Catalyst molded article and method for manufacturing the same, and method for manufacturing alcohol using the catalyst molded article

Abstract

To provide a rhenium-containing metal catalyst molded article supported on a molded carrier in an industrially useful form, and a method for manufacturing the catalyst molded article.SOLUTION: There is provided a catalyst molded article in which metal components including rhenium are supported on a molded article carrier. In a cross-section of the catalyst molded article, in a rectangular region extending 10 to 90% in length from one end of a line segment bisecting the cross-section, and having a width of 100 μm on each side of the line segment, a coefficient of variation for the amount of rhenium supported in the direction parallel to the line segment is 0.25 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a catalyst in which a metal containing rhenium is supported on a molded carrier, which is effective for various hydrogenation reactions, a method for producing the same, and a method for producing alcohol using the molded catalyst. [Background technology]

[0002] Rhenium-supported metal catalysts, in which rhenium is supported on a carrier, are used in various hydrogenation reactions. For example, it is known that a catalyst in which rhenium is supported on titanium oxide is effective in the reaction of producing alcohol by hydrogenating carbonyl compounds (e.g., Non-Patent Documents 1 and 2). It is also known that a catalyst in which rhenium is supported on titanium oxide is effective in the reaction of producing methanol by reducing carbon dioxide (e.g., Non-Patent Document 3).

[0003] Rhenium-containing metal catalysts, in which rhenium and one or more other components are supported on a carrier, are also effective in various hydrogenation reactions. For example, for the reaction of hydrogenating a carbonyl compound to produce alcohol, a method has been reported in which, in addition to rhenium, one or more components selected from the group consisting of silicon, gallium, germanium, and indium are added as catalytically active components to reduce the carbonyl compound to produce alcohol with high activity and high selectivity (e.g., Patent Documents 1 and 2). Furthermore, for the reaction of hydrogenolysis of glycerol to produce dialcohols and monoalcohols, a method has been reported in which, in addition to rhenium, iridium is added as a catalytically active component to selectively hydrogenolyze secondary alcohols to selectively produce primary alcohols (e.g., Patent Document 3).

[0004] Thus, rhenium-containing metal catalysts are effective catalysts for various hydrogenation reactions and are useful catalysts in the chemical industry. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] WO2018 / 164193 [Patent Document 2] WO2020 / 022256 [Patent Document 3] Japanese Patent Application Laid-Open No. 2013-010707 [Non-patent literature]

[0006] [Non-Patent Document 1] Journal of Organic Chemistry 24 (1959) 1847-1854 [Non-patent document 2] Journal of Catalysis 328 (2015) 197-207 [Non-patent document 3] ACS Catalysis 2019, 9, 4, 3685-3693. Summary of the Invention [Problem to be solved by the invention]

[0007] When carrying out industrial hydrogenation reactions of various compounds, for example, batch or flow reactors are used. In either type of reactor, from the viewpoint of operability in catalyst charging and separation, and in the case of flow reactors, reduction of pressure loss, the catalyst is often preferably in the form of a structure having a size of approximately 0.1 mm or more rather than a powder. However, there is no uniformly established method for industrially preparing various molded catalysts, and in reality, various methods are devised depending on the supported metal and molded support used.

[0008] The rhenium-containing metal catalyst of the present invention has the following problems. For example, various salts of industrially available metal rhenium precursors have low solubility, so during the process of supporting these rhenium salts on a support, they precipitate and segregate on the outer surface of the catalyst molded body. Therefore, in order to support a sufficient amount of rhenium species on the support, multiple support operations are required, which is uneconomical. Furthermore, since the high-valent rhenium species that can be generated in the catalyst preparation step are volatile, the supported rhenium species easily volatilize from the molded support, making it difficult to quantitatively fix the rhenium species on the support.

