JP6031562B2 - Silica-based material and method for producing the same, noble metal support and method for producing carboxylic acids using the same as a catalyst - Google Patents

Description

  The present invention relates to a silica-based material and a method for producing the same, and a noble metal support and a method for producing a carboxylic acid using the same as a catalyst.

  Silica-based materials are used as materials that take advantage of their properties in various applications. Examples thereof include liquid chromatography fillers, cosmetic bases, catalysts, catalyst carriers, flow regulators, and diluents. One of the means to satisfy physical properties such as high specific surface area in order to satisfy the requirements for these applications is to make the silica-based material porous. Becomes weaker. On the other hand, when the precursor is fired at a high temperature in order to increase the mechanical strength of the silica-based material, the specific surface area becomes small. Thus, it is difficult to obtain a silica-based material satisfying the contradicting physical properties of high mechanical strength and large specific surface area, and no silica-based material satisfying both requirements has been obtained at present.

It is known that quartz, which is one of silica-based materials, is 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 cannot be used for applications requiring a high specific surface area. In order to use it as a catalyst carrier, it may be synthesized by increasing the specific surface area of the silica-based material, but in that case, mechanical strength is sacrificed, and there is no example that combines surface area and mechanical strength. .

Patent Document 1, as a carrier of a carboxylic acid ester production catalyst, 5-40 wt% of aluminum as Al ₂ O _3, magnesium 3-30% by weight MgO, silicon as SiO ₂ of 50 to 92 wt% A range of silica-alumina-magnesia is described.

JP-A-9-52044

  The silica-alumina-magnesia support described in Patent Document 1 has the characteristics of high mechanical strength, large specific surface area, high water resistance compared to silica, and high acid resistance compared to alumina. . However, when the carrier is used as a carrier for a catalyst for producing a carboxylate ester, the mechanical strength can be satisfied under normal use conditions, but conditions such as vigorous mixing between particles, particles and stirring springs, etc., for example, suspension In a reaction under severe conditions in the reaction, there may be a problem of cracking or chipping due to such friction.

  Further, according to the study by the present inventors, when the reaction is carried out over a long period of time using the catalyst having the carrier described in Patent Document 1, it is gradually caused by expansion of the pore diameter and particle growth. It has been found that the structure of the catalyst particles changes. The expansion of the pore diameter is due to the by-product of the reaction-specific acid component and the addition of the alkali component, whereby the catalyst particles are repeatedly exposed locally to acids and bases, and one of silicon and aluminum in the silica-alumina-magnesia support. This is considered to be caused by dissolution and precipitation of the part and rearrangement of the silica / alumina crosslinked structure. It was also found that the particle growth progressed by sintering of the supported noble metal simultaneously with the expansion of the pore diameter, and as a result, the catalytic activity decreased.

  The present invention has been made in view of the above circumstances, and is a silica-based material having high mechanical strength and a large specific surface area, and having excellent acid resistance and basicity, a method for producing the same, and its The object is to provide a noble metal support containing a silica-based material.

  From the viewpoint of improving the chemical stability and mechanical strength of silica gel, the present inventors paid attention to the unique structure of silica chains (-Si-O-) constituting the silica gel, and these structures and physical properties. Research on the correlation with As a result, surprisingly, at least one element selected from the group consisting of silicon, aluminum, iron, cobalt, nickel and zinc, and a group consisting of alkali metal elements, alkaline earth metal elements and rare earth elements A silica-based material composed of a composite oxide containing at least one selected basic element has excellent acid resistance and basicity, and overcomes each of the above-mentioned drawbacks found in conventional silica-based materials. The inventors have found that the above problems can be solved, and have completed the present invention.

That is, the present invention is as follows.
[1]
Silicon,
With aluminum,
At least one fourth periodic element selected from the group consisting of iron, cobalt, nickel and zinc;
At least one basic element selected from the group consisting of alkali metal elements, alkaline earth metal elements and rare earth elements;
Are 57.6 to 90 mol%, 3.1 to 30 mol%, and 0.75 to 15 with respect to the total molar amount of the silicon, the aluminum, the fourth periodic element, and the basic element, respectively. A silica-based material containing in the range of mol%, 2 to 36.6 mol%,
When the silica-based material is observed and measured by the electron probe microanalysis method, the distribution range of the concentration of the fourth periodic element to be measured is within 10% .
Catalyst carrier .
[2]
The silica-based material contains the silicon, the aluminum, the fourth periodic element, and the basic element in an amount of 70 to 90 mol%, 5 to 15 mol%, and 0.75, respectively, with respect to the total molar amount. The catalyst support according to [1], which is contained in a range of ˜15 mol% and 2 to 15 mol%.
[3]
The catalyst carrier according to [1] or [2], wherein the composition ratio of the fourth periodic element to the aluminum is 0.02 to 2.0 on a molar basis.
[4]
The catalyst carrier according to any one of [1] to [3], wherein the composition ratio of the fourth periodic element to the basic element is 0.02 to 2.0 on a molar basis.
[5]
The catalyst carrier according to any one of [1] to [4], wherein the fourth periodic element is nickel and the basic element is magnesium.
[6]
A method for producing the catalyst carrier according to any one of [1] to [5],
Selected from the group consisting of a compound of at least one fourth periodic element selected from the group consisting of silica, an aluminum compound, iron, cobalt, nickel and zinc, an alkali metal element, an alkaline earth metal element, and a rare earth element Obtaining a composition containing at least one basic element compound,
Baking the composition or a dried product thereof to obtain a solid;
Have
At least one fourth periodic element selected from the group consisting of silicon, aluminum, iron, cobalt, nickel and zinc, and at least selected from the group consisting of alkali metal elements, alkaline earth metal elements and rare earth elements obtaining a one basic element, a catalyst carrier comprising silica-based material having including a method of producing a catalyst carrier.
[7]
The method for producing a catalyst carrier according to [6], further comprising hydrothermally treating the solid.
[8]
The catalyst carrier according to any one of [1] to [5],
Supported on the silica-based material, at least one noble metal component selected from the group consisting of ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, and gold;
A noble metal-supported catalyst for producing a carboxylic acid ester .
[9]
The noble metal-supported catalyst for carboxylic acid ester production according to [8] , wherein an average particle size of the noble metal component is 2 to 10 nm.

  According to the present invention, there is provided a silica-based material having a high mechanical strength and a large specific surface area, which is excellent in acid resistance and basicity, and a noble metal support containing the silica-based material. be able to.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

The silica-based material of the present embodiment is
Silicon,
With aluminum,
At least one fourth periodic element selected from the group consisting of iron, cobalt, nickel and zinc;
At least one basic element selected from the group consisting of alkali metal elements, alkaline earth metal elements and rare earth elements;
Are 42 to 90 mol%, 3 to 38 mol%, 0.5 to 20 mol%, 2 to 2%, respectively, with respect to the total molar amount of the silicon, the aluminum, the fourth periodic element, and the basic element. It is contained in the range of ˜38 mol%.

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

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

  In the silica-based material of the present embodiment, aluminum (Al) coexists in silica having uncrosslinked silica (Si—O) chains such as silica gel, so that Si such as Si—O—Al—O—Si bond is present. -O chain Al cross-linked structure (hereinafter also referred to as "silica / alumina cross-linked structure") is newly formed, and Al- cross-linked structure is formed without losing stability to the original acidic substance of Si-O chain. It is thought. Thereby, it is considered that Si—O bond is strengthened and hydrolysis stability (hereinafter also simply referred to as “water resistance”) is remarkably improved. Moreover, when a silica-alumina crosslinked structure is formed, it is considered that Si—O uncrosslinked chains are reduced and mechanical strength is increased as compared with the case of silica alone. That is, it is presumed that the amount of silica-alumina crosslinked structure formed correlates with the improvement in mechanical strength and water resistance of the resulting silica-based material.

  With the generation of the silica-alumina crosslinked structure, the charge becomes unstable based on the difference in valence between Si (tetravalent) and Al (trivalent). Therefore, in the silica-based material of the present embodiment, at least one basic element selected from alkali metal elements, alkaline earth metal elements, and rare earth elements coexists in addition to silicon and aluminum. Thereby, 1 to 3 basic elements are compensated and neutralized, and charge stabilization is promoted. Furthermore, it is presumed that the stability of the structure can be further improved because the ternary system can further balance the charge. One reason for this is that silica-alumina is acidic while silica-alumina-magnesia is almost neutral.

  Furthermore, the silica-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 three component elements, so that the fourth period Acid resistance and basicity are higher than those not containing elements. Therefore, even under pH swing conditions where the acid and base are repeatedly exposed, the structural stability is high, and an increase in pore diameter and a decrease in specific surface area are suppressed.

  According to the study by the present inventors, it has been clarified that when silica-alumina or silica-alumina-magnesia is repeatedly exposed to acids and bases, the structural changes of these silica-based materials occur gradually. This phenomenon is that these silica-based materials are repeatedly exposed to acids and bases locally, and some silica and aluminum in the silica-based materials dissolve and precipitate, resulting in rearrangement of the silica-alumina crosslinked structure. This is considered to be caused by the increase in the pore diameter of the silica-based material. In addition, in the case of a metal-carrying material in which a noble metal is supported on the silica-based material, sintering of the supported noble metal occurs as the pore diameter increases due to pH swing, and the specific surface area of the noble metal decreases, thereby reducing the catalyst. It was also found that the activity decreased.

  On the other hand, in the silica-based material of the present embodiment, the fourth periodic element reacts with aluminum and / or a basic element that is a constituent element of the silica-based material, so that a composite oxide containing the fourth periodic element is obtained. Is considered to be generated. As a result of the formation of such a compound acting on the stabilization of the silica-alumina crosslinked structure, it is considered that the acid resistance and basicity of the silica-based material are improved, and the structural change is greatly improved.

  Here, the “composite oxide” in the present specification represents an oxide containing two or more metals. That is, the “composite oxide” is an oxide in which two or more kinds of metal oxides form a compound, and a double oxide in which an oxoacid ion does not exist as a structural unit (for example, perovskite oxidation of nickel). Products and spinel oxides). However, it is a concept wider than a double oxide, and includes all oxides in which two or more metals are combined. An oxide in which two or more metal oxides form a solid solution is also a category of “composite oxide”.

  For example, nickel is selected as the fourth periodic element, magnesium is selected as the basic element, and a silica-based material composed of a composite oxide containing silicon-aluminum-nickel-magnesium is subjected to double-crystal high-resolution X-ray fluorescence analysis (HRXRF). ), The nickel in the silica-based material of this embodiment does not exist as nickel oxide which is a single compound. The nickel exists as a composite oxide containing nickel, such as a nickel oxide compound or a solid solution formed by combining nickel oxide and alumina and / or magnesia, or a mixture thereof.

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

In the silica-based material of the present embodiment, nickel exists as, for example, nickel aluminate (NiAl ₂ O ₄ ), which is a spinel compound of nickel oxide and alumina, or a solid solution (NiO · MgO) of nickel oxide and magnesia. It is estimated that. Similarly, for the fourth periodic element other than nickel, the oxide forms a solid solution with a spinel compound or basic metal oxide with alumina, which acts to stabilize the silica-alumina crosslinked structure. It is thought that the stability of the product has increased.

Silica based material according to the present embodiment is not limited to the specific surface area, especially when used as a carrier is preferably from 20 to 500 m ² / g, more preferably 50 to 400 m ² / g, more preferably 50 -350 m < ² > / g. When using a silica-based material as a support, the specific surface area of the silica-based material is 20 m ² / g from the viewpoint of easy support of a support component such as a noble metal and from the viewpoint of catalytic activity when the support is used as a catalyst. The above is preferable. From the viewpoint of mechanical strength and water resistance, the specific surface area of the silica-based material is preferably 500 m ² / g or less.

  When a silica-based material is used as a catalyst carrier, the pore diameter is preferably 3 to 50 nm, more preferably 3 to 30 nm, and still more preferably 3 to 10 nm. When the catalyst is used in a liquid phase reaction, the pore diameter should be 3 nm or more from the viewpoint of maintaining a high reaction activity without increasing the diffusion resistance in the pores so as not to limit the diffusion process of the reaction substrate. preferable. On the other hand, the thickness is preferably 50 nm or less from the viewpoint of difficulty in cracking the catalyst and difficulty in peeling off the supported components such as noble metals.

  The pore volume of the silica-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 support characteristics. The pores in the silica-based material are necessary for supporting the supporting component. From the viewpoint of mechanical strength and water resistance, the silica-based material of the present embodiment preferably has a specific surface area, pore diameter, and pore volume within the above ranges. Here, the specific surface area, the pore diameter, and the pore volume of the silica-based material are measured according to a method described later.

  The silica-based material composed of a composite oxide containing silicon, aluminum, the fourth periodic element, and the basic element contains 42 silicon relative to the total molar amount of silicon, aluminum, the fourth periodic element, and the basic element. -90 mol%, aluminum is included in the range of 3-38 mol%, the fourth periodic element is included in the range of 0.5-20 mol%, and the basic element is included in the range of 2-38 mol%. When the amounts of silicon, aluminum, the fourth periodic element and the basic element are within the above ranges, silicon, aluminum, the fourth periodic element, the basic element and the oxygen atom form a specific stable bond structure with each other, The bond structure is easily formed in a state of being uniformly dispersed in the silica-based material. It is preferable to contain 70 to 90 mol% of silicon, 5 to 30 mol% of aluminum, 0.75 to 15 mol% of the fourth periodic element, and 2 to 30 mol% of the basic element, and 75 to 90 mol% of silicon. More preferably, aluminum is contained in an amount of 5 to 15 mol%, the fourth periodic element is contained in an amount of 1 to 10 mol%, and a basic element is contained in an amount of 2 to 15 mol%. In particular, when the composition ratio of the fourth periodic element is set to 0.75 mol% or more and each component is uniformly dispersed throughout the material, there are few portions where the fourth periodic element does not exist in the structure, and repetitive acids and / or Alternatively, a silica-based material that exhibits resistance even when exposed to a base (high acid resistance and basicity) can be obtained. From the viewpoint of obtaining a silica-based material having high mechanical strength and a large specific surface area, the fourth periodic element is preferably 10 mol% or less and the basic element is preferably 30 mol% or less. The composition ratio of silicon and aluminum is set in a preferable range from the viewpoint of acid resistance, basicity, and water resistance of the silica-based material. The composition ratio of silicon to aluminum is preferably (silicon / aluminum) = 2-4. When (silicon / aluminum) is smaller than the above range, acid resistance and basicity tend to be low. When (silicon / aluminum) is larger than the above range, the water resistance tends to be low.

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

  In the present embodiment, there is a suitable range for the composition ratio between the fourth periodic element and aluminum or a basic element. The composition ratio of the fourth periodic element to aluminum (fourth periodic element / aluminum) is preferably 0.02 to 2.0, more preferably 0.05 to 1.75, and still more preferably 0.1 on a molar basis. ~ 1.2. The composition ratio of the fourth periodic element to the basic element (fourth periodic element / basic element) is preferably 0.02 to 2.0, more preferably 0.05 to 1.75 on a molar basis. More preferably, it is 0.1-1.2. When the composition ratio of the fourth periodic element and aluminum or the basic element is within the above range, the effect of improving the elution of aluminum and the structural change of the silica-based material tends to increase. This is presumably because the fourth periodic element, aluminum, and the basic element form a specific composite oxide within this range to form a stable bond structure. That is, if the ratio of the fourth periodic element to the basic element or aluminum is too low in the silica-based material, a preferable structure is formed locally, but is formed with a sufficient density over the entire silica-based material. Not necessarily. On the other hand, when the above composition ratio, particularly (fourth periodic element / aluminum) = 0.05 to 1.75, (fourth periodic element / basic element) = 0.05 to 1.75 is satisfied, It is believed that a preferred structure can exist to the extent that it can contribute to the stabilization of the overall material.

