectively used as a catalyst, which is preferable.

The ratio of the amount of the aldehyde to the alcohol is not particularly limited. For example, the ratio of the aldehyde to the alcohol (aldehyde/alcohol) may be in the range of 10 to 1/1000 on a molar basis, and is generally 1/2 to 1/50. .

The amount of the catalyst used can be greatly changed depending on the kind of the reaction raw material, the composition of the catalyst, the preparation method, the reaction conditions, the reaction form, and the like, and is not particularly limited. When the catalyst is allowed to react in a slurry state, the concentration of the solid content in the catalyst is preferably from 1 to 50% by mass/% by volume, more preferably from 3 to 30% by mass/% by volume, and still more preferably Use within the range of 10~25 mass/capacity%.

The production of the carboxylic acid ester can be carried out by any one of a batch type or a continuous type by any method such as a gas phase reaction, a liquid phase reaction, or a trickle reaction.

This reaction can also be carried out in the absence of a solvent, and can also be carried out using a solvent inert to the reaction component (reaction substrate, reaction product, and catalyst), for example, hexane, decane, benzene or dioxane.

The reaction form may be a previously known form such as a fixed bed type, a fluid bed type, or a stirred tank type. For example, in the case of reacting in a liquid phase, any reactor form such as a bubble column reactor, a draft tube type reactor, or a stirred tank reactor may be employed.

The oxygen used in the production of the carboxylic acid ester may be in the form of molecular oxygen, that is, oxygen itself, or a mixed gas obtained by diluting oxygen with a diluent inert to the reaction, such as nitrogen, carbonic acid gas or the like. As the oxygen raw material, air can be preferably used from the viewpoints of workability, economy, and the like.

The oxygen partial pressure varies depending on the reaction raw material such as the aldehyde species, the alcohol species, the reaction conditions, the reactor form, and the like. Practically, it is preferable to set the oxygen partial pressure at the outlet of the reactor to a concentration lower than the lower limit of the explosion range. For example, the control is 20~80 kPa. The reaction pressure may be any of a wide range of pressures from a reduced pressure to a pressure, for example, a reaction pressure in the range of 0.05 to 2 MPa. Further, from the viewpoint of safety, it is preferred to set the total pressure (for example, an oxygen concentration of 8%) in such a manner that the oxygen concentration in the gas flowing out of the reactor does not exceed the explosion limit.

When a carboxylic acid ester production reaction is carried out in a liquid phase or the like, it is preferred to add an alkali metal or alkaline earth metal compound (for example, an oxide, a hydroxide, a carbonate, or a carboxylate) to the reaction system. The pH of the reaction system was maintained at 6-9. These alkali metal or alkaline earth metal compounds may be used alone or in combination of two or more.

The reaction temperature in the production of the carboxylic acid ester may be a high temperature exceeding 200 ° C, preferably 30 to 200 ° C, more preferably 40 to 150 ° C, still more preferably 60 to 120 ° C. The reaction time is not particularly limited, and it varies depending on the conditions set, and therefore cannot be generalized, but it is usually 1 to 20 hours.

Next, a method of producing a carboxylic acid by oxidizing an aldehyde in a liquid phase containing water using the noble metal carrier of the present embodiment as a catalyst will be described as an example.

The water contained in the liquid phase is not particularly limited, and examples thereof include soft water, purified industrial water, and ion-exchanged water. It is sufficient to have water of normal water quality, and it is not preferable to contain too much impurities (Fe, Ca, Mg, etc.). Examples of the aldehyde used in the production of the carboxylic acid include C1-C10 aliphatic saturated aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, isobutyraldehyde, and glyoxal; acrolein, methacrolein, and crotonaldehyde. Such as C3-C10 aliphatic α,β-unsaturated aldehyde; C6-C20 aromatic aldehyde such as benzoic aldehyde, tolualdehyde, benzaldehyde, orthophthalaldehyde, and derivatives of such aldehydes. Among them, methacrolein and acrolein are preferred. These aldehydes can be used singly or in combination of two or more kinds thereof.

The ratio of the amount of the aldehyde to the water is not particularly limited. For example, it can be carried out in a wide range of from 1/10 to 1/1000 in terms of aldehyde/water molar ratio, but it is generally in the range of 1/2 to 1/100. Implemented within.

The aldehyde may be oxidized in a mixed liquid phase containing aldehyde and water, that is, without a solvent, but a solvent mixture may be added to a mixed liquid containing aldehyde and water to prepare a mixed liquid containing aldehyde, water, and a solvent. As the solvent, for example, ketones, nitriles, alcohols, organic acid esters, hydrocarbons, organic acids, and guanamines can be used. Examples of the ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the nitrile include acetonitrile and propionitrile. Examples of the alcohols include third butanol and cyclohexanol. Examples of the organic acid esters include ethyl acetate and methyl propionate. Examples of the hydrocarbons include hexane, cyclohexane, and toluene. Examples of the organic acid include acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, and isovaleric acid. Examples of the guanamines include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, and hexamethylphosphoniumamine. Further, the solvent may be one type or a mixture of two or more types. In the case of mixing water and a solvent, the mixing ratio thereof can be largely changed depending on the kind of the aldehyde as a reaction raw material, the composition of the catalyst, the preparation method, the reaction conditions, the reaction form, and the like, and is not particularly limited, but is high. The amount of the solvent is preferably from 8 to 65% by mass, more preferably from 8 to 55% by mass, based on the mass of the water, from the viewpoint of the selectivity and the high productivity of the aldehyde to produce the carboxylic acid. The mixture containing the aldehyde and water or the mixture containing the aldehyde, water, and solvent is preferably uniform, but may be used in a state where the use is uneven.

The amount of the catalyst to be used may vary greatly depending on the type of the reaction raw material, the composition of the catalyst, the preparation method, the reaction conditions, the reaction form, and the like, and is not particularly limited. When the catalyst is reacted in a slurry state, It is used in such a manner that the catalyst concentration in the slurry is controlled within a range of preferably 4 to 50 mass/capacity%, more preferably 4 to 30 mass/capacity%, and still more preferably 10 to 25 mass/capacity%. . That is, the mass (kg) of the catalyst relative to the volume (L) of the liquid component is controlled to be preferably in the range of 4 to 50%, more preferably 4 to 30%, still more preferably 10 to 25%. The way to use.

The production of the carboxylic acid in the liquid phase can be carried out in any of a continuous form or a batch form, and in view of productivity, it is preferably industrially continuous.

As the oxygen source for oxidation, the oxygen itself may be supplied to the reactor, or a mixed gas obtained by diluting oxygen as a diluent inert to the reaction, such as nitrogen gas or carbonic acid gas, may be supplied, and the operability, In terms of economy and the like, it is preferred to use air as an oxygen source.

The preferred oxygen partial pressure varies depending on the aldehyde species or solvent species, the reaction conditions or the reactor form, etc., and the oxygen partial pressure at the outlet of the reactor is preferably in the range of the concentration below the lower limit of the explosion range, for example, the control is 20~ 80 kPa. The reaction pressure can be carried out in any of a wide range of pressures from reduced pressure to under pressure, and is usually carried out at a pressure of 0.05 to 5 MPa. From the viewpoint of safety, it is preferred to set the total pressure so that the oxygen concentration of the reactor effluent gas does not exceed the explosion limit (8%).

The reaction temperature in the production of the carboxylic acid is preferably from 30 to 200 ° C, more preferably from 40 to 150 ° C, still more preferably from 60 to 120 ° C. The reaction time is not particularly limited and is usually from 1 to 20 hours.

Further, the content of the constituent elements (Si, Al, the fourth periodic element, the basic element) of the cerium oxide-based material, the composition ratio of the fourth periodic element to the aluminum or the basic element, the specific surface area, Measurement of pore size and pore volume, observation of shape, measurement of average particle size, measurement of bulk density (CBD), measurement of abrasion resistance, analysis of crystal structure, chemical state analysis of elements in the fourth period, precious metal loading Morphological observation of the substance can be carried out by the following method.

[Determination of the content of constituent elements of cerium oxide-based materials and precious metal supports]

The concentration of Si, Al, the fourth periodic element, and the basic element in the cerium oxide-based material is "IRIS Intrepid II XDL type" which is used as an ICP luminescence analyzer (ICP-AES, MS) manufactured by Thermo Fisher Scientific. Product name) is quantified.

The sample was prepared as follows. First, the cerium oxide-based material was weighed into a decomposition vessel made of Teflon (registered trademark), and nitric acid and hydrogen fluoride were added thereto. The obtained solution was thermally decomposed by "ETHOS‧TC type" (trade name) as a microwave decomposition apparatus manufactured by Milestone General K.K., and then evaporated to dryness on a heater. Next, nitric acid and hydrochloric acid were added to the precipitated residue, and the mixture was subjected to pressure decomposition by the above-described microwave decomposing apparatus, and the obtained decomposed liquid was made into a predetermined capacity by using pure water as a sample.

The above-mentioned ICP-AES standard method is used to quantify the sample, and the operation blank value is simultaneously subtracted, and the content of Si, Al, the fourth periodic element and the basic element in the cerium oxide-based material and the precious metal loading are obtained. The content of the metal element in the material was calculated from the composition ratio (mole reference) and the supported amount.

[determination of composition ratio]

The composition ratio of the fourth periodic element to the aluminum is calculated based on the content of Al, the fourth periodic element, and the basic element measured in the above-mentioned "determination of the content of constituent elements of the cerium oxide-based material and the noble metal carrier" (X) /Al), and the composition ratio (X/B) of the element of the fourth period to the basic element.

[Measurement of specific surface area, pore diameter and pore volume]

The gas adsorption amount measuring device "Autosorb 3MP" (trade name) manufactured by Yuasa Ionics Co., Ltd., using nitrogen gas as an adsorption gas, and measuring the specific surface area, pore diameter and pore volume of the cerium oxide-based material and the noble metal carrier (nitrogen gas) Adsorption method). The specific surface area is BET, the pore size and pore distribution are BJH, and the pore volume is the adsorption amount under P/P0 and Max.

[Shape observation]

The cerium oxide-based material (carrier) and the noble metal carrier (catalyst) particles were observed using an X-650 scanning electron microscope apparatus (SEM) manufactured by Hitachi, Ltd.

[Measurement of average particle size]

The average particle diameter (volume basis) of the cerium oxide-based material and the noble metal carrier was measured using a LS230 laser diffraction/scattering particle size distribution measuring apparatus manufactured by Beckman Coulter.

[Measurement of bulk density (CBD)]

As a pretreatment, first, 120 g of a cerium oxide-based material was weighed and placed in a stainless steel crucible, and calcined in a muffle furnace at 500 ° C for 1 hour. The calcined cerium oxide-based material was placed in a desiccator (with a cerium oxide gel) and cooled to room temperature. 100.0 g of the pretreated cerium oxide-based material was weighed and transferred to a 250 mL measuring cylinder, and the cerium oxide-based material was shaken and filled in a measuring cylinder for 15 minutes. The measuring cylinder is removed from the oscillator, the surface of the cerium oxide-based material in the measuring cylinder is leveled, and the filling volume is read. The mass of the bulk density cerium oxide material divided by the value of the filling volume.