[0009] Due to these unique properties of rhenium-containing catalysts, it was discovered during the process of completing the present invention that applying known methods for supporting metal components on powder supports to supporting them on molded supports results in non-uniformity of the supported metal components on the molded support, resulting in a significant decrease in catalytic activity. Furthermore, it was found that in catalysts to which one or more metal components are added in addition to rhenium, it is even more difficult to uniformly support both rhenium and these components. In other words, although rhenium-containing metal catalysts are expected to be effective industrial catalysts for various hydrogenation reactions as described above, it has been found that one of the reasons why many of them have not been put into practical use is that rhenium-containing metal catalyst compacts have a technical problem in that the catalytic activity is significantly lower than that of powder catalysts. Therefore, an object of the present invention is to provide a rhenium-containing metal catalyst molded body supported on a molded body support, which is an industrially useful form that suppresses activity reduction in the catalyst molded body, a method for producing the catalyst molded body, and a method for producing alcohol using the catalyst molded body. [Means for solving the problem]

[0010] The present inventors have found that the problems of volatilization of rhenium species and segregation on the molded support can be solved by manufacturing a molded catalyst using a specific manufacturing method. Furthermore, they have found that a molded catalyst in which rhenium is supported on a molded support in a specific distribution can solve the problem of decreased activity, leading to the completion of the present invention. That is, the gist of the present invention is as follows.