  When the fourth periodic element is nickel and the basic element is magnesium, the silica-based material made of a composite oxide containing silicon, aluminum, nickel, and magnesium has acid resistance and basicity, mechanical strength, and water resistance. From the viewpoint of safety, preferably, silicon is 42 to 90 mol%, aluminum is 3 to 38 mol%, nickel is 0.5 to 20 mol%, based on the total molar amount of silicon, aluminum, nickel and magnesium. Magnesium is contained in the range of 2 to 38 mol%. More preferably, silicon is 70-90 mol%, aluminum is 5-30 mol%, nickel is 0.75-15 mol%, magnesium is 2-30 mol%, more preferably, silicon is 75-90 mol%, It contains 5 to 15 mol% aluminum, 1 to 10 mol% nickel, and 2 to 15 mol% magnesium. When the elemental composition of silicon, aluminum, nickel and magnesium is within the above range, silicon, aluminum, nickel and magnesium can easily form a specific stable bond structure. In particular, in the case of a more preferable composition ratio, even if it is assumed that the above-described stable bonding structure is uniformly dispersed in the silica-based material, the existing density is sufficient to contribute to the stabilization of the entire silica-based material. Is expected to be formed. As a result, silica-based materials tend to exhibit good acid resistance, basicity and mechanical strength that can withstand repeated use.

  The solid form of the silica-based material of the present embodiment is not particularly limited as long as predetermined physical properties can be obtained.

  The dispersion state of the fourth periodic element in the silica-based material of the present embodiment is not particularly limited, but it is preferable that the fourth periodic element is uniformly distributed in the entire material from the viewpoint of stabilizing the structure of the entire silica-based material. Specifically, the cross-section of the silica material is observed and measured by an electron probe microanalysis (EPMA), and it is preferable that the fourth periodic element is present at almost the same concentration at any observation location. . In such a dispersed state, there exists a specific stable bond structure formed by silicon, aluminum, the fourth periodic element and the basic element to the extent that it can contribute to the stabilization of the whole material, and it is repeated over a long period of time. Even if used, it tends to maintain acid resistance and basicity. Here, “substantially the same concentration” means a state where the distribution range of measured values is within 10%.

  The substantial thickness or particle diameter of the silica-based material may be various sizes on the order of μm to cm, and the shape is not particularly limited. Specific examples of the shape of the silica-based material include a spherical shape, an elliptical shape, a cylindrical shape, a tablet shape, a hollow cylindrical shape, a plate shape, a rod shape, a sheet shape, and a honeycomb shape. When used as a catalyst or a catalyst carrier, the shape of the silica-based material of the present embodiment can be appropriately changed depending on the reaction type used. For example, when a silica-based material is used for the fixed bed reaction, a hollow cylindrical shape or a honeycomb shape with a small pressure loss is preferable, and a spherical shape is generally preferable under liquid phase slurry suspension conditions. In particular, when a silica-based material is used as a carrier for a catalyst used in a fluidized bed reaction, the shape is preferably a spherical particle, and the particle size is preferably an average particle size of 1 to 200 μm, more preferably It is 10-200 micrometers, More preferably, it is 30-150 micrometers. By using a silica-based material as such particles, the excellent effects of the present invention can be more effectively and reliably extracted. The average particle diameter of the silica-based material is measured according to the method described later.

  A silica-based material made of a composite oxide containing silicon, aluminum, the fourth periodic element, and the basic element has higher water resistance than silica and higher acid resistance than alumina. In addition, the silica-based material has excellent physical properties such as higher mechanical strength than silica. In addition, the silica-based material has extremely high chemical stability compared to silica-alumina or silica-alumina-magnesia. For example, in the pH swing condition that is repeatedly exposed to an acid or a base, a part of silicon and aluminum is present. Structural changes such as expansion of pore diameter and reduction of specific surface area due to dissolution and precipitation are suppressed.

  Next, the manufacturing method of the silica type material of this embodiment which has the above compositions is demonstrated.

The method for producing a silica-based material comprising a composite oxide containing silicon, aluminum, the fourth periodic element and the basic element is not particularly limited. For example, silica is produced by the following methods (1) to (6). And a step of obtaining a composition comprising an aluminum compound, a compound of a fourth periodic element, and a compound of a basic element, a step of drying the composition as necessary to obtain a dried product, and the dried product or the above composition And baking the product under conditions described later.
(1) A commercially available silica-alumina composition is reacted with a compound of a fourth periodic element and a compound of a basic element.
(2) A silica-alumina gel is formed in advance, and a compound of a fourth periodic element and a compound of a basic element are added to the gel and reacted.
(3) The silica sol is reacted with an aluminum compound, a fourth periodic element compound, and a basic element compound.
(4) A silica sol is reacted with an aluminum compound insoluble in water, a compound of a fourth periodic element insoluble in water, and a compound of a basic element insoluble in water.
(5) The silica gel is reacted with an aqueous solution of a water-soluble aluminum compound, a water-soluble fourth periodic element compound, and a water-soluble basic element compound.
(6) Solid phase reaction of silica gel with an aluminum compound, a fourth periodic element compound, and a basic element compound.

  Below, the preparation method of the silica-type material using the method of said (1)-(6) is demonstrated in detail.

  In the method (1), a commercially available silica-alumina composition is mixed with a compound containing a fourth periodic element and a compound containing a basic element to obtain a slurry. The silica-based material can be prepared by drying the slurry and firing it under the conditions described later. As the compound containing the fourth periodic element and the compound containing the basic element, water-soluble compounds represented by chlorides, carbonates, nitrates and acetates are preferable. However, water-insoluble compounds such as hydroxides and oxides can also be used.

  In the methods (2) to (6), for example, silica sol, water glass, or silica gel can be used as the silica source. As long as it has an uncrosslinked Si site | part which reacts with Al as silica gel, there is no restriction | limiting in particular about the length of a Si-O chain | strand. As the aluminum compound, water-soluble compounds represented by sodium aluminate, aluminum chloride hexahydrate, aluminum perchlorate hexahydrate, aluminum sulfate, aluminum nitrate nonahydrate, and aluminum diacetate are preferable. However, it may be a water-insoluble compound such as aluminum hydroxide or aluminum oxide, and any compound that reacts with silica sol or uncrosslinked Si in silica gel can be used for preparing a silica-based material. Examples of the compound containing the fourth periodic element or basic element include oxides, hydroxides, chlorides, carbonates, sulfates, nitrates, and acetates of these elements.

In the case of the method (2) using silica-alumina gel, sulfuric acid is previously added to water glass to prepare a silica hydrogel having a pH of 8 to 10.5, and Al ₂ (SO ₄ ) ₃ having a pH of 2 or lower. A silica-alumina hydrogel is prepared by adding the solution and further adding sodium aluminate having a pH of 5 to 5.5. Next, the moisture contained in the hydrogel is adjusted to 10 to 40% by spray drying or the like, and a compound of a fourth periodic element and a compound of a basic element are added thereto to obtain a composition. And after drying the composition, a silica-type material can be obtained by baking on the conditions mentioned later.

  In the case of the methods (3) and (4) using silica sol as a starting material, an aluminum compound, a fourth periodic element compound and a basic element compound are mixed in the silica sol, and the silica sol, aluminum compound and fourth period are mixed. A mixture sol which is a composition containing a compound of an element and a compound of a basic element is obtained, then the mixture sol is dried to obtain a gel, and the gel is fired at the temperature, time and atmospheric conditions described below. Alternatively, an alkaline aqueous solution is added to the mixture sol to coprecipitate silica, an aluminum compound, a fourth periodic element compound, and a basic element compound, and the coprecipitate is dried and then fired under the conditions described below. In addition, a silica-based material having a desired particle size is obtained by passing the mixture sol as it is using a spray dryer and pulverizing the mixture sol, or drying the mixture sol and granulating the gel. It is also possible.

  In particular, in the case of the method (4), silica sol, an aluminum compound insoluble in water, a compound of a fourth periodic element insoluble in water, and a compound of a basic element insoluble in water are reacted. The fourth periodic element compound and the basic element compound may be pulverized to a predetermined particle diameter in advance or preliminarily or coarsely pulverized. Conditions obtained by mixing the aluminum compound insoluble in water, the compound of the fourth periodic element insoluble in water, the compound of the basic element insoluble in water, and the silica sol, and then drying the reaction product, and further described below Bake with. In addition, the composition of silica-alumina-fourth periodic element-basic element after firing without preliminarily pulverizing or preliminarily coarsely pulverizing the aluminum compound, the fourth periodic element compound, and the basic element compound. May be pulverized to a predetermined particle size.

  In the case of the method (5) using silica gel as a starting material, the silica gel is reacted with an aqueous solution of a water-soluble aluminum compound, a water-soluble fourth-period element compound, and a water-soluble basic element compound. May be previously pulverized to a predetermined particle size, or may be preliminarily coarsely pulverized. In the case of the method (5), after obtaining a slurry in which silica gel is mixed with an aqueous solution of a water-soluble aluminum compound, an aqueous solution of a water-soluble fourth periodic element compound, and an aqueous solution of a water-soluble basic element compound, The slurry is dried and further baked for 1 to 48 hours under the conditions described below. Alternatively, the composition of calcined silica-alumina-fourth periodic element-basic element may be pulverized to a predetermined particle size without preliminarily pulverizing or preliminarily coarsely pulverizing the silica gel.

  Similarly, the method (6) using silica gel as a starting material is a method in which a silica gel is reacted with an aluminum compound, a compound of a fourth periodic element and a compound of a basic element to obtain a reactant which is a composition. is there. In this case, Al is reacted with uncrosslinked Si in a solid state. Silica gel, an aluminum compound, a fourth periodic element compound, and a basic element compound may be preliminarily pulverized to a predetermined particle diameter, or may be preliminarily coarsely pulverized. At this time, each substance may be pulverized alone, or both may be mixed and pulverized. The reaction product obtained by the solid phase reaction is dried if necessary and then further baked. Firing is preferably performed under the temperature, time, and atmospheric conditions described below. Silica gel, aluminum compound, 4th period element compound, basic element compound are not pulverized or preliminarily coarsely pulverized, and the reaction product obtained by the reaction is pulverized to a desired particle size. Also good.

  As another method for preparing a composition containing silica, an aluminum compound, a compound of a fourth periodic element, and a compound of a basic element, a silica-based material composed of a composite oxide containing silicon, aluminum, and the fourth periodic element, A method of adsorbing a basic element component can also be used. In this case, for example, a method using an immersion method such as adding the silica-based material in a solution in which the compound of the basic element is dissolved and performing a drying treatment, or a method using a basic element compound corresponding to the pore volume of the silica A method using an impregnation method in which the material is soaked and dried is applicable.

  A method of adsorbing a component containing a fourth periodic element to a silica-based material made of a composite oxide containing silicon, aluminum, and a basic element can also be used. In this case, for example, a method using an immersion method such as adding a silica-based material to a solution in which a compound containing a fourth periodic element is dissolved and performing a drying treatment, or a fourth periodic element corresponding to the pore volume is included. A method using an impregnation method in which a compound is soaked in the silica-based material and subjected to a drying treatment can be applied. However, a method for adsorbing a component containing a basic element or a component containing a fourth periodic element later is to highly disperse a component containing a basic element or a component containing a fourth periodic element in a silica-based material. Care must be taken such as performing the liquid drying process under mild conditions.

  To the slurry containing various raw materials obtained as described above, an inorganic substance or an organic substance may be added in order to control the slurry properties, finely adjust the properties such as the pore structure of the product and the obtained physical properties. Specific examples of inorganic substances 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 In addition to water-soluble compounds such as ammonia and ammonium nitrate, clay minerals that are dispersed in water to form a suspension can be mentioned. Specific examples of organic substances include polymers such as polyethylene glycol, methyl cellulose, polyvinyl alcohol, polyacrylic acid, and polyacrylamide.

  There are various effects obtained by adding an inorganic substance and an organic substance. Mainly, the silica-based material is formed into a spherical shape, and the pore diameter and the pore volume are controlled. More specifically, the liquid quality of the mixed slurry is an important factor for obtaining a spherical silica-based material. By adding an inorganic substance or an organic substance and adjusting the viscosity and solid content concentration of the slurry, it can be changed to a liquid quality in which a spherical silica-based material can be easily obtained. In order to control the pore diameter and pore volume, an optimal organic compound that remains in the silica-based material during the molding step and can be removed by firing and washing operations after the molding may be selected.

  Next, a composition such as a slurry, gel, or reactant containing the above-described various raw materials and additives is dried. Although it does not specifically limit as a method to dry, Spray drying is preferable from a viewpoint of controlling the particle diameter of a silica type material. In this case, as a method for forming the mixed slurry into droplets, a method using a known spraying device such as a rotating disk method, a two-fluid nozzle method, a pressure nozzle method, or the like can be given.

  The liquid to be sprayed (slurry) needs to be used in a well-mixed state. When the mixed state is poor, the performance of the silica-based material is affected, for example, the durability is lowered due to the uneven distribution of the composition. In particular, when each raw material is prepared, the viscosity of the slurry may increase and the gelation (condensation of the colloid) may occur, and there is a concern that uneven particles may be formed. Therefore, in addition to considering each material gradually mixed under stirring, etc., a mixed slurry is prepared by controlling the mixture in the metastable region of silica sol near pH 2, for example, by adding acid or alkali. May be preferred.

  The liquid to be sprayed preferably has a predetermined range of viscosity and solid content concentration. When the viscosity and the solid content concentration are lower than the predetermined range, the porous body obtained by spray drying does not become a true sphere, and there is a tendency that many depressed spherical porous bodies are generated. Moreover, when they are higher than the predetermined range, the dispersibility between the porous bodies may be adversely affected, and depending on the properties, droplets cannot be stably formed. Therefore, the viscosity of the liquid to be sprayed is preferably in the range of 5 to 10000 cp at the spraying temperature as long as spraying is possible. Further, from the viewpoint of the shape, a tendency that a higher viscosity is preferable in a sprayable range is observed, and the viscosity is more preferably in the range of 10 to 1000 cp from the balance with operability. Moreover, it is preferable from a viewpoint of a shape and a particle diameter that solid content concentration exists in the range of 10-50 mass%. In addition, as a standard of spray drying conditions, it is preferable that the hot air temperature at the entrance of the drying tower of the spray dryer is in the range of 200 to 280 ° C and the outlet temperature of the drying tower is in the range of 110 to 140 ° C.

  Next, a solid substance is obtained by baking the composition after further drying through the methods (1) to (5) or the reaction product obtained by the method (6). The firing temperature is generally in the range of 200 to 800 ° C. When the composition is fired at 800 ° C. or lower, the specific surface area of the silica-based material can be increased, and when the composition is fired at 200 ° C. or higher, dehydration and condensation reaction between gels becomes more sufficient, and the pore volume. Can be further suppressed from becoming large and bulky. A firing temperature in the range of 300 to 600 ° C. is preferable from the viewpoint of balance of physical properties and operability. However, when the composition contains a nitrate, it is preferably fired at a temperature higher than the decomposition temperature of the nitrate. The physical properties of the silica-based material such as the porosity can be changed by the firing temperature and the temperature raising rate, and an appropriate firing temperature and temperature raising condition may be selected in accordance with the target physical properties. That is, by setting the firing temperature to an appropriate condition, the durability of the composite oxide can be maintained well, and a decrease in pore volume can be suppressed. Further, it is preferable to gradually increase the temperature using a program temperature increase or the like as the temperature increase condition. As a result, the gasification and combustion of inorganic and organic substances become severe, and accordingly, it becomes easy to be exposed to a high temperature state higher than the setting, and cracking is likely to occur, and as a result, crushing is prevented as a result. be able to.