[Measurement of wear resistance]

About 50 g of the cerium oxide-based material was accurately weighed and placed in a vertical tube having an inner diameter of 1.5 inches with an opening circular plate having 3 orifices at the bottom of 1/64 inch. Air is blown from the outside into the vertical tube through the perforated disk at a rate of 15 CF (Cubic Feet), so that the particles of the cerium oxide-based material in the tube flow violently. The ratio (% by mass) of the total amount of particles of the cerium oxide-based material which is finely pulverized between 5 and 20 hours after the start of air blowing and which escapes from the upper portion of the vertical pipe is determined as " Wear resistance".

[Analysis of crystal structure]

A powder X-ray diffraction device (XRD) manufactured by Rigaku Co., Ltd. "Rint 2500" (trade name) was used for the X-ray source Cu tube (40 kV, 200 mA), and the measurement range was 5 to 65 deg (0.02 deg/step). The crystal structure of the cerium oxide-based material was analyzed under the conditions of a measurement speed of 0.2 deg/min and a slit width (scattering, diverging, and receiving light) of 1 deg, 1 deg, and 0.15 mm.

The measurement was carried out by uniformly spreading the sample on a non-reflective sample plate and fixing it with neoprene.

[Analysis of chemical state of element 4 (nickel) in the fourth cycle]

The NiKα spectrum of the cerium oxide-based material was measured by XNRA190 double crystal type high-resolution fluorescent X-ray analyzer (HRXRF) manufactured by Technos, and various parameters obtained were compared with various parameters of the standard substance (nickel metal, nickel oxide). In comparison, the chemical state such as the valence of nickel in the cerium oxide-based material is presumed.

As the measurement sample, the prepared cerium oxide-based material was used in the original state. The measurement of the Kα spectrum of Ni is carried out in a partial spectral mode. At this time, Ge (220) was used as the spectroscopic crystal, and the slit was used for a vertical divergence angle of 1°, and the excitation voltage and current were set to 35 kV and 80 mA, respectively. Further, in the standard sample, filter paper was used as the absorber, and the sample of the cerium oxide-based material was counted for each sample, and the peak intensity of the Kα spectrum was measured to be 3000 cps or less and 10,000 counts or more. Each sample was measured five times in a reverse manner, and nickel metal was measured before and after the repeated measurement. After the measured spectrum is smoothed (SG method 7:5-5 times), the peak position, half-width (FWHM), and asymmetry coefficient (AI) are calculated, and the peak position is determined as measured before and after the measurement of the sample. Deviation in measured value of nickel metal, chemical shift (ΔE).

[Observation of the dispersion state of elements in the fourth cycle]

The analysis of the profile of the cerium oxide-based material was carried out using an EPMA 1600 manufactured by Shimadzu Corporation at an acceleration voltage of 20 KeV.

[Form observation of metal support]

A 3100FEF type transmission electron microscope (TEM) manufactured by JEOL Co., Ltd. [acceleration voltage 300 kV, with an energy dispersive X-ray detector (EDX)] was used to observe a bright field image of the TEM.

As a sample, the noble metal carrier was pulverized in a mortar, and then dispersed in ethanol, ultrasonically washed for about 1 minute, and then dropped onto a sand made of Mo and air-dried.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples. The present invention is not limited to the embodiments shown below and is modified and implemented, and the modifications are also included in the scope of the present patent application. Further, the content of the constituent elements of the cerium oxide-based material in the examples and the comparative examples, the composition ratio of the fourth periodic element to the aluminum or the basic element, the specific surface area, the pore diameter, and the pore volume are determined. The measurement, the shape observation, the measurement of the average particle diameter, the measurement of the bulk density, the measurement of the abrasion resistance, the analysis of the crystal structure, the chemical state analysis of the element of the fourth cycle, and the observation of the morphology of the metal carrier were carried out as described above.

[Example 1]

An aqueous solution of 1.5 kg of aluminum nitrate nonahydrate, 0.24 kg of nickel nitrate hexahydrate, 0.98 kg of magnesium nitrate hexahydrate and 0.27 kg of 60% nitric acid in 3.0 L of pure water was prepared. The aqueous solution was gradually added dropwise to a cerium oxide sol solution having a colloidal particle diameter of 10 to 20 nm maintained at a stirring state of 15 ° C (manufactured by Nissan Chemical Co., Ltd., trade name "Snowtex N-30", SiO ₂ content: 30 mass %) In 10.0 kg, a mixed slurry of cerium oxide sol, aluminum nitrate, nickel nitrate and magnesium nitrate was obtained. Thereafter, the mixed slurry was spray-dried by a spray dryer apparatus having an outlet temperature of 130 ° C to obtain a solid matter.

Next, the obtained solid matter was filled in a stainless steel container having an opening of about 1 cm in thickness, and was heated from room temperature to 300 ° C in an electric furnace for 2 hours, and then kept at 300 ° C for 3 hours. Further, the temperature was raised to 600 ° C over 2 hours, and then calcined at 600 ° C for 3 hours. Thereafter, it was gradually cooled to obtain a cerium oxide-based material containing a composite oxide containing cerium-aluminum-nickel-magnesium.

The obtained cerium oxide-based material contained 矽85.3 mol%, aluminum 6.8 mol%, nickel 1.4 mol%, and magnesium 6.5 mol% with respect to the total amount of lanthanum, aluminum, nickel, and magnesium. The composition ratio of Ni(X)/Al was 0.21 on a molar basis, and the composition ratio of Ni(X)/Mg(B) was 0.22 on a molar basis.

The specific surface area obtained by the nitrogen adsorption method was 223 m ² /g, the pore volume was 0.26 mL/g, and the average pore diameter was 5.1 nm. The bulk density is 0.97 CBD and the abrasion resistance is 0.1% by mass. As a result of measurement by the laser particle size distribution of the scattering method, the average particle diameter was 62 μm. Moreover, as a result of observation by a scanning electron microscope (SEM), it is understood that the ceria-based material has no cracks or defects and has a substantially spherical shape. Regarding the solid form, as a result of powder X-ray diffraction (XRD), it was found that an amorphous pattern similar to that of the ceria gel was obtained.

The chemical state of nickel in the cerium oxide-based material is estimated to be the high spin valence of nickel based on the result of the double crystal type high-resolution fluorescent X-ray analysis (HRXRF), and is judged by the difference of the NiKα spectrum as a single The nickel oxide of the compound is in a different chemical state. The half-bandwidth (FWHM) of the NiKα spectrum of the cerium oxide-based material obtained from the measured spectrum was 3.474, and the chemical shift (ΔE) was 0.331. The half-bandwidth (FWHM) of the NiKα spectrum of nickel oxide measured as a standard substance was 3.249, and the chemical shift (ΔE) was 0.344.

The state of dispersion of nickel in the cerium oxide-based material is based on the results of the electron probe microanalysis (EPMA), and it is found that nickel is present in substantially the same concentration at any portion.

Next, in order to evaluate the acid resistance and alkalinity of the cerium oxide-based material, the pH swing test was carried out by the following method.

10 g of the ceria-based material obtained as described above was added to 100 mL of a buffer solution of pH 4 placed in a glass vessel, and the mixture was continuously stirred at 90 ° C for 10 minutes, and then allowed to stand to remove the supernatant. Washed and decanted. The solid matter thus obtained was added to 100 mL of a buffer solution of pH 10 placed in a glass vessel, and the mixture was continuously stirred at 90 ° C for 10 minutes, and then allowed to stand to remove the supernatant, washed with water, and decanted. The above operation was performed as one cycle, and a pH swing process of 50 cycles was performed. As a result, the specific surface area of the cerium oxide-based material after the pH swing treatment was 220 m ² /g, the pore volume was 0.27 mL/g, and the average pore diameter was 5.2 nm, which was not observed by the pH swing treatment. Structural changes in cerium oxide materials.

[Embodiment 2]

Use aluminum nitrate nonahydrate 4.0 kg instead of aluminum nitrate nonahydrate 1.5 kg, use zinc nitrate hexahydrate 0.11 kg instead of nickel nitrate hexahydrate 0.24 kg, use potassium nitrate 1.1 kg instead of magnesium nitrate hexahydrate 0.98 kg, except A cerium oxide-based material containing 矽69.7 mol%, aluminum 15.0 mol%, zinc 0.5 mol%, and potassium 14.9 mol% was obtained in the same manner as in Example 1. The composition ratio of Zn(X)/Al was 0.03 on a molar basis, and the composition ratio of Zn(X)/K(B) was 0.03 on a molar basis. The specific surface area obtained by the nitrogen adsorption method was 170 m ² /g, the pore volume was 0.27 mL/g, and the average pore diameter was 5.3 nm. The bulk density is 0.95 CBD, and the abrasion resistance is 0.1% by mass. As a result of measurement by the laser particle size distribution of the scattering method, the average particle diameter was 64 μm. Further, as a result of observation by a scanning electron microscope (SEM), it was found that the ceria-based material was free from cracks or defects, and was substantially spherical in shape. Regarding the solid form, as a result of powder X-ray diffraction (XRD), it was found that an amorphous pattern similar to that of the ceria gel was obtained.

Next, in order to evaluate the acid resistance and alkalinity of the cerium oxide-based material obtained as described above, the pH swing test was carried out by the same method as in Example 1. As a result, the specific surface area of the cerium oxide-based material after the pH swing treatment was 169 m ² /g, the pore volume was 0.26 mL/g, and the average pore diameter was 5.7 nm, and almost no pH swing treatment was observed. The structural change of the cerium oxide-based material.

[Example 3]

Using aluminum nitrate nonahydrate 2.0 kg instead of aluminum nitrate nonahydrate 1.5 kg, using cobalt nitrate hexahydrate 0.75 kg instead of nickel nitrate hexahydrate 0.24 kg, using lanthanum nitrate 0.38 kg instead of magnesium nitrate hexahydrate 0.98 kg, In the same manner as in Example 1, a cerium oxide-based material containing 矽82.7 mol%, aluminum 8.8 mol%, cobalt 4.3 mol%, and 铷4.3 mol% was obtained. The composition ratio of Co(X)/Al was 0.49 on a molar basis, and the composition ratio of Co(X)/Rb(B) was 0.99 on a molar basis. The specific surface area obtained by the nitrogen adsorption method was 196 m ² /g, the pore volume was 0.26 mL/g, and the average pore diameter was 5.1 nm. The bulk density is 0.96 CBD and the abrasion resistance is 0.1% by mass. As a result of measurement by the laser particle size distribution of the scattering method, the average particle diameter was 62 μm. Further, as a result of observation by a scanning electron microscope (SEM), it was found that the ceria-based material was free from cracks or defects, and was substantially spherical in shape. Regarding the solid form, as a result of powder X-ray diffraction (XRD), it was found that an amorphous pattern similar to that of the ceria gel was obtained.

The state of dispersion of the cobalt in the cerium oxide-based material is based on the results of the electron probe microanalysis (EPMA), and it is understood that cobalt is present in substantially the same concentration at any portion.

Next, in order to evaluate the acid resistance and alkalinity of the cerium oxide-based material obtained as described above, the pH swing test was carried out by the same method as in Example 1. As a result, the specific surface area of the cerium oxide-based material after the pH swing treatment was 198 m ² /g, the pore volume was 0.26 mL/g, and the average pore diameter was 5.0 nm, which was not observed by the pH swing treatment. Structural changes.