[0011] (1) A catalyst molded body in which a metal component containing rhenium is supported on a molded body support, wherein in a cross section of the catalyst molded body, in a rectangular region extending 10 to 90% of the length from one end of a line segment dividing the cross section into two and having a width of 100 μm on each side of the line segment, the coefficient of variation of the amount of rhenium supported in a direction parallel to the line segment is 0.25 or less. (2) The catalyst molded body according to (1) above, wherein the catalyst molded body is spherical. (3) The catalyst molded body according to (1) above, wherein the catalyst molded body is columnar. (4) The molded catalyst according to any one of (1) to (3) above, wherein the first quartile of the distribution of the amount of rhenium carried in the region is 70% or more of the third quartile. (5) The catalyst molded body according to any one of (1) to (4) above, wherein the metal component contains, as a second component, one or more elements selected from the group consisting of elements belonging to Groups 13 to 15 of the third period or later and elements belonging to Groups 8 to 10. (6) The molded catalyst according to (5) above, wherein the coefficient of variation of the amount of the second component carried in the region is 0.25 or less. (7) The molded catalyst according to (5) or (6) above, wherein the first quartile of the distribution of the amount of the second component supported in the region is 70% or more of the third quartile. (8) The molded catalyst according to any one of (1) to (7) above, wherein the molded support contains an oxide of a metal of Group 4 of the periodic table. (9) The catalyst molded body according to any one of (1) to (8) above, wherein the molded body support is spherical with a diameter of 0.34 mm to 10 mm, or cylindrical with a circumscribed circle diameter of 0.34 mm to 10 mm in cross section and a length of 0.5 mm to 50 mm. (10) The molded catalyst according to any one of (1) to (9) above, which is used as a catalyst for producing a corresponding alcohol from a carbonyl compound. (11) A method for producing an alcohol, comprising bringing a carbonyl compound into contact with the shaped catalyst in the presence of the shaped catalyst according to any one of (1) to (10) above to produce the corresponding alcohol. (12) The method for producing an alcohol according to (11) above, wherein the alcohol is produced in a flow reactor. (13) A method for producing a molded catalyst body containing a metal component containing rhenium as a first component, the method comprising sequentially carrying out the following steps [2] to [4]: Step [2]: A first component supporting step, which includes supporting a rhenium-containing compound on a molded support to obtain a metal-supported precursor. Step [3]: A calcination step, which includes calcining the metal-supported precursor to obtain a metal-supported material. Step [4]: ​​A reduction step, which includes reducing the metal support in a reducing gas to obtain a catalyst molded body containing a metal component containing rhenium. (14) A method for producing a molded catalyst body according to the above (13), which comprises the following step [1] before the step [2]: Step [1]: A second component supporting step in which one or more metals selected from elements belonging to Groups 13 to 15 of the third period or later and elements belonging to Groups 8 to 10 are supported on a molded support as a second component. (15) The method for producing a molded catalyst body according to (13) or (14) above, wherein in the step [3], the calcination treatment is carried out in an oxygen-containing gas. (16) The method for producing a molded catalyst according to any one of the above (13) to (15), which comprises a drying step after the step [1] and before the step [2]. (17) The method for producing a catalyst molded body according to any one of (13) to (16) above, wherein the step [2] is a step of supporting a rhenium-containing compound on a molded body support, and the temperature of the solution or dispersion in which the rhenium-containing compound is dissolved or dispersed is 10°C or higher when the molded body support is mixed with the solution or dispersion in which the rhenium-containing compound is dissolved or dispersed. (18) The method for producing a molded catalyst according to any one of (13) to (17) above, wherein the temperature difference between the solution or dispersion and the molded support is controlled to 50° C. or less. (19) The method for producing a molded catalyst according to (18) above, wherein the temperature difference between the solution or dispersion and the molded support is controlled to 20° C. or less. (20) The method for producing a molded catalyst according to any one of the above (13) to (19), wherein the molded support contains an oxide of a metal of Group 4 of the periodic table. (21) The method for producing a molded catalyst according to any one of the above (14) to (20), wherein the second component contains germanium. (22) The method for producing a molded catalyst body according to any one of the above (17) to (21), wherein the rhenium-containing compound comprises at least one selected from perrhenic acid and perrhenates. (23) The method for producing a molded catalyst according to any one of the above (13) to (22), wherein the molded catalyst is used as a catalyst for producing a corresponding alcohol from a carbonyl compound. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a rhenium-containing metal catalyst molded body supported on a molded body support, which is an industrially useful form that suppresses a decrease in catalytic activity in the catalyst molded body, and a method for producing the catalyst molded body. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 2 is a schematic diagram showing a cross section of a catalyst molded body having a circular cross section. [Figure 2] 1 is a schematic diagram showing a cross-sectional view of a catalyst molded body having a hollow structure, the cross-section of which is circular. [Figure 3] 1 shows line profiles of the intensities of rhenium Lα line and germanium L line in a rectangular region of the catalyst molded body of Example 1. [Figure 4] 1 is a histogram of the intensity distribution of rhenium Lα rays in the catalyst molded body of Example 1. [Figure 5] 1 is a histogram of the intensity distribution of germanium L lines in the catalyst molded body of Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0014] The following describes in detail the embodiments of the present invention. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention is not limited to these contents, and can be implemented in various modifications within the scope of its gist. In the present invention, the catalyst components (e.g., rhenium, the group of elements belonging to Groups 13 to 15 of the periodic table from the third period onwards, and one or more elements selected from the group of elements belonging to Groups 8 to 10 of the periodic table) that are supported on a molded support and used may be collectively referred to as "metal components." Furthermore, the simple substances and compounds of these metal components are sometimes referred to as "metal-containing compounds," and the simple substance and compounds of rhenium are sometimes referred to as "rhenium-containing compounds." Furthermore, a metal-containing compound supported on a carrier is sometimes called a "metal-supported material precursor," a calcined metal-supported material precursor is sometimes called a "metal-supported material," and a metal-supported material that has been subjected to a reduction treatment is sometimes called a "metal-supported catalyst."

[0015] [Catalyst molding] The molded catalyst of the present invention (hereinafter sometimes referred to as "the molded catalyst") is a molded catalyst in which a metal component including rhenium is supported on a molded support. In the cross section of the molded catalyst, in a rectangular region extending 10 to 90% of the length from one end of a line segment dividing the cross section into two and having a width of 100 μm on each side of the line segment, the coefficient of variation of the amount of rhenium supported in the direction parallel to the line segment is 0.25 or less. By controlling this coefficient of variation, the catalytic activity per supported metal can be fully exerted, thereby shortening the reaction time and reducing the catalyst cost. Here, the cross section of the catalyst molded body refers to any cross section that can be divided into two parts so that the volume ratio after division falls within the range of 1:1 to 1:2.