  The firing atmosphere is not particularly limited, but firing in air or nitrogen is common. Moreover, although baking time can be determined according to the specific surface area of the silica-type material after baking, it is generally 1 to 48 hours. Also depending on these firing conditions, the physical properties of the silica-based material such as porosity can be changed, and each firing condition may be selected according to the target physical properties.

  Although the solid material obtained through the firing step as described above may be used as the silica-based material of the present embodiment, it is preferable that the solid material is further subjected to hydrothermal treatment. Surprisingly, through the hydrothermal treatment process, the pore diameter of most of the pores has a uniform pore structure that exists in a narrow range of 3 to 5 nm, and the specific surface area and mechanical strength are also large. A silica-based material can be obtained.

  “Hydrothermal treatment” as used herein is an operation of immersing the solid in water or a solution containing water and holding the solid for a certain period of time while heating. As a result, the present inventors presume that sufficient water is present in the pores of the solid matter, mass transfer occurs using the water as a medium, and the reconstruction of the pores proceeds. Therefore, from the viewpoint of promoting rapid mass transfer, the hydrothermal treatment temperature is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, still more preferably 80 ° C. or higher, and particularly preferably 90 ° C. or higher. The temperature of the hydrothermal treatment may be a high temperature of 100 ° C. or higher, but in that case, a pressure device is required so that moisture does not evaporate excessively. Even if the temperature of the hydrothermal treatment is a low temperature of less than 60 ° C., it is possible to obtain the silica-based material of the present embodiment, but the treatment time tends to be long. Further, as is clear from the above, hydrothermal treatment at a temperature equal to or higher than the boiling point of the solution under pressure is advantageous in that the effect is manifested in a short time. However, from the viewpoint of ease of operation, it is preferable to perform hydrothermal treatment at a higher temperature, usually in the range below the boiling point. The hydrothermal treatment time varies depending on conditions such as the type of metal constituting the solid, the amount of metal, the metal composition ratio, and the treatment temperature, but preferably 1 minute to 5 hours, more preferably 5 minutes to 3 hours, and even more preferably. Within 5 minutes to 1 hour.

  The reason why the pore distribution is narrowed by hydrothermal treatment is not clear, and detailed studies are insufficient. At present, the present inventors presume the reason as follows. That is, by subjecting the above-described composition containing silica to molding, drying, firing, and the like, a crosslinking reaction between particles in the composition proceeds, and first a structure having a pore distribution of 2 to 10 nm ( Solids) are formed. In the drying process and the baking process, dehydration reaction and cross-linking reaction between gels by heating in a gas atmosphere proceed, but since these reactions are solid phase reactions, the obtained silica-based material is not necessarily uniform. There is no pore distribution. However, it is speculated that by subjecting the solid matter to further hydrothermal treatment, the reaction by the hydrolysis and re-crosslinking reaction of the solid matter proceeds and the rearrangement of the structure occurs. In addition, taking into account that the obtained pore volume is close to the porosity due to the close-packing of particles, the hydrothermal reaction by hydrothermal treatment changes to a thermodynamically stable packed structure, resulting in a pore diameter of 3 to 5 nm. It is presumed that a silica-based material having a pore distribution in a narrow range is obtained.

  Next, another preferable method for producing the silica-based material of the present embodiment will be described. This production method comprises a composition containing silica, an aluminum compound, and a compound of at least one basic element selected from the group consisting of alkali metal elements, alkaline earth metal elements, and rare earth elements, or a composition thereof A step (first step) of baking a dried product to obtain a solid, and the solid, and at least one fourth periodic element selected from the group consisting of iron, cobalt, nickel and zinc A step of neutralizing a mixture of the soluble metal salt with an acidic aqueous solution and precipitating a fourth periodic element on the solid (second step); and a step of hydrothermally treating the solid on which the fourth periodic element is precipitated ( (3rd process) and the process (4th process) which heat-processes the solid substance which passed through the process of hydrothermally treating.

  In the first step, a slurry further containing silica, an aluminum compound and a compound of the basic element is prepared, dried, and then fired to obtain a solid. What is necessary is just to mix | blend a slurry by the method similar to the above-mentioned embodiment except not containing the compound of a 4th period element. Moreover, the firing temperature should just be the same as the firing temperature in the above-mentioned 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, a component containing the fourth periodic element is added to the solid matter. Precipitate. Under the present circumstances, the solid substance mixed with acidic aqueous solution may be in the state of the water slurry which disperse | distributed it to water. At this stage, due to the neutralization reaction between the ions of the fourth periodic element in the aqueous solution and the base, for example, in the state of the hydroxide of the fourth periodic element, the component containing the fourth periodic element precipitates on the solid and is immobilized. Is done.

  Examples of the base used when neutralizing in the second step include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and ammonia. Further, an alkali metal element (Li, Na, K, Rb, Cs), an alkaline earth metal element (Be, Mg, Ca, Sr, Ba) and a rare earth element (La, A component containing one or more basic elements selected from the group consisting of Ce and Pr) may be included. Examples of the component containing such a basic element include potassium hydroxide, rubidium hydroxide, magnesium oxide, strontium oxide, lanthanum oxide, and cerium oxide.

In the second step, for example, an acidic aqueous solution of a soluble metal salt containing a fourth periodic element and a solid are mixed and neutralized with a base while stirring, and the components of the fourth periodic element are then mixed on the solid. Precipitate by precipitation. When precipitating the component of the fourth periodic element, conditions such as the concentration of the acidic aqueous solution containing the fourth periodic element, the base, the pH of the aqueous solution, and the temperature may be selected as appropriate.
The concentration of the fourth periodic element in the acidic aqueous solution (when two or more fourth periodic elements are contained, the concentration of each fourth periodic element) is preferably 0.0001 to 1.0 mol / L, more preferably The range is 0.001 to 0.5 mol / L, more preferably 0.005 to 0.2 mol / L.

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

  The time required for precipitating the component containing the fourth periodic element varies depending on conditions such as the content of alumina, the fourth periodic element and the basic element, and the temperature, but preferably 1 minute to 5 hours, more preferably 5 The range is from minutes to 3 hours, more preferably from 5 minutes to 1 hour.

  Next, in a 3rd process, the solid substance in which the component containing a 4th period element precipitated is hydrothermally processed, and a mixture is obtained. By subjecting the solid to hydrothermal treatment, the hydrolysis and re-crosslinking reaction of the silica gel proceed, and the rearrangement of the structure occurs, and at the same time, the compound of the fourth periodic element proceeds.

  The hydrothermal treatment may be the same as that in the above embodiment, and the neutralization liquid used in the second step may be heated as it is to perform the hydrothermal treatment. The hydrothermal treatment is preferably carried out at a temperature range of 60 ° C. or higher for 1 to 48 hours. Hydrothermal treatment is possible even at a low temperature of less than 60 ° C., but the treatment time tends to be longer. From the viewpoint of operability, treatment time, etc., the hydrothermal treatment is preferably performed at 60 to 90 ° C.

Furthermore, after the solid contained in the mixture obtained in the third step is washed with water and dried as necessary, heat treatment is performed in the fourth step. Thus, the silica-based material of this embodiment can be obtained.
The heat treatment temperature of the solid in the fourth step is preferably 40 to 900 ° C, more preferably 80 to 800 ° C, still more preferably 200 to 700 ° C, and particularly preferably 300 to 600 ° C.

  Heat treatment can be performed in air (or in the air), in oxidizing atmospheres (oxygen, ozone, nitrogen oxides, carbon dioxide, hydrogen peroxide, hypochlorous acid, inorganic / organic peroxides, etc.) Examples include an active gas atmosphere (helium, argon, nitrogen, etc.). The heat treatment time may be appropriately selected according to the heat treatment temperature and the amount of solid matter.

  The silica-based material of the present embodiment can be suitably used for pigments, fillers, abrasives, cosmetic bases, agricultural chemical carriers, catalyst carriers, adsorbents, film constituent materials, and the like.

  Each application will be described below with specific examples. First, pigments are required to be fine powders that are insoluble in water, oil, organic solvents, etc. and have high mechanical strength. The spherical particles made of the silica-based material of the present embodiment have high mechanical strength and are excellent in water resistance, oil resistance, and organic solvent resistance, and therefore can be preferably used as a pigment. As the pigment, small particles are generally used, and the average particle diameter is preferably 10 μm or less, more preferably 5 μm or less.

Conventionally, the synthetic silica filler used as a filler has a bulk density as small as 0.04 to 0.2 g / cm ³ , so that it is inconvenient to transport and handle. Since the silica-based material of the present embodiment can have a bulk density as high as 0.9 to 1.2 g / cm ³ , it solves the drawbacks of the conventional synthetic silica filler. In addition, since this silica-based material has high mechanical strength, it is useful as a reinforcing agent for increasing the strength of the polymer. Further, the silica-based material is useful as a matting agent, a vinyl chloride paste, an epoxy resin, a polyester resin prepolymer viscosity modifier.

  The silica-based material of the present embodiment preferably has an abrasion resistance of 1.0% by mass / 15 hours or less measured in accordance with a method described later, and thereby becomes useful as an abrasive. As an abrasive, shape and bulk density geometric properties are important. Compared to silica sand, float stone, diatomaceous earth, and the like, the silica-based material of this embodiment has a high mechanical strength, a spherical shape and a high bulk density, and thus has excellent properties as an abrasive. Moreover, although it is necessary to arrange | equalize a particle size with the object to grind | polish, since mechanical strength is strong, even if it classifies, damage etc. do not occur easily and the spherical particle thing of the particle size according to grinding | polishing object can be obtained. The average particle diameter as an abrasive can take various ranges depending on the object to be polished, and is generally preferably 1 to 300 μm, and those having an optimum particle diameter are used depending on the application. The silica-based material of this embodiment is useful for polishing glass, wood, rust removal, dirt removal, finishing of bones such as metal, wood, ivory, art crafts, ceramics, soft metal glossing, etc. It can also be used as an abrasive.

  As a cosmetic base, it is desired that the cosmetic base has high stability and good usability. The silica-based material of the present embodiment is excellent in water resistance, oil resistance, and organic solvent resistance, so it has high stability to the human body, and when it is spherical, it gives a smooth feel and has high usability. Useful as.

  The particles used as an agrochemical carrier preferably have a uniform particle size distribution, and preferably have particles of 10 μm or less removed by a treatment such as classification. When particles of 10 μm or less are removed, the physical properties of the powder, such as powdering properties, dispersibility, scattering properties, and stability over time, are remarkably improved.

  The silica-based material of the present embodiment can control the pore diameter in the range of 3 to 5 nm and has a narrow pore distribution, so that it is effectively used as an ink absorbing material for inkjet printer paper. In addition, since the silica-based material of the present embodiment has a small pore volume and a high bulk density, the disadvantages of the conventional synthetic silica filler are eliminated, and the mechanical strength is also high. Useful as a reinforcing agent to increase strength. Furthermore, the silica-based material of the present embodiment is also useful as a matting agent, vinyl chloride paste, epoxy resin, polyester resin prepolymer viscosity modifier.

  The silica-based material can also support various metal ions and can be used as a catalyst carrier. When used as a catalyst carrier, a catalytically active component is supported on this silica-based material, and the catalytically active component is appropriately selected depending on the target reaction. 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, rhenium, osmium, iridium, platinum, and gold. Among the noble metal components, at least one selected from the group consisting of ruthenium, palladium, platinum, and gold is more preferable. These noble metal components are used alone or in combination of two or more. The chemical state of the noble metal component may be any of a simple metal, an oxide, a hydroxide, a composite compound containing two or more kinds of noble metal elements, or a mixture thereof, but a preferable chemical state is a simple metal or a metal oxide. .

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

  When the average particle diameter of the noble metal particles is within the above range, a specific active species structure is formed and the reaction activity tends to be 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 an image observed with a transmission electron microscope, a black contrast portion is a composite particle, and all the diameters of each particle in the image are measured and calculated as the number average.

  The noble metal carrier may contain a second component element in addition to the noble metal component. Examples of the second component element include at least one metal selected from the group consisting of Group 4 to 16 elements of the 4th, 5th, and 6th periods of the periodic table. Specific examples of the second component element include titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, zirconium, niobium, molybdenum, cadmium, indium, tin, antimony, tellurium, hafnium, tungsten, Examples include iridium, mercury, thallium, lead, and bismuth. Furthermore, you may contain an alkali metal, alkaline-earth metal, and rare earth metal as a 2nd component element.

  These metal elements are used alone or in combination of two or more. The chemical state of these metal elements may be any of simple metals, oxides, hydroxides, composites containing two or more metal elements, or a mixture thereof. Preferred chemical states include simple metals or metal oxides. It is a thing.

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

  Supporting at least one metal element selected from the group consisting of Group 4 to 16 elements of the 4th period, 5th period and 6th period of the periodic table and / or a compound of the metal element is supported The total amount is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, based on the mass of the noble metal support, and when alkali metal, alkaline earth metal, or rare earth metal is supported. The total amount thereof is preferably 0.5 to 30% by mass, more preferably 1 to 15% by mass, based on the mass of the noble metal support.

The specific surface area of the noble metal support of the present embodiment is preferably 20 to 500 m ² / g, more preferably, as measured by the BET nitrogen adsorption method, from the viewpoint of improving reaction activity and difficulty in detaching the active component. The range is 50 to 400 m ² / g, more preferably 100 to 350 m ² / g.

  The pore structure of the noble metal support of the present embodiment is one of the extremely important physical properties from the viewpoint of the support characteristics of the noble metal component, long-term stability including peeling, and reaction characteristics when used as a catalyst. The pore diameter is a physical property value that serves as an index for developing these characteristics. If the pore diameter is smaller than 3 nm, the release property of the supported noble metal component tends to be good, but when used as a catalyst in a liquid phase reaction or the like, the diffusion resistance in the pores of the reaction substrate increases, The diffusion process tends to be rate limiting and the reaction activity tends to decrease. 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 difficulty of cracking the supported material and the difficulty of peeling the supported noble metal particles. Therefore, the pore diameter of the noble metal support is preferably 3 nm to 50 nm, more preferably 3 nm to 30 nm, and still more preferably 3 nm to 10 nm. The pore volume is preferably in the range of 0.1 to 1.0 mL / g, more preferably 0.1 to 0.5 mL / g, and still more preferably 0.1 to 0. The range is 3 mL / g. The noble metal support of the present embodiment preferably has a pore diameter and a pore volume that satisfy the above ranges.

The method for supporting the noble metal component on the silica-based material is not particularly limited as long as the above-mentioned support can be obtained, and a generally used metal support manufacturing method such as an impregnation method (adsorption method, pore filling method). , Evaporating and drying methods, spraying methods), precipitation methods (coprecipitation methods, deposition methods, kneading methods), ion exchange methods, vapor deposition methods, and the like can be applied. Each metal component other than the noble metal may be added at the time of preparing the noble metal support, but when the noble metal support is used as a catalyst, it can be added to a reaction system using the catalyst.
When the second component element is contained in addition to the noble 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 may be previously contained in the support. Good. Note that the structure of the second component element in the noble metal support is not particularly limited, and may form an alloy or intermetallic compound with the noble metal particles, or may be supported on the carrier separately from the noble metal particles. May be. Alkali metal compounds and alkaline earth metal compounds may also be previously present at the time of preparation of the noble metal support, or can be added to the reaction system during preparation of the noble metal support. As the metal raw material used for the catalyst preparation, compounds such as the above-mentioned metal inorganic compounds and organometallic compounds are used, but preferably metal halide, metal oxide, metal hydroxide, metal nitrate, metal sulfate, metal Acetates, metal phosphates, metal carbonyls, metal acetylacetonates, metal porphyrins, metal phthalocyanines.