[Example 4]

A ruthenium containing 89.9 was obtained in the same manner as in Example 1 except that 0.2 kg of iron nitrate nonahydrate was used instead of 0.24 kg of nickel nitrate hexahydrate, and 0.48 kg of yttrium nitrate nonahydrate was used instead of 0.98 kg of magnesium nitrate hexahydrate. Molar%, aluminum 7.2 mol%, iron 0.9 mol%, 镧2.0 mol% of cerium oxide-based material. The composition ratio of Fe(X)/Al was 0.12 on a molar basis, and the composition ratio of Fe(X)/La(B) was 0.45 on a molar basis. The specific surface area obtained by the nitrogen adsorption method was 232 m ² /g, the pore volume was 0.28 mL/g, and the average pore diameter was 5.0 nm. The bulk density is 0.98 CBD, and the abrasion resistance is 0.1% by mass. As a result of measurement by the laser particle size distribution of the scattering method, the average particle diameter was 64 μm. Further, as a result of observation by a scanning electron microscope (SEM), it was found that the ceria-based material was free from cracks or defects, and was substantially spherical in shape. Regarding the solid form, as a result of powder X-ray diffraction (XRD), it was found that an amorphous pattern similar to that of the ceria gel was obtained.

Next, in order to evaluate the acid resistance and alkalinity of the cerium oxide-based material obtained as described above, the pH swing test was carried out by the same method as in Example 1. As a result, the specific surface area of the cerium oxide-based material after the pH swing treatment was 230 m ² /g, the pore volume was 0.27 mL/g, and the average pore diameter was 5.3 nm, which was not observed by the pH swing treatment. Structural changes.

[Example 5]

Sulfuric acid was added to 10 kg of water glass No. 3 (SiO ₂ : 28 to 30% by mass, Na ₂ O: 9 to 10% by mass) until the pH became 9, and then aluminum sulfate was added to adjust the pH to 2. Further, sodium aluminate is added to have a pH of 5 to 5.5, and a part of the mixture is dehydrated to obtain a hydrogel containing about 10% by mass of cerium oxide-alumina. The hydrogel was spray-dried at 130 ° C by spray drying, and then washed until Na ₂ O became 0.02% by mass and SO ₄ became 0.5% by mass or less. A mixed magnesium oxide of 0.83 kg and a nickel oxide of 1.8 kg were added thereto to obtain a slurry. The slurry was filtered and washed, and then dried at 110 ° C for 6 hours, then heated to 700 ° C for 3 hours, and then calcined at 700 ° C for 3 hours. Thereafter, it was gradually cooled to obtain a cerium oxide-based material.

The obtained cerium oxide-based material contained 矽42.2 mol%, aluminum 20.4 mol%, nickel 19.8 mol%, and magnesium 17.6 mol% with respect to the total amount of lanthanum, aluminum, nickel, and magnesium. The composition ratio of Ni(X)/Al was 0.97 on a molar basis, and the composition ratio of Ni(X)/Mg(B) was 1.13 on a molar basis.

The specific surface area obtained by the nitrogen adsorption method was 73 m ² /g, the pore volume was 0.26 mL/g, and the average pore diameter was 5.4 nm. The bulk density is 1.05 CBD, and the abrasion resistance is 0.1% by mass. As a result of measurement by the laser particle size distribution of the scattering method, the average particle diameter was 63 μm. Moreover, as a result of observation by a scanning electron microscope (SEM), it is understood that the ceria-based material has no cracks or defects and has a substantially spherical shape. Regarding the solid form, as a result of powder X-ray diffraction (XRD), it was found that an amorphous pattern similar to that of the ceria gel was obtained.

Next, in order to evaluate the acid resistance and alkalinity of the cerium oxide-based material obtained as described above, the pH swing test was carried out by the same method as in Example 1. As a result, the specific surface area of the cerium oxide-based material after the pH swing treatment was 72 m ² /g, the pore volume was 0.27 mL/g, and the average pore diameter was 5.3 nm, which was not observed by the pH swing treatment. Structural changes.

[Embodiment 6]

Use 4.4 kg of alumina instead of aluminum nitrate hexahydrate 1.5 kg, use 0.93 kg of nickel oxide instead of 0.24 kg of nickel nitrate hexahydrate, use 0.42 kg of magnesium oxide instead of 0.98 kg of magnesium nitrate hexahydrate, and make the calcination temperature 600 ° C to 800 A cerium oxide-based material containing 矽42.9 mol%, aluminum 37.0 mol%, nickel 10.9 mol%, and magnesium 9.1 mol% was obtained in the same manner as in Example 1 except for the above. The composition ratio of Ni(X)/Al was 0.30 on a molar basis, and the composition ratio of Ni(X)/Mg(B) was 1.20 on a molar basis. The specific surface area obtained by the nitrogen adsorption method was 78 m ² /g, the pore volume was 0.27 mL/g, and the average pore diameter was 5.2 nm. The bulk density is 1.02 CBD, and the abrasion resistance is 0.1% by mass. As a result of measurement by the laser particle size distribution of the scattering method, the average particle diameter was 62 μm. Moreover, as a result of observation by a scanning electron microscope (SEM), it is understood that the ceria-based material has no cracks or defects and has a substantially spherical shape. Regarding the solid form, as a result of powder X-ray diffraction (XRD), it was found that an amorphous pattern similar to that of the ceria gel was obtained.

Next, in order to evaluate the acid resistance and alkalinity of the cerium oxide-based material obtained as described above, the pH swing test was carried out by the same method as in Example 1. As a result, the specific surface area of the cerium oxide-based material after the pH swing treatment was 77 m ² /g, the pore volume was 0.27 mL/g, and the average pore diameter was 5.2 nm, which was not observed by the pH swing treatment. Structural changes.

[Embodiment 7]

Use aluminum nitrate nonahydrate 1.0 kg instead of aluminum nitrate nonahydrate 1.5 kg, use nickel hydroxide 0.23 kg instead of nickel nitrate hexahydrate 0.24 kg, use magnesium hydroxide 1.9 kg instead of magnesium nitrate hexahydrate 0.98 kg, so that calcination temperature In the same manner as in Example 1, a cerium oxide-based material containing cerium 57.6 mol%, aluminum 3.1 mol%, nickel 2.8 mol%, and magnesium 36.6 mol% was obtained in the same manner as in Example 1 except for the range of 600 ° C to 650 ° C. . The composition ratio of Ni(X)/Al was 0.91 on a molar basis, and the composition ratio of Ni(X)/Mg(B) was 0.08 on a molar basis. The specific surface area obtained by the nitrogen adsorption method was 92 m ² /g, the pore volume was 0.28 mL/g, and the average pore diameter was 5.1 nm. The bulk density is 0.99 CBD and the abrasion resistance is 0.1% by mass. As a result of the measurement of the particle size distribution by the laser scattering method, the average particle diameter was 62 μm. Moreover, as a result of observation by a scanning electron microscope (SEM), it is understood that the ceria-based material has no cracks or defects and has a substantially spherical shape. Regarding the solid form, as a result of powder X-ray diffraction (XRD), it was found that an amorphous pattern similar to that of the ceria gel was obtained.

Next, in order to evaluate the acid resistance and alkalinity of the cerium oxide-based material obtained as described above, the pH swing test was carried out by the same method as in Example 1. As a result, the specific surface area of the cerium oxide-based material after the pH swing treatment was 94 m ² /g, the pore volume was 0.27 mL/g, and the average pore diameter was 5.0 nm, which was not observed by the pH swing treatment. Structural changes.

[Embodiment 8]

100 g of the ceria-based material obtained as the solid matter obtained in Example 1 was placed in 1.0 L of distilled water heated to 90 ° C, and maintained at 90 ° C for 1 hour while stirring to carry out hydrothermal treatment.

Next, the hydrothermally treated mixture was allowed to stand and the supernatant was removed, washed several times with distilled water, and the filtered solid was dried at 105 ° C for 16 hours. The obtained cerium oxide-based material had a specific surface area of 240 m ² /g, a pore volume of 0.27 mL/g, and an average pore diameter of 3.9 nm. As a result of measuring the particle size distribution of the cerium oxide-based material by the laser scatter method, the average particle diameter was 62 μm. Moreover, as a result of observation by a scanning electron microscope (SEM), it is understood that the ceria-based material has no cracks or defects and has a substantially spherical shape. As a result of powder X-ray diffraction (XRD), it was found that the same amorphous pattern as that of the ceria gel was obtained.

Next, in order to evaluate the acid resistance and alkalinity of the cerium oxide-based material obtained as described above, the pH swing test was carried out by the same method as in Example 1. As a result, the specific surface area of the cerium oxide-based material after the pH swing treatment was 242 m ² /g, the pore volume was 0.26 mL/g, and the average pore diameter was 4.0 nm, which was not observed by the pH swing treatment. Structural changes.

[Embodiment 9]

An aqueous solution of 2.0 kg of aluminum nitrate nonahydrate, 1.5 kg of magnesium nitrate, and 0.27 kg of 60% nitric acid in 3.0 L of pure water was prepared. The aqueous solution was gradually added dropwise to a cerium oxide sol solution having a colloidal particle diameter of 10 to 20 nm maintained at a stirring state of 15 ° C (manufactured by Nissan Chemical Co., Ltd., trade name "Snowtex N-30", SiO ₂ content: 30 mass %) In 10.0 kg, a mixed slurry of cerium oxide sol, aluminum nitrate and magnesium nitrate was obtained. Thereafter, the mixed slurry was aged at 50 ° C for 24 hours to be aged. After the cooked mixed slurry was cooled to room temperature, it was spray-dried by a spray dryer apparatus having an outlet temperature of 130 ° C to obtain a dried product.

Next, the obtained dried product was filled in a stainless steel container having an opening of about 1 cm in thickness, and heated from room temperature to 300 ° C in an electric furnace for 2 hours, and then kept at 300 ° C for 3 hours. Further, the temperature was raised to 600 ° C over 2 hours, and then calcined at 600 ° C for 3 hours. Thereafter, it was gradually cooled to obtain cerium oxide-alumina-magnesia as a solid matter.

Next, 1.0 L of an aqueous solution containing 27 g of nickel nitrate hexahydrate was heated to 90 °C. To the aqueous solution, 300 g of ceria-alumina-magnesia as a solid matter obtained as described above was placed, and the mixture was kept at 90 ° C for 1 hour while stirring, and the nickel was analyzed to a solid matter. Next, the mixture was allowed to stand and the supernatant was removed, washed several times with distilled water, and the filtered solid was dried at 105 ° C for 16 hours, and further calcined at 600 ° C for 5 hours in the air. Thus, a cerium oxide-based material containing 矽80.3 mol%, aluminum 8.7 mol%, nickel 1.5 mol%, and magnesium 9.5 mol% was obtained. The composition ratio of Ni(X)/Al was 0.18 on a molar basis, and the composition ratio of Ni(X)/Mg(B) was 0.16 on a molar basis.