[0016] The region for measuring the coefficient of variation of the present catalyst molded body will be described in detail with reference to Fig. 1. Fig. 1 shows a cross-sectional view of the catalyst molded body, and for example, when the catalyst molded body is spherical, the circle shown in Fig. 1 represents the cross-section of the spherical catalyst molded body itself. The line segment that divides the cross section shown in Figure 1 into two is line segment a(XY). The portion that is 10% of the length from one end X of line segment a(XY) is X1, and the portion that is 90% of the length from X is X2. The rectangular region 3 on either side of this line segment a(XY), each having a width of 100 μm (total 200 μm), is the region of the present invention, and is characterized in that the coefficient of variation of the amount of rhenium supported in the direction parallel to the line segment is 0.25 or less. Here, the line segment that divides the cross section into two refers to any line segment that divides the cross section into two so that the area ratio after division is in the range of 1:1 to 1:2.

[0017] The shape of the molded body carrier constituting the shape of the catalyst molded body is not particularly limited as long as it achieves the effects of the present invention. For example, any of the following shapes can be used: columnar, spherical, hollow spherical, honeycomb, or a shape lacking a portion thereof or having an uneven structure such as protrusions. This also includes a cylindrical shape. Furthermore, the cross-sectional shape of the columnar catalyst molded body can be any of a circle, polygon, hollow circle, trilobe, and quadrolobe. Of these, spherical and columnar shapes are preferred in terms of ease of handling. Below, the spherical and columnar shapes will be described as examples.

[0018] FIG. 1 shows a schematic cross-sectional view of a molded catalyst body. When the spherical molded body carrier is divided into two, the volume ratio of each divided part is in the range of 1:1 to 1:2, and any cross section thereof shows a circular shape, for example, as shown in FIG. 1. Next, the cross section is divided to obtain a line segment that divides the cross section into two so that the area ratio is in the range of 1:1 to 1:2. In the schematic diagram shown in FIG. 1, line segment a is the line segment when the cross section area ratio is 1:1, and line segments b and c are line segments drawn so that the cross section area ratio is 1:2. That is, the line segment for dividing the cross section into two in the present invention is located between line segments a and b or between line segments a and c. The present invention is characterized in that the coefficient of variation of the amount of rhenium supported in a rectangular region 3 (hereinafter sometimes referred to as the "catalyst center portion") that is 10 to 90% of the length from one end of the line segment and has a width of 100 μm on both sides of the line segment (total width: 200 μm) is 0.25 or less. To explain this in more detail using line segment a as an example, this means that the coefficient of variation of the amount of rhenium carried in rectangular region 3 (catalyst center) 100 μm wide on both sides of line segment a (XY) between point X1, which is 10% of the length from one end (end) X of line segment a (XY), and point X2, which is 90% of the length from X, is 0.25 or less.

[0019] Furthermore, when the molded support is columnar, for example, cylindrical, the coefficient of variation of the rhenium loading is measured in the cross section when the molded support is cut at a plane that forms an angle of 60° to 90° with respect to the height direction of the molded support in the same manner as in the case of a spherical molded support. For example, when the molded support is cut at an angle of 90° with respect to the height direction of the cylinder, the cross section is circular, similar to when the molded support is spherical. Furthermore, when the angle with respect to the height direction of the molded support is less than 90°, the cross section changes from a perfect circle to an ellipse depending on the angle. Even in this case, a line is set to divide the molded support into two so that the area ratio is in the range of 1:1 to 1:2, and the coefficient of variation of the rhenium loading in a rectangular region (catalyst center) extending 10 to 90% from one end of the line and 100 μm wide on both sides of the line is 0.25 or less.