[Preparation method of a noble metal support containing a second component element in addition to a noble metal component]
A preparation method in the case of containing a second component element in addition to the noble metal component in the noble metal support will be described by taking a precipitation method as an example. For example, as a first step, the second component and the noble metal component are precipitated on the silica-based material by neutralizing an acidic aqueous solution of a soluble metal salt containing the second component and the noble metal, thereby obtaining a precursor of the noble metal support. . At this stage, the second component and the noble metal ion in the aqueous solution are precipitated and immobilized on the silica-based material by the neutralization reaction of the second component and the noble metal ion with the base. Next, as a second step, the noble metal support can be obtained by subjecting the precursor of the noble metal support obtained in the first step to water washing and drying as necessary, followed by heat treatment.

  Examples of the soluble metal salt containing the second component element used for the preparation of the noble metal support include nitrates, acetates and chlorides of the second component element. Examples of soluble metal salts containing a noble metal component include palladium chloride and palladium acetate when selecting palladium as the noble metal, ruthenium chloride and ruthenium nitrate when ruthenium, and gold chloride when gold. When acid, sodium gold chloride, potassium dicyanoaurate, diethylamine gold trichloride and gold cyanide are silver, silver chloride and silver nitrate can be mentioned.

  Examples of the base used for preparing the noble metal support include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia and the like. In addition, the support may be one or more selected from alkali metals (Li, Na, K, Rb, Cs), alkaline earth metals (Be, Mg, Ca, Sr, Ba) and rare earth metals (La, Ce, Pr). The basic metal component may be contained.

  In the first step, an acidic aqueous solution of a soluble metal salt containing a second component element and a noble metal and a silica-based material are mixed and neutralized with a base while stirring, and the second component element and the noble metal are mixed on the silica-based material. Precipitate the components. When precipitating the second component element and the noble metal component, conditions such as the concentration of the aqueous solution containing the second component element and the noble metal component, the base, the pH of the aqueous solution, and the temperature may be selected as appropriate.

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

  What is necessary is just to adjust pH of aqueous solution with the said base so that it may become normally in the range of 5-10, preferably 6-8. 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 for precipitating the second component element and the noble metal component is not particularly limited and varies depending on conditions such as the silica-based material type, the loading amount of the second component element and the noble metal, and the ratio, but usually from 1 minute to 5 minutes Time, preferably 5 minutes to 3 hours, more preferably 5 minutes to 1 hour.

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

  The atmosphere for the heat treatment is in the air (or in the air), in an oxidizing atmosphere (oxygen, ozone, nitrogen oxide, carbon dioxide, hydrogen peroxide, hypochlorous acid, inorganic / organic peroxide, etc.) or inert gas Performed in an atmosphere (helium, argon, nitrogen, etc.). The heat treatment time may be appropriately selected according to the heat treatment temperature and the amount of the noble metal support precursor.

  After the second step described above, reduction treatment can be performed in a reducing atmosphere (hydrogen, hydrazine, formalin, formic acid, etc.) as necessary. What is necessary is just to select suitably the temperature and time of a reduction process according to the kind of reducing agent, the kind of noble metal, and the quantity of a noble metal carrier.

  After the above heat treatment or reduction treatment, in the air (or in the air) or in an oxidizing atmosphere (oxygen, ozone, nitrogen oxide, carbon dioxide, hydrogen peroxide, hypochlorous acid, inorganic / organic peroxidation as necessary Or the like. The temperature and time in that case are appropriately selected according to the type of oxidizing agent, the type of noble metal, and the amount of the noble metal support.

[Method for producing compound using noble metal support as catalyst]
The noble metal support of the present embodiment is widely used as a catalyst for chemical synthesis. This noble metal support is, for example, alkane oxidation, alcohol oxidation, aldehyde oxidation, carbonyl oxidation, alkene oxidation, alkene epoxidation, alkene oxidative addition, aldehyde and alcohol oxidative esterification, alcohol Oxidative esterification of glycol, oxidative esterification of glycol with alcohol, alkene hydrogenation, alkyne hydrogenation, phenol hydrogenation, selective hydrogenation reaction of α, β unsaturated ketone, nitro, olefin, carbonyl, It can be used as a hydrogenation reaction of aromatic rings, amination, synthesis of hydrogen peroxide directly from hydrogen and oxygen, oxidation of carbon monoxide, water gas shift reaction, or other chemical synthesis catalyst, NOx reduction catalyst, or photocatalyst.

  Hereinafter, a method for producing a carboxylic acid ester by oxidative esterification reaction in the presence of oxygen from an aldehyde and an alcohol using the noble metal support 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, glyoxal; C3-C10 aliphatic α, β-unsaturated such as acrolein, methacrolein, and crotonaldehyde. Examples include aldehydes; C6-C20 aromatic aldehydes such as benzaldehyde, tolylaldehyde, benzylaldehyde, and phthalaldehyde; and derivatives of these aldehydes. These aldehydes are used alone or as a mixture of two or more. Among them, it is preferable that the aldehyde is at least one selected from the group consisting of acrolein, methacrolein, and a mixture thereof because the noble metal support of the present embodiment can be used more effectively as a catalyst.

  Examples of the alcohol include C1-C10 aliphatic saturated alcohols such as methanol, ethanol, isopropanol, butanol, 2-ethylhexanol and octanol; C5-C10 alicyclic alcohols such as cyclopentanol and cyclohexanol; ethylene glycol, propylene C2-C10 diols such as glycol and butanediol; C3-C10 aliphatic unsaturated alcohols such as allyl alcohol and methallyl alcohol; C6-C20 aromatic alcohols such as benzyl alcohol; 3-alkyl-3-hydroxymethyloxetane and the like And hydroxy oxetane. These alcohols are used alone or as a mixture of two or more. Among them, it is preferable that the alcohol is methanol because the noble metal support of the present embodiment can be used more effectively as a catalyst.

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

  The amount of the catalyst used is not particularly limited, and can be changed greatly depending on the type of reaction raw material, the composition and preparation method of the catalyst, reaction conditions, reaction mode, and the like. When the catalyst is reacted in a slurry state, the catalyst is preferably 1 to 50 mass / volume%, more preferably 3 to 30 mass / volume%, still more preferably 10 to 25 mass / volume, as the solid content concentration in the slurry. % Range.

  The carboxylic acid ester can be produced by any method such as a gas phase reaction, a liquid phase reaction, and an irrigation reaction, either batchwise or continuously.

  The reaction can be carried out without solvent, but can also be carried out using a solvent inert to the reaction components (reaction substrate, reaction product and catalyst) such as hexane, decane, benzene, dioxane.

  The reaction format may be a conventionally known format such as a fixed bed type, a fluidized bed type, and a stirring tank type. For example, when reacting in the liquid phase, any reactor type such as a bubble column reactor, a draft tube reactor, a stirred tank reactor, etc. can be employed.

  The oxygen used in the production of the carboxylic acid ester is in the form of molecular oxygen, that is, oxygen gas itself or a mixed gas obtained by diluting the oxygen gas with a diluent inert to the reaction, such as nitrogen or carbon dioxide. Also good. As the oxygen raw material, air is preferably used from the viewpoints of operability and economy.

  The oxygen partial pressure varies depending on the reaction raw materials such as aldehyde species and alcohol species, the reaction conditions, or the reactor type, but practically, the oxygen partial pressure at the outlet of the reactor is in a range where the concentration is below the lower limit of the explosion range. For example, it is preferable to manage at 20 to 80 kPa. About reaction pressure, the arbitrary wide pressure range from pressure reduction to pressurization may be sufficient, for example, reaction pressure of the range of 0.05-2 Mpa. Further, it is preferable from the viewpoint of safety to set the total pressure (for example, oxygen concentration 8%) so that the oxygen concentration in the gas flowing out from the reactor does not exceed the explosion limit.

  When the production reaction of a carboxylic acid ester is carried out in the liquid phase or the like, an alkali metal or alkaline earth metal compound (eg, oxide, hydroxide, carbonate, carboxylate) is added to the reaction system. It is preferable to maintain pH of 6-9. These alkali metal or alkaline earth metal compounds are used singly or in combination of two or more.

  Although the reaction temperature at the time of manufacturing carboxylic acid ester may be high temperature exceeding 200 degreeC, Preferably it is 30-200 degreeC, More preferably, it is 40-150 degreeC, More preferably, it is 60-120 degreeC. The reaction time is not particularly limited and is not uniquely determined because it varies depending on the set conditions, but is usually 1 to 20 hours.

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

  Although it does not specifically limit as water contained in a liquid phase, For example, soft water, refined industrial water, ion-exchange water etc. can be mentioned. Water having normal water quality may be used, but water containing a large amount of impurities (ions such as Fe, Ca, and Mg) is not preferable. Examples of the aldehyde used in the production of carboxylic acid include C1-C10 aliphatic saturated aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, isobutyraldehyde, glyoxal; C3-C10 aliphatic α, such as acrolein, methacrolein, and crotonaldehyde. β-unsaturated aldehydes: C6-C20 aromatic aldehydes such as benzaldehyde, tolylaldehyde, benzylaldehyde, phthalaldehyde, and derivatives of these aldehydes. Of these, methacrolein and acrolein are preferable. These aldehydes can be used alone or as a mixture of two or more kinds.

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

  Although it is possible to oxidize aldehyde in a mixed liquid phase consisting of aldehyde and water, that is, under solvent-free conditions, a solvent is added to a mixed liquid consisting of aldehyde and water, and a mixed liquid consisting of aldehyde, water and solvent. It does not matter. As the solvent, for example, ketones, nitriles, alcohols, organic acid esters, hydrocarbons, organic acids, amides can be used. Examples of ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of nitriles include acetonitrile and propionitrile. Examples of alcohols include tertiary 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 organic acids include acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, and isovaleric acid. Examples of amides include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylpropionamide, and hexamethylphosphoamide. Further, the solvent may be one type or a mixed solvent of two or more types. When water and solvent are mixed, the mixing ratio can be changed greatly depending on the type of aldehyde that is the reaction raw material, the composition and preparation method of the catalyst, reaction conditions, reaction type, etc. From the viewpoint of producing carboxylic acids from aldehydes with high productivity and high productivity, the amount of the solvent is preferably 8 to 65% by mass, more preferably 8 to 55% by mass with respect to the mass of water. A mixed solution composed of aldehyde and water, or a mixed solution composed of aldehyde, water and solvent is preferably uniform, but may be used in a non-uniform state.

  The amount of the catalyst used can be significantly changed depending on the type of reaction raw material, the composition and preparation method of the catalyst, reaction conditions, reaction type, etc., and is not particularly limited, but when reacting the catalyst in a slurry state, The catalyst concentration in the slurry is preferably 4 to 50 mass / volume%, more preferably 4 to 30 mass / volume%, and still more preferably 10 to 25 mass / volume%. That is, the catalyst is used such that the mass (kg) of the catalyst with respect to the volume (L) of the liquid component falls within the range of preferably 4 to 50%, more preferably 4 to 30%, and still more preferably 10 to 25%.

  The production of the carboxylic acid in the liquid phase may be carried out in either a continuous type or a batch type, but in view of productivity, the continuous type is preferred industrially.

  As an oxygen source for oxidation, oxygen gas itself may be supplied to the reactor, or a mixed gas obtained by diluting oxygen gas with a diluent inert to the reaction, for example, nitrogen, carbon dioxide gas, or the like may be supplied. However, it is preferable to use air as the oxygen source in terms of operability and economy.

  The preferred oxygen partial pressure varies depending on the aldehyde species, solvent species, reaction conditions, reactor type, etc., but practically, the oxygen partial pressure at the reactor outlet is in a range where the concentration is below the lower limit of the explosion range, for example, It is preferable to manage to 20-80 kPa. The reaction pressure can be carried out in any wide pressure range from reduced pressure to increased pressure, but is usually carried out at a pressure of 0.05 to 5 MPa. From the viewpoint of safety, it is preferable to set the total pressure so that the oxygen concentration of the reactor effluent gas does not exceed the explosion limit (8%).

  30-200 degreeC is preferable, the reaction temperature at the time of manufacturing carboxylic acid has more preferable 40-150 degreeC, and 60-120 degreeC is further more preferable. The reaction time is not particularly limited, and is usually 1 to 20 hours.

  In addition, determination of content of constituent elements (Si, Al, fourth periodic element, basic element) of silica-based material, determination of composition ratio of fourth periodic element to aluminum or basic element, specific surface area, pore diameter and Measurement of pore volume, shape observation, measurement of average particle diameter, measurement of bulk density (CBD), measurement of wear resistance, analysis of crystal structure, chemical state analysis of fourth periodic element, morphology observation of noble metal support The following method can be used.

[Determination of content of constituent elements of silica-based material and noble metal support]
The concentrations of Si, Al, the fourth periodic element and the basic element in the silica-based material are “IRIS Intrepid II XDL type” (ICP-AES, MS) manufactured by Thermo Fisher Scientific Co., Ltd. ( Product name).
Samples are prepared as follows. First, the silica-based material is weighed in a Teflon (registered trademark) decomposition vessel, and nitric acid and hydrogen fluoride are added thereto. The obtained solution is thermally decomposed with “ETHOS · TC type” (trade name), which is a microwave decomposition apparatus manufactured by Milestone General, and then evaporated to dryness on a heater. Next, nitric acid and hydrochloric acid are added to the deposited residue, and pressure decomposition is performed with the above microwave decomposition apparatus, and the obtained decomposition solution is made to have a constant volume with pure water as a sample.
Samples were quantified by the internal standard method in the above ICP-AES, and simultaneously performed blank values were subtracted from the contents of Si, Al, fourth period element and basic element in the silica-based material, and in the noble metal support. The content of the metal element is determined, and the composition ratio (molar basis) and the supported amount are calculated.

[Determination of composition ratio]
The composition ratio of the fourth periodic element to aluminum (X / Al) based on the contents of Al, the fourth periodic element and the basic element measured in the above “determination of content of constituent elements of silica-based material and noble metal support” And the composition ratio (X / B) of the fourth periodic element with respect to the basic element.

[Measurement of specific surface area, pore diameter and pore volume]
Measure the specific surface area, pore diameter, and pore volume of silica-based materials and precious metal supports using nitrogen as the adsorbent gas with the “Autosorb 3MP” (trade name) gas adsorption measuring device manufactured by Yuasa Ionics. (Nitrogen adsorption method). The specific surface area adopts the BET method, the pore diameter and pore distribution adopt the BJH method, the pore volume adopts P / P0, and the adsorption amount at Max.

[Shape observation]
Using an X-650 scanning electron microscope (SEM) manufactured by Hitachi, Ltd., silica-based material (support) and noble metal support (catalyst) particles are observed.

[Measurement of average particle size]
The average particle diameter (volume basis) of the silica-based material and the noble metal support is measured using an LS230 laser diffraction / scattering particle size distribution analyzer manufactured by Beckman Coulter.

[Measurement of bulk density (CBD)]
As a pretreatment, first, about 120 g of a silica-based material is collected in a stainless crucible and baked in a muffle furnace at 500 ° C. for 1 hour. The fired silica-based material is placed in a desiccator (with silica gel) and cooled to room temperature. 100.0 g of the silica-based material pretreated in this way is collected, transferred to a 250 mL measuring cylinder, and the silica-based material is tapped and filled in the measuring cylinder with a shaker for 15 minutes. The graduated cylinder was removed from the shaker, the silica-based material surface in the graduated cylinder was leveled, and the filling volume was read. The bulk density is a value obtained by dividing the mass of the silica-based material by the filling volume.