The specific surface area obtained by the nitrogen adsorption method was 245 m ² /g, the pore volume was 0.26 mL/g, and the average pore diameter was 4.0 nm. The bulk density is 0.99 CBD and the abrasion resistance is 0.1% by mass. As a result of measurement by the laser particle size distribution of the scattering method, the average particle diameter was 62 μm. Moreover, as a result of observation by a scanning electron microscope (SEM), it is understood that the ceria-based material has no cracks or defects and has a substantially spherical shape. Regarding the solid form, as a result of powder X-ray diffraction (XRD), it was found that an amorphous pattern similar to that of the ceria gel was obtained.

Next, in order to evaluate the acid resistance and alkalinity of the cerium oxide-based material obtained as described above, the pH swing test was carried out by the same method as in Example 1. As a result, the specific surface area of the cerium oxide-based material after the pH swing treatment was 243 m ² /g, the pore volume was 0.27 mL/g, and the average pore diameter was 4.1 nm, which was not observed by the pH swing treatment. Structural changes in cerium oxide materials.

[Embodiment 10]

An aqueous solution of 188 g of aluminum nitrate nonahydrate, 145 g of nickel nitrate hexahydrate, 128 g of magnesium nitrate hexahydrate, and 46 g of 60% nitric acid in 552 mL of pure water was prepared. The aqueous solution was gradually added dropwise to a cerium oxide sol solution having a colloidal particle diameter of 10 to 20 nm maintained at a stirring state of 15 ° C (manufactured by Nissan Chemical Co., Ltd., trade name "Snowtex N-30", SiO ₂ content: 30 mass %) 993 g, a mixed slurry of cerium oxide sol, aluminum nitrate, nickel nitrate and magnesium nitrate was obtained. Thereafter, the mixed slurry was spray-dried by a spray dryer apparatus having an outlet temperature of 130 ° C to obtain a solid matter.

Next, heating, ‧ calcination, and gradual cooling were carried out in the same manner as in Example 1, to obtain a cerium oxide-based material containing 矽76.9 mol%, aluminum 7.7 mol%, nickel 7.7 mol%, and magnesium 7.7 mol%. The composition ratio of Ni(X)/Al was 1.0 on a molar basis, and the composition ratio of Ni(X)/Mg(B) was 1.0 on a molar basis. The specific surface area obtained by the nitrogen adsorption method was 130 m ² /g, the pore volume was 0.25 mL/g, and the average pore diameter was 7.8 nm. The bulk density is 0.96 CBD and the abrasion resistance is 0.1% by mass. As a result of measurement by the laser particle size distribution of the scattering method, the average particle diameter was 62 μm. Further, as a result of observation by a scanning electron microscope (SEM), it was found that the ceria-based material was free from cracks or defects, and was substantially spherical in shape.

Next, in order to evaluate the acid resistance and alkalinity of the cerium oxide-based material obtained as described above, the pH swing test was carried out by the same method as in Example 1. As a result, the specific surface area of the cerium oxide-based material after the pH swing treatment was 131 m ² /g, the pore volume was 0.26 mL/g, and the average pore diameter was 7.9 nm, and almost no pH swing treatment was observed. The structural change of the cerium oxide-based material.

[Example 11]

In the same manner as in Example 10, Mn 70.4 mol%, aluminum 7.4 mol was obtained in the same manner as in Example 10 except that 190 g of nickel nitrate nickel was used instead of 145 g of nickel nitrate hexahydrate, and 704 mL of pure water was used instead of 552 mL of pure water. %, nickel 11.1 mol%, magnesium 7.4 mol% of cerium oxide-based material. The composition ratio of Ni(X)/Al was 1.5 on a molar basis, and the composition ratio of Ni(X)/Mg(B) was 1.5 on a molar basis. The specific surface area obtained by the nitrogen adsorption method was 100 m ² /g, the pore volume was 0.20 mL/g, and the average pore diameter was 8.2 nm. The bulk density is 0.95 CBD, and the abrasion resistance is 0.1% by mass. As a result of measurement by the laser particle size distribution of the scattering method, the average particle diameter was 63 μm. Further, as a result of observation by a scanning electron microscope (SEM), it was found that the ceria-based material was free from cracks or defects, and was substantially spherical in shape.

Next, in order to evaluate the acid resistance and alkalinity of the cerium oxide-based material obtained as described above, the pH swing test was carried out by the same method as in Example 1. As a result, the specific surface area of the cerium oxide-based material after the pH swing treatment was 99 m ² /g, the pore volume was 0.20 mL/g, and the average pore diameter was 8.3 nm, and almost no pH swing treatment was observed. The structural change of the cerium oxide-based material.

[Embodiment 12]

30 g of the cerium oxide-based material obtained in Example 9 was added to 100 mL of distilled water placed in a glass vessel, and while stirring at 60 ° C, a specific amount of a palladium chloride aqueous solution was added dropwise thereto, and 0.5 N of hydrogen hydroxide was further added thereto. The aqueous solution was adjusted to have a pH of 8 in an aqueous sodium solution. After stirring for 1 hour in this state, the mixture was allowed to stand and the supernatant was removed, and the solid matter washed with distilled water until no Cl ions were detected was dried at 105 ° C for 16 hours, and then at 300 ° C in air. Calcined for 5 hours. Next, the obtained solid matter was subjected to a reduction treatment at 400 ° C for 3 hours in a hydrogen atmosphere to obtain a noble metal carrier carrying 2.4% by mass of palladium.

The noble metal support had a specific surface area of 247 m ² /g by a nitrogen gas adsorption method, a pore volume of 0.26 mL/g, and an average pore diameter of 4.0 nm. As a result of measurement by the laser particle size distribution of the scattering method, the average particle diameter of the obtained noble metal carrier was 62 μm. As a result of observation by a scanning electron microscope (SEM), it was found that the noble metal carrier was free from cracks or defects and had a substantially spherical shape.

Further, the morphology of the noble metal carrier was observed by a transmission electron microscope (TEM), and it was confirmed that the particles had a maximum distribution (number average particle diameter: 4.3 nm (calculated number: 100)) of palladium particles having a particle size of 4 to 5 nm. It is supported on a cerium oxide-based material as a carrier.

Next, in order to evaluate the acid resistance and alkalinity of the noble metal carrier obtained as described above, the pH swing test was carried out by the same method as in Example 1. As a result, the noble metal support after the pH swing treatment had a specific surface area of 245 m ² /g, a pore volume of 0.26 mL/g, and an average pore diameter of 4.1 nm, and no structure due to pH swing treatment was found. Variety. Further, it was confirmed by a transmission electron microscope (TEM) that the average particle diameter of the palladium particles was 4.4 nm (calculated number: 100), and sintering of the palladium particles was hardly observed.

[Example 13]

30 g of the cerium oxide-based material obtained in Example 4 was added to 100 mL of distilled water placed in a glass vessel, and while stirring at 80 ° C, a specific amount of cerium chloride aqueous solution was added dropwise thereto, and 0.5 N of hydric hydroxide was further added thereto. The aqueous solution was adjusted to have a pH of 8 in an aqueous sodium solution. After stirring for 1 hour in this state, the mixture was allowed to stand and the supernatant was removed, and the solid matter washed with distilled water until no Cl ions were detected was dried at 105 ° C for 16 hours, and then at 300 ° C in air. Calcined for 3 hours. Next, the obtained solid matter was subjected to a reduction treatment at 350 ° C for 3 hours in a hydrogen atmosphere to obtain a noble metal carrier carrying 2.1% by mass of ruthenium.

The noble metal support had a specific surface area of 241 m ² /g by a nitrogen gas adsorption method, a pore volume of 0.27 mL/g, and an average pore diameter of 3.9 nm. As a result of measurement by the laser particle size distribution of the scattering method, the average particle diameter of the obtained noble metal carrier was 62 μm. As a result of observation by a scanning electron microscope (SEM), it was found that the noble metal carrier was free from cracks or defects and had a substantially spherical shape.

Further, the morphology of the noble metal carrier was observed by a transmission electron microscope (TEM), and it was confirmed that the particles had a maximum distribution (number average particle diameter: 4.4 nm (calculated number: 100)) of the particles of 4 to 5 nm. It is supported on a cerium oxide-based material as a carrier.

Next, in order to evaluate the acid resistance and alkalinity of the noble metal carrier obtained as described above, the pH swing test was carried out by the same method as in Example 1. As a result, the noble metal support after the pH swing treatment had a specific surface area of 240 m ² /g, a pore volume of 0.26 mL/g, and an average pore diameter of 4.2 nm, and no structure due to pH swing treatment was found. Variety. Further, it was confirmed by a transmission electron microscope (TEM) that the average particle diameter of the cerium particles was 4.7 nm (calculated number: 100), and sintering of the cerium particles was hardly observed.

[Embodiment 14]

30 g of the cerium oxide-based material obtained in Example 2 was added to 100 mL of distilled water placed in a glass vessel, and while stirring at 80 ° C, a specific amount of a gold chloride aqueous solution was added dropwise thereto, and 0.5 N hydrogen was further added thereto. The pH of the aqueous solution was adjusted to 8 with an aqueous solution of sodium oxide. After stirring for 1 hour in this state, the mixture was allowed to stand and the supernatant was removed, and the solid matter washed with distilled water until no Cl ions were detected was dried at 105 ° C for 16 hours, and then at 400 ° C in air. The calcination was carried out for 3 hours, whereby a noble metal carrier carrying 1.8% by mass of gold was obtained.

The noble metal support had a specific surface area of 175 m ² /g by a nitrogen gas adsorption method, a pore volume of 0.27 mL/g, and an average pore diameter of 4.0 nm. As a result of measurement by the laser particle size distribution of the scattering method, the average particle diameter of the obtained noble metal carrier was 62 μm. As a result of observation by a scanning electron microscope (SEM), it was found that the noble metal carrier was free from cracks or defects and had a substantially spherical shape.

In addition, the morphology of the noble metal carrier was observed by a transmission electron microscope (TEM). As a result, it was confirmed that the particles had a maximum distribution (number average particle diameter: 3.5 nm (calculated number: 100)) of gold particles at 3 to 4 nm. It is supported on a cerium oxide-based material as a carrier.

Next, in order to evaluate the acid resistance and alkalinity of the noble metal carrier obtained as described above, the pH swing test was carried out by the same method as in Example 1. As a result, the noble metal support after the pH swing treatment had a specific surface area of 173 m ² /g, a pore volume of 0.26 mL/g, and an average pore diameter of 4.5 nm, and almost no pH swing treatment was observed. Structural changes. Further, it was confirmed by a transmission electron microscope (TEM) that the average particle diameter of the gold particles was 3.9 nm (calculated number: 100), and sintering of the gold particles was hardly observed.

Table 1 shows the physical properties of the cerium oxide-based materials of Examples 1 to 11 and the noble metal carriers of Examples 12 to 14.

[Table 1]

[Comparative Example 1]

The raw material cerium oxide sol solution is sold under the trade name "Snowtex N-40" (SiO ₂ content: 40% by mass) manufactured by Nissan Chemical Co., Ltd., and sold under the trade name "Snowtex N-30" manufactured by Nissan Chemical Co., Ltd., without adding nitric acid. A solid matter was obtained in the same manner as in Example 1 except that aluminum, nickel nitrate, and magnesium nitrate were used as the separate components of cerium oxide until spray drying of the mixed slurry was carried out using a spray dryer apparatus. Next, the solid matter obtained was heated from room temperature to 300 ° C in 2 hours using a rotary kiln, and then kept at 300 ° C for 1 hour. Further, the temperature was raised to 600 ° C over 2 hours, and then calcined at 600 ° C for 1 hour. Thereafter, it was gradually cooled to obtain cerium oxide.