[0020] When a molded support having a hollow structure such as a hollow sphere or cylinder is used, the above regions can be defined as rectangular regions 3 and 3' in the cross section of the molded catalyst, extending 10 to 90% of the length from one end of a line segment dividing the cross section into two and each having a width of 100 μm (total width of 200 μm) on both sides of the line segment (X-Y and X'-Y') excluding the hollow portion 2. That is, as shown in Fig. 2, the rectangular regions 3 and 3' (X1-X2 and X1'-X2') are defined as rectangular regions 3 and 3' extending 10 to 90% of the length from one end of the line segment (X-Y and X'-Y') excluding the hollow portion and each having a width of 100 μm on both sides of the line segment.

[0021] <Rhenium distribution in the catalyst molded body> As described above, the molded catalyst of the present invention is characterized in that the coefficient of variation of the amount of rhenium supported in the region (catalyst center portion) is 0.25 or less, i.e., rhenium is uniformly supported on the molded support in the catalyst center portion. The coefficient of variation of the amount of supported rhenium is preferably 0.25 or less, more preferably 0.22 or less, even more preferably 0.20 or less, still more preferably 0.15 or less, and particularly preferably 0.10 or less. By setting the coefficient of variation of the amount of supported rhenium in the center of the catalyst within the above range, it is possible to suppress a decrease in the active surface area of ​​rhenium due to aggregation of the supported rhenium, and it is possible to improve the catalytic activity per amount of rhenium. Furthermore, by setting the coefficient of variation of the amount of rhenium supported at the center of the catalyst within the above range, it is possible to suppress aggregation of the supported rhenium. For example, in the hydrogenation reaction of a carbonyl compound, it is possible to improve reaction selectivity by suppressing side reactions such as carbon reduction reactions accompanying decarboxylation, defunctionalization reactions due to dehydration and hydrogenation of the product, and esterification reactions between the raw carboxylic acid and the product alcohol.

[0022] The ratio of the first quartile to the third quartile of the amount of rhenium supported at the center of the catalyst is preferably 70% or more, more preferably 72% or more, even more preferably 75% or more, and particularly preferably 80% or more. By setting the ratio of the first quartile to the third quartile of the amount of rhenium supported within the above range, it is possible to suppress a decrease in the active surface area of ​​rhenium due to agglomeration of the supported rhenium, and to improve catalytic activity per amount of rhenium. Furthermore, in the hydrogenation reaction of a carbonyl compound, by setting the first quartile relative to the third quartile of the amount of supported rhenium within the above range, it is possible to suppress aggregation of the supported rhenium, and to further improve the reaction selectivity, for example, by suppressing side reactions in the hydrogenation reaction of a carbonyl compound, such as carbon reduction reactions, dehydration of the product, defunctionalization reactions due to hydrogenation, and esterification reactions between the raw carboxylic acid and the product alcohol.

[0023] When the rhenium-containing catalyst contains a second component, the coefficient of variation of the amount of the second component supported at the catalyst center is preferably 0.25 or less, more preferably 0.22 or less, even more preferably 0.20 or less, even more preferably 0.15 or less, and particularly preferably 0.10 or less. By setting the coefficient of variation of the amount of the second component supported within the above range, rhenium and the second component can be uniformly mixed, thereby enhancing the effect of adding the second component. That is, the catalytic activity and / or selectivity for various hydrogenation reactions can be improved. For example, in the hydrogenation reaction of carbonyl compounds, the catalytic activity and selectivity for the hydrogenation reaction of carbonyl compounds can be improved.

[0024] When the rhenium-containing catalyst contains a second component, the ratio of the first quartile of the second component loading at the catalyst center relative to the third quartile is preferably 70% or more, more preferably 72% or more, even more preferably 75% or more, and particularly preferably 80% or more. By setting the ratio of the first quartile of the second component loading relative to the third quartile within the above range, rhenium and the second component can be uniformly mixed, thereby enhancing the effect of adding the second component. In other words, the catalytic activity and / or selectivity for various hydrogenation reactions can be improved. For example, in the hydrogenation reaction of carbonyl compounds, the catalytic activity and selectivity for the hydrogenation reaction of carbonyl compounds can be improved.