[Measurement of wear resistance]
About 50 g of silica-based material is precisely weighed and put into a vertical tube having an inner diameter of 1.5 inches and having a perforated disk having three orifices of 1/64 inch at the bottom. Air is blown from the outside through a perforated disk into a vertical tube at a speed of 15 CF (Cubic Feet) per hour, and the particles of silica-based material in the tube are vigorously flowed. The ratio (mass%) of the total amount of silica-based material particles that have been refined and dissipated from the top of the vertical tube within 5 to 20 hours from the start of air blowing to the initially charged amount is expressed as “resistance resistance”. It is calculated as “abrasion”.

[Analysis of crystal structure]
X-ray source Cu tube (40 kV, 200 mA), measurement range 5 to 65 deg (0.02 deg / step), measurement speed using Rigaku's powder X-ray diffractometer (XRD) “Rint 2500 type” (trade name) The crystal structure of the silica-based material is analyzed under the conditions of 0.2 deg / min and slit width (scattering, divergence, light reception) of 1 deg, 1 deg, and 0.15 mm.
The measurement is performed by uniformly spreading the sample on a non-reflective sample plate and fixing it with neoprene rubber.

[Chemical state analysis of the fourth periodic element (nickel)]
The NiKα spectrum of silica-based materials was measured with XFRA190 double-crystal high-resolution X-ray fluorescence spectrometer (HRXRF) manufactured by Technos, and the obtained parameters were compared with those of standard materials (nickel metal, nickel oxide). The chemical state such as the valence of nickel in the silica-based material is estimated.
The prepared silica-based material is used as it is as a measurement sample. The measurement of the Ni Kα spectrum is performed in the partial spectrum mode. At this time, Ge (220) is used as the spectral crystal, and the slit has a vertical divergence angle of 1 °, and the excitation voltage and current are set to 35 kV and 80 mA, respectively. In addition, a filter paper is used as an absorber in the standard sample, and a counting time is selected for each sample in the silica-based material sample, and measurement is performed so that the peak intensity of the Kα spectrum is 3000 cps or less and 10,000 counts or more. The measurement is repeated five times for each sample, and nickel metal is measured before and after the repeated measurement. After smoothing the measured spectrum (SG method 7 points-5 times), the peak position, full width at half maximum (FWHM), and asymmetry coefficient (AI) were calculated. The peak position was the nickel metal measured before and after the measurement of the sample. It is treated as a deviation from the measured value, chemical shift (ΔE).

[Observation of dispersion state of fourth period element]
The analysis of the cross section of the silica-based material is measured using Shimadzu Corporation EPMA1600 at an acceleration voltage of 20 KeV.

[Observation of morphology of metal support]
A bright field image of TEM is observed using a 3100FEF transmission electron microscope (TEM) manufactured by JEOL [acceleration voltage 300 kV, with energy dispersive X-ray detector (EDX) attached].
As a sample, a precious metal-carrying material is crushed in a mortar, dispersed in ethanol, subjected to ultrasonic cleaning for about 1 minute, then dropped onto Mo microgrit and air-dried.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. Those skilled in the art can implement various modifications as well as the following embodiments, and such modifications are also included in the scope of the claims. In addition, determination of the content of the constituent elements of the silica-based material in Examples and Comparative Examples, determination of the composition ratio of the fourth periodic element with respect to aluminum or basic element, measurement of specific surface area, pore diameter and pore volume, shape observation, The measurement of the average particle diameter, the measurement of the bulk density, the measurement of wear resistance, the analysis of the crystal structure, the analysis of the chemical state of the fourth periodic element, and the observation of the form of the metal support were as described above.

[Example 1]
An aqueous solution prepared by dissolving 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. . Into 10.0 kg of a silica sol solution (manufactured by Nissan Chemical Co., trade name “Snowtex N-30”, SiO ₂ content: 30% by mass) with a colloidal particle diameter of 10 to 20 nm in a stirred state in which the aqueous solution is maintained at 15 ° C. The mixture was gradually added dropwise to obtain a mixed slurry of silica sol, aluminum nitrate, nickel nitrate and magnesium nitrate. Thereafter, the mixed slurry was spray-dried with a spray dryer apparatus whose outlet temperature was set to 130 ° C. to obtain a solid.

  Next, the obtained solid was filled in a stainless steel container having an open top with a thickness of about 1 cm, heated from room temperature to 300 ° C. over 2 hours in an electric furnace, and then held at 300 ° C. for 3 hours. Further, the temperature was raised to 600 ° C. in 2 hours, and then calcined by holding at 600 ° C. for 3 hours. Then, it annealed and the silica type material which consists of complex oxide containing silicon-aluminum-nickel-magnesium was obtained.

The obtained silica-based material was 85.3 mol% silicon, 6.8 mol% aluminum, 1.4 mol% nickel, and magnesium based on the total molar amount of silicon, aluminum, nickel and magnesium. It contained 6.5 mol%. 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 determined 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 was 0.97 CBD, and the wear resistance was 0.1% by mass. The average particle diameter was 62 μm from the result of measurement by laser / scattering particle size distribution measurement. Further, from observation with a scanning electron microscope (SEM), the silica-based material was not cracked or chipped, and the shape was almost spherical. As for the solid form, an amorphous pattern similar to that of silica gel was obtained from the results of powder X-ray diffraction (XRD).

  Regarding the chemical state of nickel in silica-based materials, it is estimated from the results of double-crystal high-resolution X-ray fluorescence analysis (HRXRF) that nickel is high-spin divalent. From the difference in NiKα spectra, nickel oxide is a single compound. Were found to be in different chemical states. The full width at half maximum (FWHM) of the Ni Kα spectrum of the silica-based material obtained from the measured spectrum was 3.474 and the chemical shift (ΔE) was 0.331. The full width at half maximum (FWHM) of the Ni Kα spectrum of nickel oxide measured as a standard substance was 3.249, and the chemical shift (ΔE) was 0.344.

  The dispersion state of nickel in the silica-based material was a state where nickel was present at almost the same concentration at any location from the result of electron probe microanalysis (EPMA).

Next, in order to evaluate the acid resistance and basicity of the silica-based material, a pH swing test was performed by the following method.
10 g of the silica-based material obtained as described above was added to 100 mL of a pH 4 buffer solution in a glass container, and after stirring at 90 ° C. for 10 minutes, the mixture was left to stand to remove the supernatant, washed with water, Decanted. The solid material thus obtained was added to 100 mL of a pH 10 buffer solution placed in a glass container, and stirring was continued at 90 ° C. for 10 minutes. Then, the solid was left to stand to remove the supernatant, washed with water, and decanted. The above operation was made into 1 cycle, and the pH swing process of 50 cycles in total was implemented. As a result, the specific surface area of the silica-based material after the pH swing treatment is 220 m ² / g, the pore volume is 0.27 mL / g, and the average pore diameter is 5.2 nm. Was not recognized.

[Example 2]
Instead of aluminum nitrate 9 hydrate 1.5 kg, aluminum nitrate 9 hydrate 4.0 kg, nickel nitrate hexahydrate 0.24 kg, zinc nitrate hexahydrate 0.11 kg, magnesium nitrate hexahydrate 69.7 mol% silicon, 15.0 mol% aluminum, 0.5 mol% zinc, 14 mol potassium and similar to Example 1 except that 1.1 kg potassium nitrate was used instead of 0.98 kg. A silica-based material containing 9 mol% was obtained. 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 determined 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 was 0.95 CBD, and the wear resistance was 0.1% by mass. The average particle diameter was 64 μm from the result of measurement by laser / scattering particle size distribution measurement. Further, from observation with a scanning electron microscope (SEM), the silica-based material was not cracked or chipped, and the shape was almost spherical. As for the solid form, an amorphous pattern similar to that of silica gel was obtained from the results of powder X-ray diffraction (XRD).

Next, in order to evaluate the acid resistance and basicity of the silica-based material obtained as described above, a pH swing test was performed by the same method as in Example 1. As a result, the specific surface area of the silica-based material after the pH swing treatment is 169 m ² / g, the pore volume is 0.26 mL / g, and the average pore diameter is 5.7 nm. Was hardly recognized.

Example 3
Instead of aluminum nitrate 9 hydrate 1.5 kg, aluminum nitrate 9 hydrate 2.0 kg, nickel nitrate hexahydrate 0.24 kg, cobalt nitrate hexahydrate 0.75 kg, magnesium nitrate hexahydrate Except that 0.38 kg of rubidium nitrate was used in place of 0.98 kg, the same procedure as in Example 1 was carried out, 82.7 mol% of silicon, 8.8 mol% of aluminum, 4.3 mol% of cobalt, and rubidium. A silica-based material containing 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 determined 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 was 0.96 CBD, and the wear resistance was 0.1% by mass. The average particle diameter was 62 μm from the result of measurement by laser / scattering particle size distribution measurement. Further, from observation with a scanning electron microscope (SEM), the silica-based material was not cracked or chipped, and the shape was almost spherical. As for the solid form, an amorphous pattern similar to that of silica gel was obtained from the results of powder X-ray diffraction (XRD).

  From the result of electron probe microanalysis (EPMA), the dispersion state of cobalt in the silica-based material was a state where cobalt was present at almost the same concentration at any location.

Next, in order to evaluate the acid resistance and basicity of the silica-based material obtained as described above, a pH swing test was performed by the same method as in Example 1. As a result, the specific surface area of the silica-based material after the pH swing treatment was 198 m ² / g, the pore volume was 0.26 mL / g, the average pore diameter was 5.0 nm, and no structural change was observed due to the pH swing treatment. It was.

Example 4
Example except that 0.24 kg of nickel nitrate hexahydrate was used instead of 0.2 kg of iron nitrate nonahydrate, and 0.48 kg of lanthanum nitrate nonahydrate was used instead of 0.98 kg of magnesium nitrate hexahydrate. In the same manner as in Example 1, a silica-based material containing 89.9 mol% silicon, 7.2 mol% aluminum, 0.9 mol% iron, and 2.0 mol% lanthanum was obtained. 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 determined 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 was 0.98 CBD, and the wear resistance was 0.1% by mass. The average particle diameter was 64 μm from the result of measurement by laser / scattering particle size distribution measurement. Further, from observation with a scanning electron microscope (SEM), the silica-based material was not cracked or chipped, and the shape was almost spherical. As for the solid form, an amorphous pattern similar to that of silica gel was obtained from the results of powder X-ray diffraction (XRD).

Next, in order to evaluate the acid resistance and basicity of the silica-based material obtained as described above, a pH swing test was performed by the same method as in Example 1. As a result, the specific surface area of the silica-based material after the pH swing treatment was 230 m ² / g, the pore volume was 0.27 mL / g, the average pore diameter was 5.3 nm, and no structural change was observed due to the pH swing treatment. It was.

Example 5
To 10 kg of water glass No. 3 (SiO ₂ : 28 to 30% by mass, Na ₂ O: 9 to 10% by mass), sulfuric acid was added until the pH reached 9, and then aluminum sulfate was added to adjust the pH to 2. . Further, sodium aluminate was added to adjust the pH to 5 to 5.5, and a part was dehydrated to obtain a hydrogel containing about 10% by mass of silica-alumina. This hydrogel was spray-dried at 130 ° C. by spray drying, and then washed so that Na ₂ O was 0.02 mass% and SO ₄ was 0.5 mass% or less. To this, 0.83 kg of magnesium oxide and 1.8 kg of nickel oxide were added and mixed to obtain a slurry. The slurry was filtered, washed, dried at 110 ° C. for 6 hours, then heated to 700 ° C. over 3 hours, and held at 700 ° C. for 3 hours for firing. Then, it cooled and obtained the silica type material.

The obtained silica-based material was 42.2 mol% silicon, 20.4 mol% aluminum, 19.8 mol% nickel, 17 magnesium based on the total molar amount of silicon, aluminum, nickel and magnesium. Contained 6 mol%. 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 determined 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 was 1.05 CBD, and the wear resistance was 0.1% by mass. The average particle size was 63 μm from the result of measurement by laser / scattering particle size distribution measurement. Further, from observation with a scanning electron microscope (SEM), the silica-based material was not cracked or chipped, and the shape was almost spherical. As for the solid form, an amorphous pattern similar to that of silica gel was obtained from the results of powder X-ray diffraction (XRD).

Next, in order to evaluate the acid resistance and basicity of the silica-based material obtained as described above, a pH swing test was performed by the same method as in Example 1. As a result, the specific surface area of the silica-based material after the pH swing treatment was 72 m ² / g, the pore volume was 0.27 mL / g, the average pore diameter was 5.3 nm, and no structural change was observed due to the pH swing treatment. It was.

Example 6
In place of 1.5 kg of aluminum nitrate nonahydrate 4.4 kg of aluminum oxide, in place of nickel nitrate hexahydrate 0.24 kg, nickel oxide 0.93 kg, magnesium nitrate hexahydrate 0.98 kg in place of magnesium oxide Except for using 0.42 kg and changing the firing temperature from 600 ° C. to 800 ° C., in the same manner as in Example 1, 42.9 mol% of silicon, 37.0 mol% of aluminum, and 10.9 mol% of nickel A silica-based material containing 9.1 mol% of magnesium was obtained. 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 determined 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 was 1.02 CBD, and the wear resistance was 0.1% by mass. The average particle diameter was 62 μm from the result of measurement by laser / scattering particle size distribution measurement. Further, from observation with a scanning electron microscope (SEM), the silica-based material was not cracked or chipped, and the shape was almost spherical. As for the solid form, an amorphous pattern similar to that of silica gel was obtained from the results of powder X-ray diffraction (XRD).

Next, in order to evaluate the acid resistance and basicity of the silica-based material obtained as described above, a pH swing test was performed by the same method as in Example 1. As a result, the specific surface area of the silica-based material after the pH swing treatment was 77 m ² / g, the pore volume was 0.27 mL / g, the average pore diameter was 5.2 nm, and no structural change was observed due to the pH swing treatment. It was.

Example 7
Instead of aluminum nitrate 9 hydrate 1.5 kg, aluminum nitrate 9 hydrate 1.0 kg, nickel nitrate hexahydrate 0.24 kg, nickel hydroxide 0.23 kg, magnesium nitrate hexahydrate 0.98 kg In the same manner as in Example 1 except that 1.9 kg of magnesium hydroxide was used and the firing temperature was changed from 600 ° C. to 650 ° C., 57.6 mol% of silicon, 3.1 mol% of aluminum, nickel As a result, a silica-based material containing 2.8 mol% of magnesium and 36.6 mol% of magnesium was obtained. 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 determined 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 was 0.99 CBD, and the wear resistance was 0.1% by mass. The average particle diameter was 62 μm from the result of measurement by laser / scattering particle size distribution measurement. Further, from observation with a scanning electron microscope (SEM), the silica-based material was not cracked or chipped, and the shape was almost spherical. As for the solid form, an amorphous pattern similar to that of silica gel was obtained from the results of powder X-ray diffraction (XRD).

Next, in order to evaluate the acid resistance and basicity of the silica-based material obtained as described above, a pH swing test was performed by the same method as in Example 1. As a result, the specific surface area of the silica-based material after the pH swing treatment was 94 m ² / g, the pore volume was 0.27 mL / g, the average pore diameter was 5.0 nm, and no structural change was observed due to the pH swing treatment. It was.

Example 8
100 g of the silica-based material, which is a solid material obtained in Example 1, was put into 1.0 L of distilled water heated to 90 ° C., and hydrothermally treated by holding at 90 ° C. for 1 hour while stirring.
Next, the mixture after hydrothermal treatment was allowed to stand to remove the supernatant, washed several times with distilled water, and the solid after filtration was dried at 105 ° C. for 16 hours. The obtained silica-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. The average particle diameter of the silica-based material was 62 μm from the result of measurement by laser / scattering particle size distribution measurement. Further, from observation with a scanning electron microscope (SEM), the silica-based material was not cracked or chipped, and the shape was almost spherical. From the result of powder X-ray diffraction (XRD), an amorphous pattern similar to that of silica gel was obtained.