The specific surface area obtained by the nitrogen adsorption method was 215 m ² /g, the pore volume was 0.26 mL/g, and the average pore diameter was 5.5 nm. The bulk density is 0.55 CBD, and the abrasion resistance is 3.3% by mass. As a result of measurement by the laser particle size distribution of the scattering method, the average particle diameter was 66 μm. Further, as a result of observation by a scanning electron microscope (SEM), cracks or defects were found in cerium oxide. The shape of the cerium oxide is substantially spherical. Regarding the solid form, as a result of powder X-ray diffraction (XRD), it was found that an amorphous pattern was obtained.

Next, in order to evaluate the acid resistance and alkalinity of the cerium oxide obtained as described above, the pH swing test was carried out by the same method as in Example 1. As a result, the specific surface area of the cerium oxide after the pH swing treatment was 198 m ² /g, the pore volume was 0.27 mL/g, and the average pore diameter was 9.8 nm, and the structural change due to the pH swing treatment was found.

[Comparative Example 2]

A cerium oxide-alumina composition containing cerium 93.0 mol% and aluminum 7.0 mol% was obtained in the same manner as in Example 1 except that nickel nitrate and magnesium nitrate were not used. The specific surface area obtained by the nitrogen adsorption method was 220 m ² /g, the pore volume was 0.30 mL/g, and the average pore diameter was 5.2 nm. The bulk density is 0.94 CBD, and the abrasion resistance is 0.2% by mass. As a result of measurement by the laser particle size distribution of the scattering method, the average particle diameter of the ceria-alumina composition was 62 μm. Further, as a result of observation by a scanning electron microscope (SEM), it was found that the ceria-alumina composition had no cracks or defects and was substantially spherical in shape. Regarding the solid form, as a result of powder X-ray diffraction (XRD), it was found that an amorphous pattern was obtained.

Next, in order to evaluate the acid resistance and alkalinity of the cerium oxide-alumina obtained as described above, the pH swing test was carried out by the same method as in Example 1. As a result, the ceria-alumina composition after pH swing treatment had a specific surface area of 210 m ² /g, a pore volume of 0.32 mL/g, and an average pore diameter of 9.5 nm, which was found to be treated by a pH swing treatment. The resulting structural changes.

[Comparative Example 3]

A cerium oxide-alumina-magnesia composition containing cerium 86.5 mol%, aluminum 6.9 mol%, and magnesium 6.6 mol% was obtained in the same manner as in Example 1 except that nickel nitrate was not used. The specific surface area obtained by the nitrogen adsorption method was 213 m ² /g, the pore volume was 0.27 mL/g, and the average pore diameter was 5.1 nm. The bulk density is 0.96 CBD and the abrasion resistance is 0.1% by mass. As a result of measurement by the laser particle size distribution of the scattering method, the average particle diameter of the ceria-alumina-magnesia composition was 62 μm. Further, as a result of observation by a scanning electron microscope (SEM), it was found that the ceria-alumina-magnesia composition had no cracks or defects and was substantially spherical in shape. Regarding the solid form, as a result of powder X-ray diffraction (XRD), it was found that an amorphous pattern similar to that of the ceria gel was obtained.

Next, in order to evaluate the acid resistance and alkalinity of the ceria-alumina-magnesia composition obtained as described above, the pH swing test was carried out by the same method as in Example 1. As a result, the specific surface area of the ceria-alumina-magnesia after the pH swing treatment was 204 m ² /g, the pore volume was 0.26 mL/g, and the average pore diameter was 8.5 nm, which was found to be treated by pH swing. Structural changes caused by it.

[Comparative Example 4]

Use aluminum nitrate nonahydrate 2.3 kg instead of aluminum nitrate nonahydrate 1.5 kg, use nickel nitrate hexahydrate 0.37 kg instead of nickel nitrate hexahydrate 0.24 kg, use magnesium nitrate hexahydrate 0.21 kg instead of magnesium nitrate hexahydrate 0.98 kg The cerium oxide sol solution (manufactured by Nissan Chemical Co., Ltd., trade name "Snowtex N-30", SiO ₂ content: 30% by mass) 1.0 kg was used instead of the cerium oxide sol solution 10.0 kg, and the same as Example 1 In the same manner, a cerium oxide-alumina-nickel oxide-magnesia composition containing cerium 37.3 mol%, aluminum 46.2 mol%, nickel 10.1 mol%, and magnesium 6.5 mol% was obtained. The composition ratio of Ni(X)/Al was 0.22 on a molar basis, and the composition ratio of Ni(X)/Mg(B) was 1.56 on a molar basis. The specific surface area obtained by the nitrogen adsorption method was 195 m ² /g, the pore volume was 0.3 mL/g, and the average pore diameter was 5.3 nm. The bulk density is 0.85 CBD, and the abrasion resistance is 0.5% by mass. As a result of measurement by the laser particle size distribution of the scattering method, the average particle diameter was 64 μm. Further, as a result of observation by a scanning electron microscope (SEM), it was found that the ceria-alumina-nickel oxide-magnesia composition was found to be cracked or defective. The shape is roughly spherical. Regarding the solid form, as a result of powder X-ray diffraction (XRD), it was found that a crystal pattern derived from alumina was obtained.

Next, in order to evaluate the acid resistance and alkalinity of the ceria-alumina-nickel oxide-magnesia composition obtained as described above, the pH swing test was carried out by the same method as in Example 1. As a result, the ceria-alumina-nickel oxide-magnesia composition after pH swing treatment had a specific surface area of 180 m ² /g, a pore volume of 0.29 mL/g, and an average pore diameter of 8.7 nm. Structural changes caused by pH swing processing.

[Comparative Example 5]

Use aluminum nitrate nonahydrate 1.0 kg instead of aluminum nitrate nonahydrate 1.5 kg, use nickel nitrate hexahydrate 0.05 kg instead of nickel nitrate hexahydrate 0.24 kg, use magnesium nitrate hexahydrate 0.23 kg instead of magnesium nitrate hexahydrate 0.98 kg Otherwise, in the same manner as in Example 1, cerium oxide-alumina-nickel oxide-oxidation containing cerium 93.1 mol%, aluminum 5.0 mol%, nickel 0.3 mol%, and magnesium 1.6 mol% was obtained. Magnesium composition. The composition ratio of Ni(X)/Al was 0.07 on a molar basis, and the composition ratio of Ni(X)/Mg(B) was 0.22 on a molar basis. The specific surface area obtained by the nitrogen adsorption method was 210 m ² /g, the pore volume was 0.27 mL/g, and the average pore diameter was 5.4 nm. The bulk density was 0.9 CBD and the abrasion resistance was 2.0% by mass. As a result of measurement by the laser particle size distribution of the scattering method, the average particle diameter was 65 μm. Further, as a result of observation by a scanning electron microscope (SEM), it was found that the ceria-alumina-nickel oxide-magnesia composition was found to be cracked or defective. The shape is roughly spherical. Regarding the solid form, as a result of powder X-ray diffraction (XRD), it was found that an amorphous pattern similar to that of the ceria gel was obtained.

Next, in order to evaluate the acid resistance and alkalinity of the ceria-alumina-nickel oxide-magnesia composition obtained as described above, the pH swing test was carried out by the same method as in Example 1. As a result, the ceria-alumina-nickel oxide-magnesia composition after pH swing treatment had a specific surface area of 195 m ² /g, a pore volume of 0.27 mL/g, and an average pore diameter of 8.5 nm. Structural changes caused by pH swing processing.

[Comparative Example 6]

In the same manner as in Example 1, except that 0.24 kg of manganese nitrate hexahydrate was used instead of nickel nitrate hexahydrate 0.24 kg, 矽85.3 mol%, aluminum 6.8 mol%, manganese 1.4 mol%, magnesium 6.5 were obtained. Molar% cerium oxide-alumina-manganese oxide-magnesia composition. The specific surface area obtained by the nitrogen adsorption method was 220 m ² /g, the pore volume was 0.27 mL/g, and the average pore diameter was 5.1 nm. The bulk density is 0.98 CBD, and the abrasion resistance is 0.1% by mass. As a result of measurement by the laser particle size distribution of the scattering method, the average particle diameter was 62 μm. Further, as a result of observation by a scanning electron microscope (SEM), the shape was substantially spherical. Regarding the solid form, as a result of powder X-ray diffraction (XRD), it was found that an amorphous pattern similar to that of the ceria gel was obtained.

Next, in order to evaluate the acid resistance and alkalinity of the cerium oxide-alumina-manganese-magnesia composition obtained as described above, the pH swing test was carried out by the same method as in Example 1. As a result, the ceria-alumina-manganese-magnesia composition after the pH swing treatment had a specific surface area of 210 m ² /g, a pore volume of 0.27 mL/g, and an average pore diameter of 8.1 nm. Structural changes caused by pH swing processing.

[Comparative Example 7]

A noble metal support carrying palladium on the ceria-alumina-magnesia composition was obtained in the same manner as in Example 12 except that nickel nitrate was not used. The obtained precious metal carrier contained 矽81.7 mol%, aluminum 8.8 mol%, and magnesium 9.5 mol% with respect to the total amount of lanthanum, aluminum, and magnesium. The loading of palladium was 2.1% by mass.

The specific surface area obtained by the nitrogen adsorption method was 243 m ² /g, the pore volume was 0.27 mL/g, and the average pore diameter was 4.1 nm. As a result of measurement by the laser particle size distribution of the scattering method, the average particle diameter of the noble metal carrier was 62 μm. Further, as a result of observation by a scanning electron microscope (SEM), it was found that the noble metal carrier was free from cracks or defects and had a substantially spherical shape.

Further, the morphology of the noble metal carrier was observed by a transmission electron microscope (TEM), and it was confirmed that the particles had a maximum distribution (number average particle diameter: 4.2 nm (calculated number: 100)) of palladium particles having a particle diameter of 4 to 5 nm. Loaded on a carrier.

Next, in order to evaluate the acid resistance and alkalinity of the noble metal support obtained above, the pH swing test was carried out by the same method as in Example 1. As a result, the specific surface area of the metal support after the pH swing treatment was 224 m ² /g, the pore volume was 0.28 mL/g, and the average pore diameter was 8.4 nm, and the structural change due to the pH swing treatment was found. . Further, it was confirmed by a transmission electron microscope (TEM) that the average particle diameter of the composite particles was 6.7 nm (calculated number: 100), and it was observed that the pore diameter of the noble metal carrier was enlarged while the palladium particles were sintered.