[0025] When the rhenium-containing catalyst contains a second component, the ratio of the coefficient of variation of the amount of the second component supported to the coefficient of variation of the amount of rhenium supported in the catalyst center is usually 0.2 or more, preferably 0.5 or more, more preferably 0.75 or more, and particularly preferably 0.8 or more, and is usually 5 or less, preferably 2 or less, more preferably 1.5 or less, and particularly preferably 1.25 or less. By setting the ratio of the coefficient of variation of the amount of the second component supported to the coefficient of variation of the amount of rhenium supported in the catalyst center within the above range, rhenium and the second component can be uniformly mixed, thereby enhancing the effect of adding the second component. That is, the catalytic activity and / or selectivity for various hydrogenation reactions can be improved. For example, in the hydrogenation reaction of carbonyl compounds, the catalytic activity and selectivity for the hydrogenation reaction of carbonyl compounds can be improved.

[0026] <Measurement of metal distribution in catalyst molded body> The metal distribution in the catalyst compact is quantified with a spatial resolution of several nanometers from a field of view of several millimeters to several tens of nanometers using SEM-EDS, which is a scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy (EDS).

[0027] More specifically, it is measured by the following method. First, the catalyst molded body is cut into the above range (volume ratio after division is in the range of 1:1 to 1:2) to obtain cross sections, which are then coated with carbon as a conductive treatment. Next, for example, using a Hitachi High-Technologies Corporation Schottky scanning electron microscope SU5000 equipped with a Bruker AXS QUANTAX FlatQUAD-EDS detector, EDS measurements are performed under SEM conditions of 15 kV acceleration voltage, 50 spot intensity, 11.0 mm working distance, 70x measurement magnification, 512 x 384 image pixels, pulse input 130 kcps, acquisition time 300 seconds, and dwell time 16 μs, and an intensity map of the rhenium Lα line and germanium L line of the cross section of the catalyst molded body is obtained by SEM-EDS. From the obtained intensity map, a line profile is measured in a rectangular region of 100 μm on both sides of the line segment that divides the catalyst molded body into two so that the area ratio after division is in the range of 1:1 to 1:2. The line profile intensity distribution is obtained at 3.56 μm intervals. In the case of the above conditions, the calculation is based on the intensity data of the rhenium Lα line and germanium L line obtained from a portion approximately 5 μm inside from the surface.

[0028] The metal distribution in the cross section of the obtained molded catalyst is statistically processed using the following method. Specifically, the characteristic X-rays of each element are measured at each point in a region 10 to 90% long from one end of a line segment divided into two so that the area ratio after division is within the range of 1:1 to 1:2, at intervals of 3.56 μm, and the coefficient of variation of the characteristic X-ray intensity distribution is calculated. The coefficient of variation (CV) is a dimensionless quantity defined by the following formula (1), where σ is the standard deviation and μ is the mean value. Furthermore, because the characteristic X-ray intensity and the metal amount are proportional to each other, the coefficient of variation of the characteristic X-ray intensity is equal to the coefficient of variation of the metal loading amount.

[0029]

number

[0030] The first quartile relative to the third quartile of the characteristic X-ray intensity at the center of the molded catalyst body is also calculated. As with the coefficient of variation, the first quartile relative to the third quartile is a dimensionless quantity, so the first quartile relative to the third quartile of the characteristic X-ray intensity is equal to the first quartile relative to the third quartile of the loading amount. Hereinafter, these values ​​will be referred to as the "coefficient of variation of the loading amount" and the "first quartile relative to the third quartile of the loading amount." Similar analysis is carried out on three or more points for each catalyst molded body, and the coefficient of variation of the loading amount and the arithmetic mean of the first quartile relative to the third quartile of the loading amount are calculated.