Next, in order to evaluate the acid resistance and basicity of the silica-based material obtained as described above, a pH swing test was performed by the same method as in Example 1. As a result, the specific surface area of the silica-based material after the pH swing treatment was 242 m ² / g, the pore volume was 0.26 mL / g, the average pore diameter was 4.0 nm, and no structural change was observed due to the pH swing treatment. It was.

Example 9
An aqueous solution prepared by dissolving 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. Into 10.0 kg of a silica sol solution (manufactured by Nissan Chemical Co., trade name “Snowtex N-30”, SiO ₂ content: 30% by mass) with a colloidal particle diameter of 10 to 20 nm in a stirred state in which the aqueous solution is maintained at 15 ° C. The mixture was gradually added dropwise to obtain a mixed slurry of silica sol, aluminum nitrate and magnesium nitrate. Thereafter, the mixed slurry was aged by holding at 50 ° C. for 24 hours. The aged mixed slurry was cooled to room temperature and then spray-dried with a spray dryer apparatus whose outlet temperature was set to 130 ° C. to obtain a dried product.
Next, the obtained dried product was filled in a stainless steel container having an open top with a thickness of about 1 cm, heated from room temperature to 300 ° C. over 2 hours in an electric furnace, and then kept at 300 ° C. for 3 hours. Further, the temperature was raised to 600 ° C. in 2 hours, and then calcined by holding at 600 ° C. for 3 hours. Then, it annealed and obtained the silica-alumina-magnesia which is a solid substance.

Next, 1.0 L of an aqueous solution containing 27 g of nickel nitrate hexahydrate was heated to 90 ° C. Into this aqueous solution, 300 g of silica-alumina-magnesia, which was a solid obtained as described above, was added and kept at 90 ° C. for 1 hour with stirring to precipitate a nickel component on the solid. The mixture was then allowed to stand to remove the supernatant, washed several times with distilled water, filtered and the solid material was dried at 105 ° C. for 16 hours and further calcined in air at 600 ° C. for 5 hours. Thus, a silica-based material containing 80.3 mol% silicon, 8.7 mol% aluminum, 1.5 mol% nickel, and 9.5 mol% magnesium 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 determined 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 was 0.99 CBD, and the wear resistance was 0.1% by mass. The average particle diameter was 62 μm from the result of measurement by laser / scattering particle size distribution measurement. Further, from observation with a scanning electron microscope (SEM), the silica-based material was not cracked or chipped, and the shape was almost spherical. As for the solid form, an amorphous pattern similar to that of silica gel was obtained from the results of powder X-ray diffraction (XRD).

Next, in order to evaluate the acid resistance and basicity of the silica-based material obtained as described above, a pH swing test was performed by the same method as in Example 1. As a result, the specific surface area of the silica-based material after the pH swing treatment is 243 m ² / g, the pore volume is 0.27 mL / g, and the average pore diameter is 4.1 nm. Was not recognized.

Example 10
An aqueous solution in which 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 were dissolved in 552 mL of pure water was prepared. Gradually into 993 g of a silica sol solution (manufactured by Nissan Chemical Co., trade name “Snowtex N-30”, SiO ₂ content: 30 mass%) with a colloidal particle size of 10 to 20 nm in a stirred state in which the aqueous solution was maintained at 15 ° C. The slurry was added dropwise to obtain a mixed slurry of silica sol, aluminum nitrate, nickel nitrate and magnesium nitrate. Thereafter, the mixed slurry was spray-dried with a spray dryer apparatus whose outlet temperature was set to 130 ° C. to obtain a solid.

Next, heating, firing, and slow cooling were performed in the same manner as in Example 1 to obtain 76.9 mol% silicon, 7.7 mol% aluminum, 7.7 mol% nickel, and 7.7 mol% magnesium. A silica-based material containing was obtained. 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 determined 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 was 0.96 CBD, and the wear resistance was 0.1% by mass. The average particle diameter was 62 μm from the result of measurement by laser / scattering particle size distribution measurement. Further, from observation with a scanning electron microscope (SEM), the silica-based material was not cracked or chipped, and the shape was almost spherical.

Next, in order to evaluate the acid resistance and basicity of the silica-based material obtained as described above, a pH swing test was performed by the same method as in Example 1. As a result, the specific surface area of the silica-based material after the pH swing treatment is 131 m ² / g, the pore volume is 0.26 mL / g, and the average pore diameter is 7.9 nm. Was hardly recognized.

Example 11
74.1 mol% of silicon and 7.4 mol of aluminum were the same as in Example 10 except that 218 g of nickel nitrate 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. %, A silica-based material containing 11.1 mol% nickel and 7.4 mol% magnesium. 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 determined 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 was 0.95 CBD, and the wear resistance was 0.1% by mass. The average particle size was 63 μm from the result of measurement by laser / scattering particle size distribution measurement. Further, from observation with a scanning electron microscope (SEM), the silica-based material was not cracked or chipped, and the shape was almost spherical.

Next, in order to evaluate the acid resistance and basicity of the silica-based material obtained as described above, a pH swing test was performed by the same method as in Example 1. As a result, the specific surface area of the silica-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. Was hardly recognized.

Example 12
30 g of the silica-based material obtained in Example 9 was added to 100 mL of distilled water placed in a glass container, and while stirring at 60 ° C., a predetermined amount of palladium chloride aqueous solution was dropped, and 0.5 N sodium hydroxide was further added. An aqueous solution was added to adjust the pH of the aqueous solution to 8. After stirring for 1 hour, the mixture was allowed to stand to remove the supernatant, and the solid washed with distilled water until no Cl ions were detected was dried at 105 ° C. for 16 hours, and then 300 ° C. in air. For 5 hours. Next, the obtained solid was subjected to reduction treatment at 400 ° C. for 3 hours in a hydrogen atmosphere to obtain a noble metal-supported product supporting 2.4% by mass of palladium.

This noble metal support had a specific surface area of 247 m ² / g, a pore volume of 0.26 mL / g, and an average pore diameter of 4.0 nm as determined by the nitrogen adsorption method. The average particle size of the obtained noble metal-supported product was 62 μm from the result of measurement by laser / scattering particle size distribution measurement. From observation with a scanning electron microscope (SEM), the noble metal support was not cracked or chipped, and the shape was almost spherical.
Further, when the form of the noble metal support was observed with a transmission electron microscope (TEM), palladium particles having a maximum distribution (number average particle diameter: 4.3 nm (calculated number: 100)) in the particles of 4 to 5 nm were supported. It was confirmed that it was supported on a silica-based material.

Next, in order to evaluate the acid resistance and basicity of the noble metal support obtained as described above, a pH swing test was performed in the same manner as in Example 1. As a result, the specific surface area of the noble metal support after the pH swing treatment was 245 m ² / g, the pore volume was 0.26 mL / g, the average pore diameter was 4.1 nm, and no structural change was observed due to the pH swing treatment. It was. Moreover, the average particle diameter of the palladium particle | grains by a transmission electron microscope (TEM) is 4.4 nm (calculation number: 100), and the sintering of palladium particle | grains was hardly observed.

Example 13
30 g of the silica-based material obtained in Example 4 was added to 100 mL of distilled water placed in a glass container, and while stirring at 80 ° C., a predetermined amount of an aqueous ruthenium chloride solution was added dropwise, and 0.5 N sodium hydroxide was further added. An aqueous solution was added to adjust the pH of the aqueous solution to 8. After stirring for 1 hour, the mixture was allowed to stand to remove the supernatant, and the solid washed with distilled water until no Cl ions were detected was dried at 105 ° C. for 16 hours, and then 300 ° C. in air. For 3 hours. Next, the obtained solid was subjected to a reduction treatment at 350 ° C. for 3 hours in a hydrogen atmosphere to obtain a noble metal-supported product supporting 2.1% by mass of ruthenium.

The noble metal support had a specific surface area of 241 m ² / g, a pore volume of 0.27 mL / g, and an average pore diameter of 3.9 nm according to the nitrogen adsorption method. The average particle size of the obtained noble metal-supported product was 62 μm from the result of measurement by laser / scattering particle size distribution measurement. From observation with a scanning electron microscope (SEM), the noble metal support was not cracked or chipped, and the shape was almost spherical.
Further, when the form of the noble metal support was observed with a transmission electron microscope (TEM), ruthenium particles having a maximum distribution (number average particle diameter: 4.4 nm (calculated number: 100)) in the particles of 4 to 5 nm were supported. It was confirmed that it was supported on a silica-based material.

Next, in order to evaluate the acid resistance and basicity of the noble metal support obtained as described above, a pH swing test was performed in the same manner as in Example 1. As a result, the specific surface area of the noble metal support after the pH swing treatment was 240 m ² / g, the pore volume was 0.26 mL / g, the average pore diameter was 4.2 nm, and no structural change was observed due to the pH swing treatment. It was. Further, the average particle diameter of ruthenium particles by a transmission electron microscope (TEM) was 4.7 nm (calculated number: 100), and almost no sintering of ruthenium particles was observed.

Example 14
30 g of the silica-based material obtained in Example 2 was added to 100 mL of distilled water in a glass container, and a predetermined amount of chloroauric acid aqueous solution was added dropwise with stirring at 80 ° C. An aqueous sodium solution was added to adjust the pH of the aqueous solution to 8. After stirring for 1 hour, the mixture was allowed to stand to remove the supernatant, and the solid washed with distilled water until no Cl ions were detected was dried at 105 ° C. for 16 hours, and then 400 ° C. in air. Was carried out for 3 hours to obtain a precious metal-carrying product carrying 1.8% by mass of gold.

The noble metal support had a specific surface area of 175 m ² / g, a pore volume of 0.27 mL / g, and an average pore diameter of 4.0 nm as determined by the nitrogen adsorption method. The average particle size of the obtained noble metal-supported product was 62 μm from the result of measurement by laser / scattering particle size distribution measurement. From observation with a scanning electron microscope (SEM), the noble metal support was not cracked or chipped, and the shape was almost spherical.
Further, when the form of the noble metal-supported material was observed with a transmission electron microscope (TEM), gold particles having a maximum distribution (number average particle diameter: 3.5 nm (calculated number: 100)) in the particles of 3 to 4 nm were supported. It was confirmed that it was supported on a silica-based material.

Next, in order to evaluate the acid resistance and basicity of the noble metal support obtained as described above, a pH swing test was performed in the same manner as in Example 1. As a result, the specific surface area of the noble metal support after the pH swing treatment was 173 m ² / g, the pore volume was 0.26 mL / g, the average pore diameter was 4.5 nm, and almost no structural change was observed due to the pH swing treatment. There wasn't. Moreover, the average particle diameter of the gold particles by a transmission electron microscope (TEM) was 3.9 nm (calculated number: 100), and almost no sintering of the gold particles was observed.

  Table 1 shows the physical properties of the silica-based materials of Examples 1 to 11 and the noble metal support of Examples 12 to 14.

[Comparative Example 1]
Silica sol solution as a raw material is made by Nissan Chemical Co., Ltd., trade name “Snowtex N-30”, made by the company, trade name “Snowtex N-40” (SiO ₂ content: 40 mass%), aluminum nitrate, nickel nitrate A solid was obtained in the same manner as in Example 1 except that the composition of the silica alone was not added without adding magnesium nitrate until the mixed slurry was spray-dried with a spray dryer. Next, the obtained solid was heated from room temperature to 300 ° C. with a rotary kiln over 2 hours and then held at 300 ° C. for 1 hour. Further, the temperature was raised to 600 ° C. in 2 hours, and then calcined by holding at 600 ° C. for 1 hour. Thereafter, it was gradually cooled to obtain silica.
The specific surface area determined 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 was 0.55 CBD, and the wear resistance was 3.3% by mass. The average particle diameter was 66 μm from the result of measurement by laser / scattering particle size distribution measurement. Moreover, from the observation with a scanning electron microscope (SEM), the silica was cracked or chipped. The shape of silica was almost spherical. For the solid form, an amorphous pattern was obtained from the results of powder X-ray diffraction (XRD).
Next, in order to evaluate the acid resistance and basicity of the silica obtained as described above, a pH swing test was performed in the same manner as in Example 1. As a result, the specific surface area of the silica after the pH swing treatment was 198 m ² / g, the pore volume was 0.27 mL / g, the average pore diameter was 9.8 nm, and structural changes due to the pH swing treatment were observed.

[Comparative Example 2]
A silica-alumina composition containing 93.0 mol% silicon and 7.0 mol% aluminum was obtained in the same manner as in Example 1 except that nickel nitrate and magnesium nitrate were not used. The specific surface area determined 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 was 0.94 CBD, and the wear resistance was 0.2% by mass. The average particle size of the silica-alumina composition was 62 μm based on the results of laser / scattering particle size distribution measurement. Moreover, from the observation with a scanning electron microscope (SEM), the silica-alumina composition was not cracked or chipped, and the shape was almost spherical. For the solid form, an amorphous pattern was obtained from the results of powder X-ray diffraction (XRD).

Next, in order to evaluate the acid resistance and basicity of the silica-alumina obtained as described above, a pH swing test was performed in the same manner as in Example 1. As a result, the specific surface area of the silica-alumina composition after the pH swing treatment was 210 m ² / g, the pore volume was 0.32 mL / g, the average pore diameter was 9.5 nm, and structural changes due to the pH swing treatment were observed. It was.

[Comparative Example 3]
A silica-alumina-magnesia composition containing 86.5 mol% silicon, 6.9 mol% aluminum, and 6.6 mol% magnesium in the same manner as in Example 1 except that nickel nitrate was not used. Got. The specific surface area determined 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 was 0.96 CBD, and the wear resistance was 0.1% by mass. The average particle size of the silica-alumina-magnesia composition was 62 μm from the result of laser / scattering particle size distribution measurement. Further, from the observation with a scanning electron microscope (SEM), the silica-alumina-magnesia composition had no cracks or chips, and the shape was almost spherical. As for the solid form, an amorphous pattern similar to that of silica gel was obtained from the results of powder X-ray diffraction (XRD).

Next, in order to evaluate the acid resistance and basicity of the silica-alumina-magnesia composition obtained as described above, a pH swing test was conducted by the same method as in Example 1. As a result, the specific surface area of silica-alumina-magnesia after the pH swing treatment was 204 m ² / g, the pore volume was 0.26 mL / g, the average pore diameter was 8.5 nm, and structural changes due to the pH swing treatment were observed. It was.

[Comparative Example 4]
Instead of aluminum nitrate nonahydrate 1.5 kg, aluminum nitrate nonahydrate 2.3 kg, nickel nitrate hexahydrate 0.24 kg instead of nickel nitrate hexahydrate 0.37 kg, magnesium nitrate hexahydrate Instead of 0.98 kg, magnesium nitrate hexahydrate 0.21 kg, silica sol solution (trade name “Snowtex N-30”, manufactured by Nissan Chemical Co., Ltd., SiO ₂ content: 30% by mass) instead of 10.0 kg Except that 1.0 kg of silica sol solution was used, 37.3 mol% silicon, 46.2 mol% aluminum, 10.1 mol% nickel, and 6.5 mol% magnesium were the same as in Example 1. A silica-alumina-nickel oxide-magnesia composition 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 determined 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 was 0.85 CBD, and the wear resistance was 0.5% by mass. The average particle diameter was 64 μm from the result of measurement by laser / scattering particle size distribution measurement. Moreover, from the observation with a scanning electron microscope (SEM), the silica-alumina-nickel oxide-magnesia composition was found to be cracked or chipped. The shape was almost spherical. About the solid form, the crystal pattern derived from an alumina was obtained from the result of the powder X-ray diffraction (XRD).