[Example 15]

300 g of the cerium oxide-based material of Example 1 was placed in a glass vessel containing 1 L of distilled water, and a predetermined amount of a gold chloride aqueous solution was rapidly added dropwise while stirring at 60 °C. Next, a 0.5 N aqueous sodium hydroxide solution was further added, and the pH of the aqueous solution was adjusted to 8, and the mixture was stirred for 1 hour in this state. Thereafter, the glass container was allowed to stand, and the supernatant was removed, and the precipitate was collected. The precipitate was washed with distilled water until Cl ions were not detected, and dried at 105 ° C for 16 hours, and then further in air at 400. After calcination at ° C for 5 hours, a noble metal support (2% Au/Si-Al-Ni-Mg composite oxide) supporting 2.0% by mass of Au was obtained.

The noble metal support had a specific surface area of 242 m ² /g by a nitrogen gas adsorption method, a pore volume of 0.27 mL/g, and an average pore diameter of 3.9 nm. As a result of measurement by the laser particle size distribution of the scattering method, the average particle diameter was 62 μm. Further, as a result of observation by a scanning electron microscope (SEM), it was found that the noble metal carrier was free from cracks or defects and had a substantially spherical shape.

According to the powder X-ray diffraction (XRD) of the above noble metal carrier, a diffraction peak belonging to Au was observed. The fine structure of the noble metal support was observed using a transmission electron microscope (TEM), and as a result, Au particles having a particle diameter of 2 to 3 nm were uniformly supported on the surface of the carrier. The number average particle diameter of the Au particles was 3.1 nm (calculated number: 100).

Next, in order to evaluate the acid resistance and alkalinity of the above-mentioned noble metal carrier, a pH swing test was carried out by the same method as in Example 1. As a result, the noble metal support after the pH swing treatment had a specific surface area of 243 m ² /g, a pore volume of 0.27 mL/g, and an average pore diameter of 3.9 nm, and no precious metal caused by the pH swing treatment was found. The structure of the load changes. Further, it was confirmed by a transmission electron microscope (TEM/STEM) that the average particle diameter of the Au particles was 3.2 nm (calculated number: 100), and particle growth of the Au particles was hardly observed.

240 g of the above-mentioned noble metal carrier (2% Au/Si-Al-Ni-Mg composite oxide) was placed in a reactor of a stirring type stainless steel having a catalytic separator and a liquid phase of 1.2 liters as a catalyst. The reaction was carried out while stirring the contents at a speed of 4 m/sec at the front end of the stirring blade in the reactor, and an oxidative carboxylic acid ester was formed from the aldehyde and the alcohol. 36.7 mass% of the methacrolein/methanol solution was continuously supplied to the reactor at 0.6 liter/hr, and 1 to 4 mass% of the NaOH/methanol solution was continuously fed at 0.06 liter/hr. Air was blown at a reaction temperature of 80 ° C and a reaction pressure of 0.5 MPa so that the outlet oxygen concentration became 4.0% by volume (corresponding to an oxygen partial pressure of 0.02 MPa), and the pH of the reaction system was adjusted to 7 to adjust the supply to the reactor. NaOH concentration. The reaction product was continuously discharged from an overflow line connected to the outlet of the reactor, and the composition was analyzed by gas chromatography to investigate the reactivity.

The conversion of methacrolein at the time of 500 hours after the start of the reaction was 45.8%, the selectivity of methyl methacrylate was 87.5%, and the activity of methyl methacrylate per unit mass of the catalyst was 4.36 mol/hour. /kg-catalyst. The rate of conversion of methacrolein to the time of 1000 hours after the start of the reaction was 45.5%, the selectivity of methyl methacrylate was 87.4%, and the activity of methyl methacrylate was 4.33 mol/hr/kg-catalyst. The reactivity was hardly changed.

The catalyst was discharged after 1000 hours from the start of the reaction, and observed by a scanning electron microscope (SEM). As a result, almost no cracks or defects were observed in the catalyst particles. Further, the catalyst obtained by the nitrogen gas adsorption method had a specific surface area of 243 m ² /g, a pore volume of 0.27 mL/g, and an average pore diameter of 4.0 nm.

Next, a catenary of 1000 hours after the start of the reaction was observed by a transmission electron microscope (TEM/STEM), and it was confirmed that the nanoparticles having a maximum distribution (number average particle diameter: 3.3 nm) having a particle diameter of 2 to 3 nm were obtained. Supported on the carrier, no sintering of the Au particles was observed.

[Example 16]

300 g of the carrier obtained in Example 1 was added to 1 L of distilled water placed in a glass container, and while stirring at 60 ° C, a dilute hydrochloric acid solution of palladium chloride equivalent to 2.5% by mass was rapidly added dropwise and An aqueous solution of lead nitrate is used as Pd and Pb. Thereafter, the contents of the glass vessel were kept for 1 hour, and a stoichiometric amount of 1.2 times was added thereto for reduction. The supernatant was removed by decantation and the precipitate was collected, and the precipitate was washed with distilled water until C1 ions were not detected, and vacuum-dried at 60 ° C to obtain 2.5 mass% of the precipitate. A noble metal carrier of Pd and Pb (PdPb/Si-Al-Ni-Mg composite oxide).

The noble metal support had a specific surface area of 240 m ² /g by a nitrogen gas adsorption method, a pore volume of 0.26 mL/g, and an average pore diameter of 4.0 nm. As a result of measurement by the laser particle size distribution of the scattering method, the average particle diameter was 62 μm. Further, as a result of observation by a scanning electron microscope (SEM), it was found that the noble metal carrier was free from cracks or defects and had a substantially spherical shape.

According to the powder X-ray diffraction (XRD) of the above noble metal carrier, diffraction peaks (2θ = 38.6°, 44.8°, 65.4°, 78.6°) of the intermetallic compound belonging to Pd3Pb1 were observed. The fine structure of the noble metal support was observed using a transmission electron microscope (TEM), and as a result, PdPb particles having a particle diameter of 5 to 6 nm were uniformly supported on the surface of the carrier. The number average particle diameter of the PdPb particles was 5.5 nm (calculated number: 100).

Next, in order to evaluate the chemical stability of the noble metal carrier obtained as described above, the pH swing test was carried out by the same method as in Example 1. As a result, the noble metal support after the pH swing treatment had a specific surface area of 241 m ² /g, a pore volume of 0.27 mL/g, and an average pore diameter of 4.0 nm, and no structure due to pH swing treatment was observed. Variety. Further, it was confirmed by a transmission electron microscope (TEM) that the average particle diameter of the PdPb particles was 5.1 nm (calculated number: 100), and particle growth of the PdPb particles was hardly observed.

Methyl methacrylate was produced by using methacrolein in the same manner as in Example 15 except that 240 g of the noble metal support (PdPb/Si-Al-Ni-Mg composite oxide) obtained above was used as a catalyst.

The conversion of methacrolein at the time of 500 hours after the start of the reaction was 44.2%, the selectivity of methyl methacrylate was 91.5%, and the activity of methyl methacrylate per unit mass of the catalyst was 4.40 mol/hr. /kg-catalyst. The conversion of methacrolein at the time of 1000 hours after the start of the reaction was 44.6%, the selectivity of methyl methacrylate was 91.3%, and the activity of methyl methacrylate was 4.43 mol/hr/kg-catalyst. The reactivity was hardly changed.

The catalyst was discharged after 1000 hours from the start of the reaction, and observed by a scanning electron microscope (SEM). As a result, almost no cracks or defects were observed in the catalyst particles. Further, the catalyst obtained by the nitrogen gas adsorption method had a specific surface area of 241 m ² /g, a pore volume of 0.27 mL/g, and an average pore diameter of 4.1 nm.

Next, a catenary after 1000 hours after the start of the reaction was observed by a transmission electron microscope (TEM/STEM), and it was confirmed that the nanoparticles having a maximum distribution (number average particle diameter: 5.2 nm) having a particle diameter of 5 to 6 nm were obtained. Supported on the carrier, no sintering of PdPb particles was observed.

[Example 17]

A methacrylic acid was produced by using methacrolein in the same manner as in Example 15 except that 240 g of a noble metal support (Au/Si-Al-Zn-K composite oxide) obtained in Example 14 was used as a catalyst. Methyl ester.

The conversion of methacrolein at the time of 500 hours after the start of the reaction was 33.5%, the selectivity of methyl methacrylate was 86.7%, and the activity of methyl methacrylate per unit mass of the catalyst was 3.16 mol/hour. /kg-catalyst. The conversion of methacrolein at the time of 1000 hours after the start of the reaction was 33.2%, the selectivity of methyl methacrylate was 86.5%, and the activity of methyl methacrylate was 3.12 mol/hr/kg-catalyst. The reactivity was hardly changed.

The catalyst was discharged after 1000 hours from the start of the reaction, and observed by a scanning electron microscope (SEM). As a result, almost no cracks or defects were observed in the catalyst particles. Further, the catalyst obtained by the nitrogen gas adsorption method had a specific surface area of 171 m ² /g, a pore volume of 0.26 mL/g, and an average pore diameter of 4.7 nm.

Next, a catenary after 1000 hours after the start of the reaction was observed by a transmission electron microscope (TEM/STEM), and it was confirmed that the nanoparticles having a maximum distribution (number average particle diameter: 4.1 nm) having a particle diameter of 3 to 4 nm were obtained. Supported on the carrier, no sintering of the Au particles was observed.

[Comparative Example 8]

A noble metal carrier (2% Au/SiO ₂ -Al ₂ supported on 2.0% by mass of Au) was obtained in the same manner as in Example 15 except that the carrier was replaced with the cerium oxide-based material obtained in Comparative Example 3. O ₃ -MgO).

The noble metal support had a specific surface area of 232 m ² /g by a nitrogen gas adsorption method, a pore volume of 0.28 mL/g, and an average pore diameter of 4.0 nm. As a result of measurement by the laser particle size distribution of the scattering method, the average particle diameter was 62 μm. Further, as a result of observation by a scanning electron microscope (SEM), it was found that the noble metal carrier was free from cracks or defects and had a substantially spherical shape.

The fine structure of the noble metal support was observed by a transmission electron microscope (TEM). As a result, it was confirmed that the Au particles having a particle diameter of 3 to 4 nm were uniformly supported on the surface of the carrier. The number average particle diameter of the Au particles was 3.4 nm (calculated number: 100).

Next, in order to evaluate the acid resistance and alkalinity of the noble metal carrier obtained as described above, the pH swing test was carried out by the same method as in Example 1. As a result, the specific surface area of the noble metal carrier after the pH swing treatment was 242 m ² /g, the pore volume was 0.27 mL/g, and the average pore diameter was 8.2 nm, and the structural change due to the pH swing treatment was found. . Further, it was confirmed by a transmission electron microscope (TEM) that the average particle diameter of the Au particles was 5.6 nm (calculated number: 100), and the growth of the particles of the Au particles was observed.

The reaction was carried out in the same manner as in Example 15 except that the above noble metal carrier (2% Au/SiO ₂ -Al ₂ O ₃ -MgO) was used. As a result, the conversion of methacrolein at the time of 500 hours after the start of the reaction was 39.4%, the selectivity of methyl methacrylate was 82.1%, and the activity of methyl methacrylate per unit mass of the catalyst was 3.52. Mol / hour / kg - catalyst. The conversion of methacrolein at the time of 1000 hours after the start of the reaction was 31.1%, the selectivity of methyl methacrylate was 78.2%, and the activity of methyl methacrylate was 2.39 mol/hr/kg-catalyst. The reaction activity was found to be decreased.