[0031] The structure of the catalyst molded body will be described in detail below. <Metal components> (First component and second component) The metal components supported on the present molded catalyst include rhenium as a first component, and when the present molded catalyst includes a second component, the second component includes one or more metal components selected from the group of elements belonging to Groups 13 to 15 of the third period or later of the periodic table and the group of elements belonging to Groups 8 to 10 of the periodic table. Of these, the second component more preferably contains a group of elements belonging to groups 13 to 15 of the third period or later of the periodic table. The one or more metal components selected from the group of elements belonging to Groups 13 to 15 of the third period or later in the periodic table more preferably contain one or more elements selected from the group consisting of silicon, germanium, and indium, even more preferably one or more elements containing germanium, and particularly preferably one containing germanium. On the other hand, the one or more metal components selected from the group of elements belonging to Groups 8 to 10 of the periodic table more preferably contain one or more elements selected from the group consisting of iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, and platinum, even more preferably one or more elements including nickel, ruthenium, palladium, and iridium, even more preferably one containing nickel, ruthenium, palladium, or iridium, and particularly preferably one containing palladium or iridium. In the present invention, the periodic table refers to the long-form periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005).

[0032] (Amount of first component and second component supported) In the present catalyst molded body, the amount of rhenium supported is not particularly limited, but the mass ratio of rhenium to the total mass of the catalyst molded body is usually 0.1 mass% or more, preferably 1 mass% or more, more preferably 3 mass% or more, and usually 20 mass% or less, preferably 10 mass% or less, more preferably 8 mass% or less. By setting the amount of rhenium supported within the above range, sufficient catalytic activity can be exhibited, thereby shortening the reaction time. Furthermore, the reaction selectivity is high and catalyst costs can be reduced. For example, in the hydrogenation reaction of carbonyl compounds, aggregation of the supported rhenium can be suppressed, and side reactions such as carbon reduction reactions associated with decarboxylation, dehydration of the product and defunctionalization reactions associated with hydrogenation, and esterification reactions between the raw carboxylic acid and the product alcohol can be suppressed, thereby further improving reaction selectivity.

[0033] The lower limit of the amount of the second component supported, expressed as a mass ratio to the first component, rhenium, is preferably 0.01 or more, more preferably 0.1 or more, and the upper limit is preferably 10 or less, more preferably 5 or less, even more preferably 3 or less, and of these, 2 or less is preferred, with 1 or less being particularly preferred. By adjusting the type of second component to be combined with rhenium and / or the ratio of the supported amount thereof within the above range, the effect of adding the second component can be enhanced, i.e., the catalytic activity and / or selectivity for various hydrogenation reactions can be improved.

[0034] For example, in the hydrogenation reaction of carbonyl compounds, the addition of one or more metal components selected from the group of elements belonging to Groups 13 to 15 of the third period or later of the periodic table not only improves the catalytic activity of the hydrogenation reaction of carbonyl compounds, but also enables the production of alcohols while highly suppressing side reactions such as the esterification reaction between the raw material carboxylic acid and the product alcohol, and the dehydration and defunctionalization reaction of the product alcohol due to hydrogenation, which occur significantly in particular in the later stage of the reaction. The reason why these combinations achieve improved catalytic activity and reaction selectivity, which are generally considered to be contradictory, is that the addition of the second component controls the electronic state of rhenium, the active component in hydrogenation catalysts, to a state suitable for the reduction reaction of carbonyl functional groups, and the affinity of the reactant for the second component improves its adsorption force onto the catalyst surface, and the adsorption orientation of the reactant on the catalyst surface is highly controlled.

[0035] (third component) In addition to the above metal components (i.e., rhenium and the second component), the present molded catalyst may further contain another metal component as a third component, as necessary, as long as it does not adversely affect the reaction, such as the reduction reaction, using the present molded catalyst. Examples of the other metal component include at least one metal selected from metal species such as silver, gold, molybdenum, tungsten, aluminum, and boron. Among these third components, at least one metal selected from silver, gold, molybdenum, and tungsten is preferred.

[0036] (Amount of the third component supported) The content of these third components contained in the present catalyst molded body, in terms of element mass ratio to rhenium, is usually not more than 10, preferably not more than 5, more preferably not more than 1, and even more preferably not more than 0.5. By selecting an appropriate combination and appropriate content of these additional metal components, high catalytic activity can be obtained while maintaining high selectivity.