Next, in order to evaluate the acid resistance and basicity of the silica-alumina-nickel oxide-magnesia composition obtained as described above, a pH swing test was performed in the same manner as in Example 1. As a result, the specific surface area of the silica-alumina-nickel oxide-magnesia composition after the pH swing treatment was 180 m ² / g, the pore volume was 0.29 mL / g, and the average pore diameter was 8.7 nm. A structural change was observed.

[Comparative Example 5]
Instead of aluminum nitrate 9 hydrate 1.5 kg, aluminum nitrate 9 hydrate 1.0 kg, nickel nitrate hexahydrate 0.24 kg, nickel nitrate hexahydrate 0.05 kg, magnesium nitrate hexahydrate Except that 0.28 kg of magnesium nitrate hexahydrate was used instead of 0.98 kg, 93.1 mol% silicon, 5.0 mol% aluminum, 0.3 wt% nickel were obtained in the same manner as in Example 1. A silica-alumina-nickel oxide-magnesia composition containing mol% and 1.6 mol% magnesium was obtained. 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 determined 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 wear resistance was 2.0 mass%. The average particle diameter was 65 μm from the result of measurement by laser / scattering particle size distribution measurement. Moreover, from the observation with a scanning electron microscope (SEM), the silica-alumina-nickel oxide-magnesia composition was found to be cracked or chipped. The shape was almost spherical. As for the solid form, an amorphous pattern similar to that of silica gel was obtained from the results of powder X-ray diffraction (XRD).

Next, in order to evaluate the acid resistance and basicity of the silica-alumina-nickel oxide-magnesia composition obtained as described above, a pH swing test was performed in the same manner as in Example 1. As a result, the specific surface area of the silica-alumina-nickel oxide-magnesia composition after the pH swing treatment was 195 m ² / g, the pore volume was 0.27 mL / g, and the average pore diameter was 8.5 nm. A structural change was observed.

[Comparative Example 6]
Except that 0.24 kg of manganese nitrate hexahydrate was used instead of 0.24 kg of nickel nitrate hexahydrate, 85.3 mol% of silicon and 6.8 mol% of aluminum were obtained in the same manner as in Example 1. A silica-alumina-manganese oxide-magnesia composition containing 1.4 mol% manganese and 6.5 mol% magnesium was obtained. The specific surface area determined 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 was 0.98 CBD, and the wear resistance was 0.1% by mass. The average particle diameter was 62 μm from the result of measurement by laser / scattering particle size distribution measurement. Moreover, the shape was substantially spherical from the observation with a scanning electron microscope (SEM). As for the solid form, an amorphous pattern similar to that of silica gel was obtained from the results of powder X-ray diffraction (XRD).

Next, in order to evaluate the acid resistance and basicity of the silica-alumina-manganese oxide-magnesia composition obtained as described above, a pH swing test was performed in the same manner as in Example 1. As a result, the specific surface area of the silica-alumina-manganese oxide-magnesia composition after the pH swing treatment was 210 m ² / g, the pore volume was 0.27 mL / g, and the average pore diameter was 8.1 nm. A structural change was observed.

[Comparative Example 7]
A noble metal-supported product in which palladium was supported on a silica-alumina-magnesia composition was obtained in the same manner as in Example 12 except that nickel nitrate was not used. The obtained noble metal support contained 81.7 mol% silicon, 8.8 mol% aluminum, and 9.5 mol% magnesium with respect to the total molar amount of silicon, aluminum, and magnesium. The supported amount of palladium was 2.1% by mass.

The specific surface area determined 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. The average particle size of this noble metal-supported product was 62 μm from the results of laser / scattering particle size distribution measurement. Further, from observation with a scanning electron microscope (SEM), the noble metal support was not cracked or chipped, and the shape was almost spherical.
Further, when the form of the noble metal support was observed with a transmission electron microscope (TEM), palladium particles having a maximum distribution (number average particle diameter: 4.2 nm (calculated number: 100)) in the particles of 4 to 5 nm were supported. It was confirmed that it was supported on the surface.

Next, in order to evaluate the acid resistance and basicity of the noble metal support obtained above, a pH swing test was performed 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, the average pore diameter was 8.4 nm, and structural changes due to the pH swing treatment were observed. . Moreover, the average particle diameter of the composite particles by a transmission electron microscope (TEM) was 6.7 nm (calculated number: 100), and sintering of palladium particles was observed as the pore diameter of the noble metal support increased.

Example 15
300 g of the silica-based material of Example 1 was added to a glass container containing 1 L of distilled water, and a predetermined amount of aqueous chloroauric acid solution was quickly added dropwise while stirring at 60 ° C. Subsequently, 0.5N aqueous sodium hydroxide solution was further added to adjust the pH of the aqueous solution to 8, and the stirring was continued for 1 hour. Thereafter, the glass container is allowed to stand, and then the supernatant is removed to collect the precipitate. The precipitate is washed with distilled water until no Cl ions are detected, and is dried at 105 ° C. for 16 hours. Firing in air at 400 ° C. for 5 hours gave a noble metal-supported product (2% Au / Si—Al—Ni—Mg composite oxide) supporting 2.0% by mass of Au.

The noble metal support had a specific surface area of 242 m ² / g, a pore volume of 0.27 mL / g, and an average pore diameter of 3.9 nm according to the nitrogen adsorption method. The average particle diameter was 62 μm from the result of measurement by laser / scattering particle size distribution measurement. Further, from observation with a scanning electron microscope (SEM), the noble metal support was not cracked or chipped, and the shape was almost spherical.

  According to the powder X-ray diffraction (XRD) result of the noble metal-supported product, a diffraction peak attributed to Au was observed. When the fine structure of the above-mentioned noble metal support was observed using a transmission electron microscope (TEM), 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 Au particles was 3.1 nm (calculated number: 100).

Next, in order to evaluate the acid resistance and basicity of the noble metal support, a pH swing test was performed in the same manner as in Example 1. As a result, the specific surface area of the noble metal support after the pH swing treatment was 243 m ² / g, the pore volume was 0.27 mL / g, and the average pore diameter was 3.9 nm. Was not recognized. Further, the average particle diameter of Au particles by a transmission electron microscope (TEM / STEM) was 3.2 nm (calculated number: 100), and almost no particle growth of Au particles was observed.

  As a catalyst, 240 g of the above-mentioned noble metal support (2% Au / Si—Al—Ni—Mg composite oxide) was charged in a stirred stainless steel reactor equipped with a catalyst separator and having a liquid phase portion of 1.2 liters. . The content of the stirring blade in the reactor was stirred at a speed of 4 m / sec, and the oxidative carboxylic acid ester was formed from the aldehyde and alcohol. A 36.7% by weight methacrolein / methanol solution was continuously supplied to the reactor at 0.6 liter / hour, and a 1-4% by weight NaOH / methanol solution was continuously supplied to the reactor at 0.06 liter / hour. Air was blown into the reactor such that the reaction temperature was 80 ° C., the reaction pressure was 0.5 MPa, and the outlet oxygen concentration was 4.0 vol% (corresponding to an oxygen partial pressure of 0.02 MPa). The supplied NaOH concentration was adjusted. The reaction product was continuously extracted through an overflow line from the reactor outlet, and its composition was analyzed by gas chromatography to examine the reactivity.

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

When the catalyst was removed after 1000 hours from the start of the reaction and examined with a scanning electron microscope (SEM), the catalyst particles were hardly cracked or chipped. Further, the specific surface area of the catalyst as determined by the nitrogen adsorption method was 243 m ² / g, the pore volume was 0.27 mL / g, and the average pore diameter was 4.0 nm.

  Next, when the catalyst after 1000 hours from the start of the reaction was observed with a transmission electron microscope (TEM / STEM), nanoparticles having a maximum distribution (number average particle size: 3.3 nm) in a particle size of 2 to 3 nm were found. It was confirmed that it was supported on the carrier, and sintering of Au particles was not observed.

Example 16
300 g of the carrier obtained in Example 1 was added to 1 L of distilled water in a glass container and stirred at 60 ° C., and diluted with hydrochloric acid in palladium chloride in an amount corresponding to 2.5% by mass as Pd and Pb, respectively. And the lead nitrate aqueous solution was dripped quickly. Thereafter, the contents of the glass container were held for 1 hour, and hydrazine was added to the stoichiometric amount 1.2 times and reduced. The supernatant is removed from the reduced contents by decantation, and the precipitate is recovered. The precipitate is washed with distilled water until no Cl ions are detected, and further dried at 60 ° C. under vacuum to remove Pd and Pb. A noble metal support (PdPb / Si—Al—Ni—Mg composite oxide) supported by 2.5% by mass was obtained.

The noble metal support had a specific surface area of 240 m ² / g, a pore volume of 0.26 mL / g, and an average pore diameter of 4.0 nm as determined by the nitrogen adsorption method. The average particle diameter was 62 μm from the result of measurement by laser / scattering particle size distribution measurement. Further, from observation with a scanning electron microscope (SEM), the noble metal support was not cracked or chipped, and the shape was almost spherical.

  According to the result of powder X-ray diffraction (XRD) of the above-mentioned noble metal support, diffraction peaks (2θ = 38.6 °, 44.8 °, 65.4 °, 78.6) attributed to the intermetallic compound of Pd3Pb1. °) was observed. When the fine structure of the above-mentioned noble metal support was observed using a transmission electron microscope (TEM), PdPb particles having a particle diameter of 5 to 6 nm were uniformly supported on the support surface. 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 support obtained as described above, a pH swing test was performed in the same manner as in Example 1. As a result, the specific surface area of the noble metal support after the pH swing treatment was 241 m ² / g, the pore volume was 0.27 mL / g, the average pore diameter was 4.0 nm, and no structural change was observed due to the pH swing treatment. It was. Moreover, the average particle diameter of the PdPb particles by a transmission electron microscope (TEM) was 5.1 nm (calculated number: 100), and almost no particle growth of the PdPb particles was observed.

  Methyl methacrylate was produced from 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 the catalyst.

  The conversion rate of methacrolein after the elapse of 500 hours from the start of the reaction was 44.2%, the selectivity of methyl methacrylate was 91.5%, and the methyl methacrylate production activity per unit mass of the catalyst was 4.40 mol / hour / kg. -It was a catalyst. The methacrolein conversion rate after 1000 hours from the start of the reaction was 44.6%, the selectivity of methyl methacrylate was 91.3%, and the methyl methacrylate production activity was 4.43 mol / hour / kg-catalyst. The activity hardly changed.

When the catalyst was removed after 1000 hours from the start of the reaction and examined with a scanning electron microscope (SEM), the catalyst particles were hardly cracked or chipped. Further, the specific surface area of the catalyst as determined by the nitrogen adsorption method was 241 m ² / g, the pore volume was 0.27 mL / g, and the average pore diameter was 4.1 nm.

  Next, the catalyst after 1000 hours from the start of the reaction was observed with a transmission electron microscope (TEM / STEM). As a result, nanoparticles having a maximum distribution (number average particle size: 5.2 nm) at a particle size of 5 to 6 nm were obtained. It was confirmed that it was supported on a carrier, and sintering of PdPb particles was not observed.

Example 17
Methyl methacrylate was produced from methacrolein in the same manner as in Example 15 except that 240 g of the noble metal support (Au / Si—Al—Zn—K composite oxide) obtained in Example 14 was used as the catalyst. did.

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

When the catalyst was removed after 1000 hours from the start of the reaction and examined with a scanning electron microscope (SEM), the catalyst particles were hardly cracked or chipped. Further, the specific surface area of the catalyst as determined by the nitrogen adsorption method was 171 m ² / g, the pore volume was 0.26 mL / g, and the average pore diameter was 4.7 nm.

  Next, when the catalyst after 1000 hours from the start of the reaction was observed with a transmission electron microscope (TEM / STEM), nanoparticles having a maximum distribution (number average particle diameter: 4.1 nm) in a particle diameter of 3 to 4 nm were found. It was confirmed that it was supported on the carrier, and almost no sintering of Au particles was observed.

[Comparative Example 8]
A noble metal support (2.0% Au / SiO ₂ —Al ₂ O ₃ —) supporting 2.0% by mass of Au in the same manner as in Example 15 except that the support was replaced with the silica-based material obtained in Comparative Example 3. MgO) was obtained.

The noble metal support had a specific surface area of 232 m ² / g, a pore volume of 0.28 mL / g, and an average pore diameter of 4.0 nm as determined by the nitrogen adsorption method. The average particle diameter was 62 μm from the result of measurement by laser / scattering particle size distribution measurement. Further, from observation with a scanning electron microscope (SEM), the noble metal support was not cracked or chipped, and the shape was almost spherical.

  When the microstructure of the noble metal-supported material was observed using a transmission electron microscope (TEM), 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 Au particles was 3.4 nm (calculated number: 100).

Next, in order to evaluate the acid resistance and basicity of the noble metal support obtained as described above, a pH swing test was performed in the same manner as in Example 1. As a result, the specific surface area of the noble metal support after the pH swing treatment was 242 m ² / g, the pore volume was 0.27 mL / g, the average pore diameter was 8.2 nm, and structural changes due to the pH swing treatment were observed. . Moreover, the average particle diameter of Au particles by a transmission electron microscope (TEM) was 5.6 nm (calculated number: 100), and particle growth of Au particles was observed.

The reaction was performed in the same manner as in Example 15 except that the noble metal support (2% Au / SiO ₂ —Al ₂ O ₃ —MgO) was used. As a result, the methacrolein conversion rate after 500 hours from the start of the reaction was 39.4%, the methyl methacrylate selectivity was 82.1%, and the methyl methacrylate production activity per unit mass of the catalyst was 3.52 mol / Time / kg-catalyst. The methacrolein conversion rate after 1000 hours from the start of the reaction was 31.1%, the methyl methacrylate selectivity was 78.2%, and the methyl methacrylate production activity was 2.39 mol / hour / kg-catalyst. A decrease in activity was observed.

When the catalyst was removed after 1000 hours from the start of the reaction and examined with a scanning electron microscope (SEM), the catalyst particles were hardly cracked or chipped. Further, the specific surface area of the catalyst as determined by the nitrogen adsorption method was 212 m ² / g, the pore volume was 0.27 mL / g, the average pore diameter was 8.2 nm, and a change in the structure of the catalyst was observed.

  Next, the catalyst after 1000 hours from the start of the reaction was observed with a transmission electron microscope (TEM). As a result, the number average particle diameter of the Au particles was 5.5 nm. Was observed.

Example 18
0.5 g of the same noble metal support (2% Au / Si—Al—Ni—Mg composite oxide) as in Example 15, 0.5 g of methacrolein, 6.3 g of water, 3.2 g of acetonitrile as a solvent, and magnetic stirrer. The SUS316 high-pressure autoclave reactor (total volume 120 ml) was charged, the autoclave was closed, and the system was replaced with nitrogen gas, and then a mixed gas of nitrogen containing 7% by volume of oxygen was added to the gas phase part. The total system pressure was increased to 3.0 MPa.
Subsequently, the reactor was fixed to the oil bath, and the reaction temperature was set to 100 ° C. with stirring for 4 hours. After cooling, the autoclave was removed by removing the residual pressure, the catalyst was filtered off, and the filtrate was analyzed by gas chromatography. As a result, methacrolein conversion was 49.7%, methacrylic acid selectivity was 95.3%, and methacrylic acid yield was 47.4%.