The catalyst was discharged after 1000 hours from the start of the reaction, and observed by a scanning electron microscope (SEM). As a result, almost no cracks or defects were observed in the catalyst particles. Further, the specific surface area of the catalyst obtained by the nitrogen gas adsorption method was 212 m ² /g, the pore volume was 0.27 mL/g, and the average pore diameter was 8.2 nm, and the structure of the catalyst was found to change.

Next, a catenary electron microscope (TEM) was used to observe the catalyst after 1000 hours from the start of the reaction. As a result, the number average particle diameter of the Au particles was 5.5 nm, and the pore diameter was enlarged while the Au particles were sintered.

[Embodiment 18]

0.5 g of a noble metal support (2% Au/Si-Al-Ni-Mg composite oxide), 0.5 g of methacrolein, 6.3 g of water, and 3.2 g of acetonitrile as a solvent were charged in the same manner as in Example 15. In a SUS316 autoclave reactor (total capacity: 120 ml) of a magnetic stirrer, the autoclave was closed, and after the inside of the system was replaced with nitrogen gas, a mixed gas of nitrogen gas containing 7 vol% of oxygen was introduced into the gas phase portion. The internal pressure is boosted to 3.0 MPa.

Next, the reactor was fixed in an oil bath, and the reaction temperature was set to 100 ° C under stirring to carry out a reaction for 4 hours. After cooling, after removing the residual pressure and opening the autoclave, the catalyst was separated by filtration, and the filtrate was analyzed by a gas chromatograph. As a result, the methacrolein conversion rate was 49.7%, the methacrylic acid selectivity was 95.3%, and the methacrylic acid yield was 47.4%.

[Embodiment 19]

A noble metal support (2% Au/Si-Al-Ni-Mg composite oxide) similar to that of Example 15 was used in the same manner as in Example 18 except that the solvent was changed to acetone, and methacrolein was used. Production of methacrylic acid. As a result, the methacrolein conversion rate was 61.1%, the methacrylic acid selectivity was 96.6%, and the methacrylic acid yield was 59.0%.

[Example 20]

A noble metal support (2% Au/Si-Al-Ni-Mg composite oxide) similar to that of Example 15 was used in the same manner as in Example 18 except that the solvent was changed to the third butanol. Acrolein produces methacrylic acid. As a result, the methacrolein conversion rate was 64.7%, the methacrylic acid selectivity was 96.8%, and the methacrylic acid yield was 62.6%.

[Example 21]

1.0 L of an aqueous solution containing a specific amount of aqueous solution of gold chloride and nickel nitrate hexahydrate was heated to 90 °C. 300 g of the ceria-based material obtained in Example 1 was placed in the aqueous solution, and the mixture was stirred at 90 ° C for 1 hour while stirring, and the gold component and nickel were analyzed to form a ceria-based material.

Next, the supernatant was allowed to stand and removed, and washed with distilled water several times, followed by filtration. After drying at 105 ° C for 16 hours, it was calcined in air at 500 ° C for 3 hours, thereby obtaining a noble metal carrier (AuNiO/Si-Al-Ni-Mg carrying 1.5% by mass of gold and 1.5% by mass of nickel). Composite oxide).

With respect to the noble metal carrier, the specific surface area obtained by the nitrogen gas adsorption method was 227 m ² /g, the pore volume was 0.26 mL/g, and the average pore diameter was 4.9 nm. As a result of measurement by the laser particle size distribution of the scattering method, the average particle diameter was 65 μm. Further, as a result of observation by a scanning electron microscope (SEM), it was found that the noble metal carrier was free from cracks or defects and had a substantially spherical shape.

The fine structure of the noble metal support was observed by a transmission electron microscope (TEM), and as a result, metal particles having a particle diameter of 2 to 3 nm were uniformly supported on the surface of the ceria material. The number average particle diameter of the metal particles was 3.0 nm (calculated number: 100).

Next, in order to evaluate the chemical stability of the noble metal carrier obtained as described above, the pH swing test was carried out by the same method as in Example 1. As a result, the noble metal support after the pH swing treatment had a specific surface area of 229 m ² /g, a pore volume of 0.27 mL/g, and an average pore diameter of 4.9 nm, and no structure due to pH swing treatment was observed. Variety. Further, it was confirmed by a transmission electron microscope (TEM) that the average particle diameter of the metal particles was 3.0 nm (calculated number: 100), and particle growth of the metal particles was hardly observed.

Using the above noble metal carrier (AuNiO/Si-Al-Ni-Mg composite oxide), methacrylic acid was produced by using methacrolein in the same manner as in Example 16. As a result, the methacrolein conversion rate was 59.9%, the methacrylic acid selectivity was 96.1%, and the methacrylic acid yield was 57.6%.

[Example 22]

50 g of the noble metal support (AuNiO/Si-Al-Ni-Mg composite oxide) similar to Example 21, 100 g of methacrolein, 580 g of water, and 320 g of acetone as a solvent were placed in a mixture of SUS316 and stirred. In the autoclave (15 L), the autoclave was closed and the inside of the system was replaced with nitrogen, and then a mixed gas of nitrogen gas containing 7 vol% of oxygen was introduced into the gas phase portion, and the internal pressure was increased to 3.0 MPa.

After the reaction was carried out for 8 hours at a reaction temperature of 110 ° C, the mixture was cooled, the residual pressure was removed, and the autoclave was opened, and then the reaction liquid was analyzed by a gas chromatograph. As a result, the methacrolein conversion rate was 53.7%, the methacrylic acid selectivity was 95.9%, and the methacrylic acid yield was 51.5%.

[Example 23]

Use 4.4 kg of alumina instead of aluminum nitrate hexahydrate 1.5 kg, use 0.93 kg of nickel oxide instead of 0.24 kg of nickel nitrate hexahydrate, use 0.42 kg of magnesium oxide instead of 0.98 kg of magnesium nitrate hexahydrate, and replace the calcination temperature with 600 ° C. A carrier containing 矽42.9 mol%, aluminum 37.0 mol%, nickel 10.9 mol%, and magnesium 9.1 mol% was obtained in the same manner as in (1) of Example 1 except for 800 °C. The composition ratio of Ni(X)/Al was 0.30 on a molar basis, and the composition ratio of Ni(X)/Mg(B) was 1.20 on a molar basis. The specific surface area obtained by the nitrogen adsorption method was 78 m ² /g, the pore volume was 0.27 mL/g, and the average pore diameter was 5.2 nm. The bulk density is 1.02 CBD, and the abrasion resistance is 0.1% by mass. As a result of measurement by the laser particle size distribution of the scattering method, the average particle diameter was 62 μm. Further, as a result of observation by a scanning electron microscope (SEM), the carrier was free from cracks or defects, and the shape was substantially spherical. Regarding the solid form, as a result of powder X-ray diffraction (XRD), it was found that an amorphous pattern similar to that of the ceria gel was obtained.

300 g of the cerium oxide-based material obtained as described above was added to a glass vessel in which 1 L of distilled water was placed, and while stirring at 60 ° C, a specific amount of a gold chloride aqueous solution and nickel nitrate hexahydrate were rapidly added dropwise. Diluted hydrochloric acid solution. Next, a 0.5 N aqueous sodium hydroxide solution was further added, and the pH of the aqueous solution was adjusted to 8, and the mixture was stirred for 1 hour in this state. Thereafter, a stoichiometric amount of 1.2 times was added to the contents of the glass vessel for reduction. The supernatant was removed by decantation and the precipitate was collected, and the precipitate was washed with distilled water until Cl ions were not detected, and further dried under vacuum at 60 ° C to obtain 3.0% by mass. A noble metal carrier of Au and Ni (AuNi/Si-Al-Ni-Mg composite oxide).

The noble metal support had a specific surface area of 105 m ² /g by a nitrogen gas adsorption method, a pore volume of 0.27 mL/g, and an average pore diameter of 4.0 nm. As a result of measurement by the laser particle size distribution of the scattering method, the average particle diameter was 62 μm. Further, as a result of observation by a scanning electron microscope (SEM), it was found that the noble metal carrier was free from cracks or defects and had a substantially spherical shape.

The fine structure of the noble metal support was observed by a transmission electron microscope (TEM), and as a result, metal particles having a particle diameter of 4 to 5 nm were uniformly supported on the surface of the carrier. The number average particle diameter of the metal particles was 4.5 nm (calculated number: 100).

Next, in order to evaluate the chemical stability of the noble metal carrier obtained as described above, the pH swing test was carried out by the same method as in Example 1. As a result, the noble metal support after the pH swing treatment had a specific surface area of 107 m ² /g, a pore volume of 0.27 mL/g, and an average pore diameter of 4.1 nm, and no structure due to pH swing treatment was found. Variety. Further, it was confirmed by a transmission electron microscope (TEM) that the average particle diameter of the metal particles was 4.7 nm (calculated number: 100), and particle growth of the metal particles was hardly observed.

Using the above noble metal carrier (AuNi/Si-Al-Ni-Mg composite oxide), methacrylic acid was produced by using methacrolein in the same manner as in Example 18. As a result, the methacrolein conversion rate was 38.9%, the methacrylic acid selectivity was 94.9%, and the methacrylic acid yield was 36.7%.

[Example 24]

300 g of the carrier obtained in Example 2 was added to a glass container in which 1 L of distilled water was placed, and while stirring at 60 ° C, a specific amount of a solution of a gold chloride acid solution and a hydrochloric acid solution of a platinum chloride acid was rapidly added dropwise. . Next, a 0.5 N aqueous sodium hydroxide solution was further added, and the pH of the aqueous solution was adjusted to 8, and the mixture was stirred for 1 hour in this state. Thereafter, a stoichiometric amount of 1.2 times was added to the contents of the glass vessel for reduction. The supernatant was removed by decantation and the precipitate was collected, and the precipitate was washed with distilled water until Cl ions were not detected, and vacuum-dried at 60 ° C to obtain 2.0% by mass. A noble metal carrier of Au and Pt (AuPt/Si-Al-Zn-K composite oxide).

The noble metal carrier had a specific surface area of 220 m ² /g by a nitrogen gas adsorption method, a pore volume of 0.27 mL/g, and an average pore diameter of 3.9 nm. As a result of measurement by the laser particle size distribution of the scattering method, the average particle diameter was 62 μm. Further, as a result of observation by a scanning electron microscope (SEM), it was found that the noble metal carrier was free from cracks or defects and had a substantially spherical shape.

The fine structure of the noble metal support was observed using a transmission electron microscope (TEM), and as a result, metal particles having a particle diameter of 3 to 4 nm were uniformly supported on the surface of the carrier. The number average particle diameter of the metal particles was 3.5 nm (calculated number: 100).

Next, in order to evaluate the chemical stability of the noble metal carrier obtained as described above, the pH swing test was carried out by the same method as in Example 1. As a result, the noble metal support after the pH swing treatment had a specific surface area of 217 m ² /g, a pore volume of 0.27 mL/g, and an average pore diameter of 4.0 nm, and no structure due to pH swing treatment was observed. Variety. Further, it was confirmed by a transmission electron microscope (TEM) that the average particle diameter of the metal particles was 3.7 nm (calculated number: 100), and particle growth of the metal particles was hardly observed.

Using the above noble metal carrier (AuPt/Si-Al-Zn-K composite oxide), methacrylic acid was produced by using methacrolein in the same manner as in Example 18. As a result, the methacrolein conversion rate was 63.1%, the methacrylic acid selectivity was 96.3%, and the methacrylic acid yield was 60.8%.

[Example 25]

Using the same noble metal support (Pd/Si-Al-Ni-Mg composite oxide) as in Example 12, methacrylic acid was produced by using methacrolein in the same manner as in Example 18. As a result, the methacrolein conversion rate was 6.0%, the methacrylic acid selectivity was 66.6%, and the methacrylic acid yield was 4.0%.

[Example 26]

10 g of a noble metal support (Pd/Si-Al-Ni-Mg composite oxide) which is the same as that of Example 12 and a 10% by mass aqueous solution of ethylene glycol were placed in the liquid phase portion to be 0.5 liter. Stirred stainless steel reactor. The contents were stirred at a speed of 1.5 m/sec at the front end of the stirring blade in the reactor, and an oxidation reaction of ethylene glycol was carried out. The reaction temperature was set to 50° C., and air was blown at 350 ml/min under normal pressure, and a 2.5% by mass aqueous NaOH solution was supplied to the reactor so that the pH of the reaction system was 8 to 10. After the hour reaction, the catalyst was separated by filtration, and the filtrate was evaporated to dryness on a rotary evaporator to obtain 63 g of a white powder of sodium hydroxyacetate.

[Example 27]

1 g of the noble metal support (Pd/Si-Al-Ni-Mg composite oxide) as the catalyst of Example 12 and 150 g of liquid phenol were placed in a stirred stainless steel reactor (500 ml). . After the inside of the system was replaced with nitrogen, hydrogen gas was introduced into the gas phase portion, and the internal pressure was raised to 2.5 MPa. The reaction temperature was 140 ° C, and the content was stirred at a speed of 1.5 m / sec at the front end of the stirring blade, and hydrogenation reaction of cyclohexanone by phenol was carried out. After the reaction was carried out for 1 hour, the mixture was cooled, the residual pressure was removed, and the autoclave was opened. The catalyst was separated by filtration, and the filtrate was analyzed by a gas chromatograph. As a result, the phenol conversion rate was 99.7%, and the cyclohexanone selectivity was 91.3%.

[Example 28]

30 g of the cerium oxide-based material obtained in Example 4 was added to 100 mL of distilled water in a glass container, and while stirring at 80 ° C, a specific amount of a cerium chloride aqueous solution and an aqueous zinc nitrate solution were added dropwise thereto, and then added. The pH of the above aqueous solution was adjusted to 8 with a 0.5 N aqueous sodium hydroxide solution. After stirring for 1 hour in this state, the mixture was allowed to stand and the supernatant was removed, and the solid matter washed with distilled water until no Cl ions were detected was dried at 105 ° C for 16 hours, and then at 300 ° C in air. Calcined for 3 hours. Then, the obtained solid matter was subjected to reduction treatment at 350 ° C for 3 hours in a hydrogen atmosphere, thereby obtaining a noble metal support (RuZn supported on 10.4% by mass of zinc and having an atomic ratio of zinc to lanthanum of 0.11). /Si-Al-Fe-La composite oxide).

0.5 g of the above noble metal support (RuZn/Si-Al-Fe-La composite oxide) and 280 mL of a 10% by mass aqueous zinc sulfate solution were placed in a 1 liter Hessite autoclave, and stirred while stirring. Hydrogen was replaced, and after raising the temperature to 150 ° C, it was kept for 22 hours, and the catalyst slurry was treated beforehand. Thereafter, 140 mL of benzene was introduced, and a partial hydrogenation reaction of benzene was carried out while stirring at a high pressure of 5 MPa at a full pressure. The reaction liquid was discharged over time, and the composition of the liquid phase was analyzed by gas chromatography. As a result, the selectivity of cyclohexene when the conversion ratio of benzene was 50% was 81.5%.

[Example 29]

30 g of the cerium oxide-based material obtained in Example 1 was added to 100 mL of distilled water placed in a glass vessel, and a certain amount of cerium chloride, chloroplatinic acid, and chlorinated were added dropwise while stirring at 80 ° C. The diluted hydrochloric acid solution of tin was further added with a 0.5 N aqueous sodium hydroxide solution, and the pH of the aqueous solution was adjusted to 8. After stirring for 1 hour in this state, the mixture was allowed to stand and the supernatant was removed, and the solid matter washed with distilled water until no Cl ions were detected was dried at 105 ° C for 16 hours, and then at 300 ° C in air. Calcined for 3 hours. Then, the obtained solid matter was subjected to a reduction treatment at 350 ° C for 3 hours in a hydrogen atmosphere to obtain a noble metal carrier (RuSnPt/ supported on 6.1 mass% of ruthenium, 5.0 mass% of tin, and 3.4 mass% of platinum. Si-Al-Ni-Mg composite oxide).

0.15 g of the above noble metal support (RuSnPt/Si-Al-Ni-Mg composite oxide) and 5 g of water, 23% by mass of succinic acid, 60% by mass of glutaric acid, and 17% by mass of adipic acid 2.1 g of a mixture of diacid, glutaric acid and adipic acid was placed in a 30 mL autoclave, and after replacing the atmosphere in the autoclave with nitrogen at room temperature, hydrogen gas was introduced into the gas phase portion and the entire system was replaced. The pressure was raised to 2.0 MPa and the temperature was raised to 180 °C. Hydrogen gas was introduced at a time point of reaching 180 ° C, and after the internal pressure was 15 MPa, the hydrogenation reduction reaction was carried out for 10 hours. After the completion of the reaction, the catalyst was separated by decantation, and the catalyst was washed with ion-exchanged water.

Combining the reaction liquid separated by decantation and the catalyst cleaning liquid, the conversion rate of each dicarboxylic acid and the yield of the diol are analyzed by liquid chromatography and gas chromatography, and the result is succinic acid and glutaric acid. The conversion rates of acid and adipic acid were 93%, 93%, 95%, respectively, and the yields of 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol were 51%, respectively. 75%, 61%.

[Industrial availability]

According to the present invention, it is possible to provide a cerium oxide-based material having a strong mechanical strength, a large specific surface area, and excellent acid resistance and alkalinity, and a noble metal carrier containing the cerium oxide-based material.

Claims (15)

A cerium oxide-based material comprising: cerium, aluminum, at least one fourth periodic element selected from the group consisting of iron, cobalt, nickel, and zinc, and selected from the group consisting of alkali metal elements, alkaline earth metal elements, and rare earth elements At least one basic element in the group of the components; and the total amount of moles of the above-mentioned lanthanum, the aluminum, the fourth periodic element, and the basic element is 42 to 90 mol%, 3 to 38, respectively. % of moles, 0.5 to 20 moles, and 2 to 38 moles. The cerium oxide-based material according to claim 1, wherein the composition ratio of the fourth periodic element to the aluminum is 0.02 to 2.0 on a molar basis. The cerium oxide-based material according to claim 1, wherein a composition ratio of the fourth periodic element to the basic element is 0.02 to 2.0 on a molar basis. The cerium oxide-based material according to claim 2, wherein a composition ratio of the fourth periodic element to the basic element is 0.02 to 2.0 on a molar basis. The cerium oxide-based material according to any one of claims 1 to 4, wherein the fourth periodic element is nickel, and the basic element is magnesium, and the total amount of the cerium, the aluminum, the nickel, and the magnesium is The amount of the above-mentioned bismuth is contained in the range of 42 to 90 mol%, and the above-mentioned aluminum is contained in the range of 3 to 38 mol%, and the nickel is contained in the range of 0.5 to 20 mol%, in the case of 2 to 38 The above magnesium is contained in the range of % of the ear. A method for producing a cerium oxide-based material, comprising: a step of obtaining a composition comprising cerium oxide, an aluminum compound, a compound selected from the group consisting of at least one fourth periodic element of a group consisting of iron, cobalt, nickel, and zinc, and selected from the group consisting of alkali metal elements and alkaline earth a compound of at least one basic element in a group consisting of a metal element and a rare earth element; and a step of obtaining a solid substance by calcining the above composition or a dried product of the composition; and obtaining a cerium oxide-based material, the oxidizing The molar amount of the lanthanoid material relative to the following lanthanum, the following aluminum, the following fourth periodic element, and the following basic elements are respectively 42 to 90 mol %, 3 to 38 mol %, 0.5 to 20 The molar %, 2 to 38 mole % range includes: bismuth, aluminum, at least one fourth periodic element selected from the group consisting of iron, cobalt, nickel, and zinc, and is selected from the group consisting of alkali metal elements and alkaline earth At least one basic element of the group consisting of a metal element and a rare earth element. The method for producing a cerium oxide-based material according to claim 6, which further comprises the step of hydrothermally treating the solid matter. A method for producing a cerium oxide-based material, comprising: calcining a compound containing cerium oxide, an aluminum compound, and at least one basic element selected from the group consisting of an alkali metal element, an alkaline earth metal element, and a rare earth element; a step of obtaining a solid matter by the composition or the dried product of the composition; and acidifying the solid matter with a soluble metal salt containing at least one fourth periodic element selected from the group consisting of iron, cobalt, nickel, and zinc The mixture of aqueous solutions is neutralized to form the elements of the fourth cycle described above. a step of analyzing the solid matter; a step of hydrothermally treating the solid matter in which the fourth periodic element is precipitated; and a step of heat-treating the solid matter subjected to the hydrothermal treatment step; and obtaining cerium oxide The material, the total amount of the cerium oxide material relative to the following cerium, the following aluminum, the following fourth periodic element, and the following basic elements are respectively 42 to 90 mol%, 3 to 38 mol%, respectively. The range of 0.5 to 20 mol% and 2 to 38 mol% includes: bismuth, aluminum, at least one fourth periodic element selected from the group consisting of iron, cobalt, nickel, and zinc, and is selected from the group consisting of alkali At least one basic element among the group consisting of a metal element, an alkaline earth metal element, and a rare earth element. A noble metal support comprising: the cerium oxide-based material according to any one of claims 1 to 5, and the ruthenium, osmium, palladium, silver, iridium supported on the cerium oxide-based material At least one precious metal component of the group consisting of ruthenium, osmium, platinum, and gold. The noble metal carrier according to claim 9, wherein the noble metal component has an average particle diameter of 2 to 10 nm. A process for producing a carboxylic acid ester by reacting an aldehyde with an alcohol in the presence of a noble metal support of claim 9 or 10 and oxygen. The method for producing a carboxylic acid ester according to claim 11, wherein the aldehyde is at least one selected from the group consisting of acrolein, methacrolein, and a mixture thereof. The method for producing a carboxylic acid ester according to claim 11, wherein the aldehyde is at least one selected from the group consisting of acrolein, methacrolein, and a mixture thereof, and the alcohol is methanol. A method for producing a carboxylic acid, which is obtained by oxidizing an aldehyde to produce a carboxylic acid in the presence of a noble metal carrier as claimed in claim 9 or 10. The method for producing a carboxylic acid according to claim 14, wherein the aldehyde is at least one selected from the group consisting of acrolein, methacrolein, and a mixture thereof.