Example 19
Using the same noble metal support (2% Au / Si—Al—Ni—Mg composite oxide) as in Example 15 except that acetone was used as the solvent, methacrylic acid was converted from methacrolein. Manufactured. As a result, methacrolein conversion was 61.1%, methacrylic acid selectivity was 96.6%, and methacrylic acid yield was 59.0%.

Example 20
Using the same noble metal support (2% Au / Si—Al—Ni—Mg composite oxide) as in Example 15 except that the solvent was tertiary butanol, methacrolein to methacrylic acid was used. Manufactured. 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 predetermined amount of chloroauric acid aqueous solution and nickel nitrate hexahydrate was heated to 90 ° C. 300 g of the silica-based material obtained in Example 1 was added to this aqueous solution, and stirring was continued for 1 hour while maintaining the temperature at 90 ° C. with stirring, so that a gold component and a nickel component were precipitated on the silica-based material.
Next, the mixture was allowed to stand to remove the supernatant, washed several times with distilled water, and then filtered. This was dried at 105 ° C. for 16 hours and then calcined in air at 500 ° C. for 3 hours to thereby carry a noble metal support (AuNiO / Si—Al—Ni supporting 1.5% by weight of gold and 1.5% by weight of nickel). -Mg composite oxide).

The noble metal support had a specific surface area of 227 m ² / g, a pore volume of 0.26 mL / g, and an average pore diameter of 4.9 nm as determined by the nitrogen adsorption method. The average particle diameter was 65 μm from the result of measurement by laser / scattering particle size distribution measurement. Further, from observation with a scanning electron microscope (SEM), the noble metal support was not cracked or chipped, and the shape was almost spherical.

  When the microstructure of the noble metal support was observed using a transmission electron microscope (TEM), metal particles having a particle diameter of 2 to 3 nm were uniformly supported on the surface of the silica 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 support obtained as described above, a pH swing test was performed in the same manner as in Example 1. As a result, the specific surface area of the noble metal support after the pH swing treatment was 229 m ² / g, the pore volume was 0.27 mL / g, the average pore diameter was 4.9 nm, and no structural change was observed due to the pH swing treatment. It was. Moreover, the average particle diameter of the metal particles by a transmission electron microscope (TEM) was 3.0 nm (calculated number: 100), and almost no particle growth of the metal particles was observed.

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

[Example 22]
50 g of the same noble metal support (AuNiO / Si—Al—Ni—Mg composite oxide) as in Example 21, 100 g of methacrolein, 580 g of water, and 320 g of acetone as a solvent were charged into a stirring type autoclave (15 L) made of SUS316. After closing and replacing the inside of the system with nitrogen gas, a mixed gas of nitrogen containing 7% by volume of oxygen was introduced into the gas phase portion, and the total pressure in the system was increased to 3.0 MPa.
After reacting for 8 hours at a reaction temperature of 110 ° C., the mixture was cooled, the residual pressure was removed, the autoclave was opened, and the reaction solution was analyzed by gas chromatography. 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
In place of 1.5 kg of aluminum nitrate nonahydrate, 4.4 kg of aluminum oxide, 0.93 kg of nickel oxide in place of 0.24 kg of nickel nitrate hexahydrate, and oxidized in place of 0.98 kg of magnesium nitrate hexahydrate Except for using 0.42 kg of magnesium and changing the firing temperature from 600 ° C. to 800 ° C., in the same manner as in (1) of Example 1, silicon was 42.9 mol%, aluminum was 37.0 mol%, nickel was A carrier containing 10.9 mol% and 9.1 mol% magnesium was obtained. 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 determined 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 was 1.02 CBD, and the wear resistance was 0.1% by mass. The average particle diameter was 62 μm from the result of measurement by laser / scattering particle size distribution measurement. Further, from observation with a scanning electron microscope (SEM), the carrier was not cracked or chipped, and the shape was almost spherical. As for the solid form, an amorphous pattern similar to that of silica gel was obtained from the results of powder X-ray diffraction (XRD).

  300 g of the silica-based material obtained as described above is added to a glass container containing 1 L of distilled water, and while stirring at 60 ° C., dilute hydrochloric acid of a predetermined amount of chloroauric acid aqueous solution and nickel nitrate hexahydrate. The solution was quickly added dropwise. Subsequently, 0.5N aqueous sodium hydroxide solution was further added to adjust the pH of the aqueous solution to 8, and the stirring was continued for 1 hour. Thereafter, hydrazine was added to the contents of the glass container 1.2 times the stoichiometric amount and reduced. The supernatant is removed from the reduced content by decantation, and the precipitate is recovered. The precipitate is washed with distilled water until Cl ions are no longer detected, and further dried at 60 ° C. under vacuum to remove Au and Ni. A noble metal support (AuNi / Si—Al—Ni—Mg composite oxide) supported in an amount of 3.0% by mass was obtained.

The noble metal support had a specific surface area of 105 m ² / g, a pore volume of 0.27 mL / g, and an average pore diameter of 4.0 nm as determined by the nitrogen adsorption method. The average particle diameter was 62 μm from the result of measurement by laser / scattering particle size distribution measurement. Further, from observation with a scanning electron microscope (SEM), the noble metal support was not cracked or chipped, and the shape was almost spherical.

  When the microstructure of the noble metal support was observed using a transmission electron microscope (TEM), 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 support obtained as described above, a pH swing test was performed in the same manner as in Example 1. As a result, the specific surface area of the noble metal support after the pH swing treatment was 107 m ² / g, the pore volume was 0.27 mL / g, the average pore diameter was 4.1 nm, and no structural change was observed due to the pH swing treatment. It was. Moreover, the average particle diameter of the metal particles by a transmission electron microscope (TEM) was 4.7 nm (calculated number: 100), and almost no particle growth of the metal particles was observed.

  Methacrylic acid was produced from methacrolein in the same manner as in Example 18 using the above-mentioned noble metal support (AuNi / Si—Al—Ni—Mg composite oxide). 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 containing 1 L of distilled water, and a dilute hydrochloric acid solution of a predetermined amount of chloroauric acid aqueous solution and chloroplatinic acid was rapidly added dropwise with stirring at 60 ° C. Subsequently, 0.5N aqueous sodium hydroxide solution was further added to adjust the pH of the aqueous solution to 8, and the stirring was continued for 1 hour. Thereafter, hydrazine was added to the contents of the glass container 1.2 times the stoichiometric amount and reduced. The supernatant is removed from the reduced content by decantation, and the precipitate is recovered. The precipitate is washed with distilled water until Cl ions are no longer detected, and further dried at 60 ° C. under vacuum to remove Au and Pt. A noble metal support (AuPt / Si—Al—Zn—K composite oxide) supported at 2.0% by mass was obtained.

The noble metal support had a specific surface area of 220 m ² / g, a pore volume of 0.27 mL / g, and an average pore diameter of 3.9 nm according to the nitrogen adsorption method. The average particle diameter was 62 μm from the result of measurement by laser / scattering particle size distribution measurement. Further, from observation with a scanning electron microscope (SEM), the noble metal support was not cracked or chipped, and the shape was almost spherical.

  When the fine structure of the noble metal support was observed using a transmission electron microscope (TEM), metal particles having a particle diameter of 3 to 4 nm were uniformly supported on the support surface. 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 support obtained as described above, a pH swing test was performed in the same manner as in Example 1. As a result, the specific surface area of the noble metal support after the pH swing treatment was 217 m ² / g, the pore volume was 0.27 mL / g, the average pore diameter was 4.0 nm, and no structural change was observed due to the pH swing treatment. It was. Moreover, the average particle diameter of the metal particles by a transmission electron microscope (TEM) was 3.7 nm (calculated number: 100), and almost no particle growth of the metal particles was observed.

  Methacrylic acid was produced from methacrolein in the same manner as in Example 18 using the above-mentioned noble metal support (AuPt / Si—Al—Zn—K composite oxide). 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
Methacrylic acid was produced from methacrolein in the same manner as in Example 18 using the same noble metal support (Pd / Si—Al—Ni—Mg composite oxide) as in Example 12. As a result, methacrolein conversion was 6.0%, methacrylic acid selectivity was 66.6%, and methacrylic acid yield was 4.0%.

Example 26
As a catalyst, 10 g of the same noble metal support (Pd / Si—Al—Ni—Mg composite oxide) as in Example 12 and a 10% by mass ethylene glycol aqueous solution were used. I put it in a vessel. The ethylene glycol oxidation reaction was carried out while stirring the contents at a tip speed of 1.5 m / sec of the stirring blade in the reactor. The reaction temperature was 50 ° C., air was blown at 350 ml / min at normal pressure, and the reaction was carried out for 4 hours while supplying a 2.5 mass% NaOH aqueous solution to the reactor so that the pH of the reaction system would be 8-10. Thereafter, the catalyst was filtered off, and the filtrate was evaporated to dryness with a rotary evaporator to obtain 63 g of white powder of sodium hydroxyacetate.

Example 27
As a catalyst, 1 g of the same noble metal support (Pd / Si—Al—Ni—Mg composite oxide) as in Example 12 and 150 g of liquid phenol were charged into a stirred stainless steel reactor (500 ml). After replacing the inside of the system with nitrogen gas, hydrogen gas was introduced into the gas phase portion, and the total pressure in the system was increased to 2.5 MPa. The reaction temperature was 140 ° C., and the hydrogenation reaction of phenol to cyclohexanone was carried out while stirring the contents at a tip speed of 1.5 m / sec. The reaction was carried out for 1 hour and then cooled, the residual pressure was removed, the autoclave was opened, the catalyst was filtered off, and the filtrate was analyzed by gas chromatography. As a result, the phenol conversion was 99.7% and the cyclohexanone selectivity was 91.3%.

Example 28
30 g of the silica-based material obtained in Example 4 was added to 100 mL of distilled water placed in a glass container, and while stirring at 80 ° C., a predetermined amount of an aqueous ruthenium chloride solution and an aqueous zinc nitrate solution were added dropwise. A 5N aqueous sodium hydroxide solution was added to adjust the pH of the aqueous solution to 8. After stirring for 1 hour, the mixture was allowed to stand to remove the supernatant, and the solid washed with distilled water until no Cl ions were detected was dried at 105 ° C. for 16 hours, and then 300 ° C. in air. For 3 hours. Next, the obtained solid material is subjected to a reduction treatment at 350 ° C. for 3 hours in a hydrogen atmosphere, thereby supporting 10.4% by mass of ruthenium and zinc having a zinc / ruthenium atomic ratio of 0.11. A noble metal support (RuZn / Si—Al—Fe—La composite oxide) was obtained.

  0.5 g of the above-mentioned noble metal support (RuZn / Si—Al—Fe—La composite oxide) and 280 mL of 10% by mass zinc sulfate aqueous solution were charged into a 1 liter Hastelloy autoclave and replaced with hydrogen while stirring. After raising the temperature to 150 ° C., the slurry was kept for 22 hours to pretreat the catalyst slurry. Thereafter, 140 mL of benzene was injected, and a partial hydrogenation reaction of benzene was carried out while stirring at a high pressure at a total pressure of 5 MPa. The reaction solution was taken out over time and the composition of the liquid phase was analyzed by gas chromatography. As a result, the selectivity for cyclohexene at a benzene conversion rate of 50% was 81.5%.

Example 29
30 g of the silica-based material obtained in Example 1 was added to 100 mL of distilled water in a glass container, and a dilute hydrochloric acid solution with a predetermined amount of ruthenium chloride, chloroplatinic acid, and tin chloride was added while stirring at 80 ° C. The solution was added dropwise, and a 0.5N aqueous sodium hydroxide solution was further added to adjust the pH of the aqueous solution to 8. After stirring for 1 hour, the mixture was allowed to stand to remove the supernatant, and the solid washed with distilled water until no Cl ions were detected was dried at 105 ° C. for 16 hours, and then 300 ° C. in air. For 3 hours. Next, the obtained solid was subjected to reduction treatment at 350 ° C. for 3 hours in a hydrogen atmosphere to carry 6.1% by mass of ruthenium, 5.0% by mass of tin, and 3.4% by mass of platinum. A noble metal support (RuSnPt / Si—Al—Ni—Mg composite oxide) was obtained.

  Succinic acid and glutaric acid composed of 0.15 g of the above-mentioned 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 Then, 2.1 g of the mixture of adipic acid was charged into a 30 mL autoclave, the atmosphere in the autoclave was replaced with nitrogen at room temperature, hydrogen gas was introduced into the gas phase part, and the total internal pressure was increased to 2.0 MPa. The temperature was raised to 180 ° C. When the temperature reached 180 ° C., hydrogen gas was introduced to bring the total pressure in the system to 15 MPa, and then a hydrogen reduction reaction was carried out for 10 hours. After completion of the reaction, the catalyst was separated by decantation, and the catalyst was washed with ion-exchanged water. As a result of analyzing the conversion rate of each dicarboxylic acid and the yield of diol by liquid chromatography and gas chromatography, combining the reaction solution separated by decantation and the catalyst washing solution, the conversion rates of succinic acid, glutaric acid and adipic acid were The yields of 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol were 51%, 75%, and 61%, respectively.

  According to the present invention, there is provided a silica-based material having a high mechanical strength and a large specific surface area, which is excellent in acid resistance and basicity, and a noble metal support containing the silica-based material. be able to.

Claims (9)

Silicon,
With aluminum,
At least one fourth periodic element selected from the group consisting of iron, cobalt, nickel and zinc;
At least one basic element selected from the group consisting of alkali metal elements, alkaline earth metal elements and rare earth elements;
Are 57.6 to 90 mol%, 3.1 to 30 mol%, and 0.75 to 15 with respect to the total molar amount of the silicon, the aluminum, the fourth periodic element, and the basic element, respectively. A silica-based material containing in the range of mol%, 2 to 36.6 mol%,
When the silica-based material is observed and measured by the electron probe microanalysis method, the distribution range of the concentration of the fourth periodic element to be measured is within 10% .
Catalyst carrier . The silica-based material contains the silicon, the aluminum, the fourth periodic element, and the basic element in an amount of 70 to 90 mol%, 5 to 15 mol%, and 0.75, respectively, with respect to the total molar amount. The catalyst carrier according to claim 1, which is contained in a range of ˜15 mol% and 2 to 15 mol%. The catalyst carrier according to claim 1 or 2, wherein the composition ratio of the fourth periodic element to the aluminum is 0.02 to 2.0 on a molar basis. The catalyst carrier according to any one of claims 1 to 3, wherein a composition ratio of the fourth periodic element to the basic element is 0.02 to 2.0 on a molar basis. The catalyst carrier according to any one of claims 1 to 4, wherein the fourth periodic element is nickel and the basic element is magnesium. A method for producing the catalyst carrier according to any one of claims 1 to 5,
Selected from the group consisting of a compound of at least one fourth periodic element selected from the group consisting of silica, an aluminum compound, iron, cobalt, nickel and zinc, an alkali metal element, an alkaline earth metal element, and a rare earth element Obtaining a composition containing at least one basic element compound,
Baking the composition or a dried product thereof to obtain a solid;
Have
At least one fourth periodic element selected from the group consisting of silicon, aluminum, iron, cobalt, nickel and zinc, and at least selected from the group consisting of alkali metal elements, alkaline earth metal elements and rare earth elements obtaining a one basic element, a catalyst carrier comprising silica-based material having including a method of producing a catalyst carrier. The method for producing a catalyst carrier according to claim 6, further comprising a hydrothermal treatment of the solid matter. The catalyst carrier according to any one of claims 1 to 5,
Supported on the silica-based material, at least one noble metal component selected from the group consisting of ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, and gold;
A noble metal-supported catalyst for producing a carboxylic acid ester . The noble metal-supported catalyst for carboxylic acid ester production according to claim 8 , wherein an average particle size of the noble metal component is 2 to 10 nm.