[0037] To further improve the catalytic activity and reaction selectivity, the present molded catalyst may be used by adding to the catalyst, together with the metal components, one or more compounds selected from the group consisting of alkali metal elements lithium, sodium, potassium, rubidium, and cesium, one or more compounds selected from the group consisting of alkaline earth metal elements magnesium, calcium, strontium, and barium, and one or more compounds selected from the group consisting of halogen elements fluorine, chlorine, bromine, and iodine. In this case, there is no particular limitation on the ratio of these added components to the rhenium component.

[0038] <Molded body carrier> The shape of the molded carrier in the present invention is not limited, but the apparent volume per particle is 2×10 -2 mm 3 For example, a spherical substance with a diameter of 0.34 mm or more, or a cylindrical substance with a diameter of 0.34 mm or more and a length of 0.22 mm or more is called a molded body. The molded body carrier of the present invention has an apparent volume per particle of 2×10 -2 mm 3 As long as the above is satisfied, the shape may be any of a columnar, spherical, hollow spherical, honeycomb, or a shape lacking a portion thereof, or having an uneven structure such as protrusions. The cross-sectional shape of the columnar catalyst molded body may be any of a circle, polygon, hollow circle, three-lobe, four-lobe, etc. In the present invention, from the viewpoint of economy and ease of handling, a cylindrical, prismatic or other cylindrical, or spherical molded carrier is preferred.

[0039] The term "spherical" in the present invention refers to a shape in which the cross section of the molded body cut along any plane is a circle. In the present invention, the term "columnar shape" refers to a shape in which a cross section of a molded body cut along a specific plane is rectangular or square, and is not a cone shape. Examples of the columnar shape include a cylindrical shape, a triangular prism, a quadrangular prism, a pentagonal prism, and a hexagonal prism.

[0040] When the shaped carrier is spherical, the diameter is usually 0.34 mm or more, preferably 0.5 mm or more, more preferably 1 mm or more, and usually 10 mm or less, preferably 8 mm or less, more preferably 5 mm or less. If cylindrical, the diameter is usually 0.34 mm or more, preferably 0.5 mm or more, more preferably 1 mm or more, and usually 10 mm or less, preferably 5 mm or less, more preferably 3 mm or less, and the length is usually 0.5 mm or more, preferably 1 mm or more, more preferably 3 mm or more, and usually 50 mm or less, preferably 30 mm or less, more preferably 10 mm or less. In the case of a rectangular column shape, the diameter of the circumscribed circle of the cross section of the rectangular column is usually 0.34 mm or more, preferably 0.5 mm or more, more preferably 1 mm or more, and usually 10 mm or less, preferably 5 mm or less, more preferably 3 mm or less, and the length is usually 0.5 mm or more, preferably 1 mm or more, more preferably 3 mm or more, and usually 50 mm or less, preferably 30 mm or less, more preferably 10 mm or less.

[0041] The apparent volume per particle of the compact carrier is usually 2 x 10 -2 mm 3 or more, preferably 5 x 10 -2 mm 3 More than 0.5mm, preferably 0.5mm 3 More preferably, 2 mm or more 3 More than 5x10 3 mm 3 Less than or equal to 5 x 10 2 mm 3 Less than or equal to 50 mm, even more preferably 3 The following is the result. By setting the shape and size of the shaped support within the above ranges, a catalyst with high activity per unit mass can be obtained. Furthermore, by setting the shape and size of the shaped support within the above ranges, separation of the catalyst shaped support from the reaction solution after the reaction can be facilitated, and pressure loss during a flow reaction can be reduced.

[0042] The molded support used in the present invention can be an inert support. In the present invention, the inert support is a support that does not substantially exhibit hydrogenation activity by itself, and specifically is defined as a molded support that does not substantially contain chromium, rhenium, or any of the metals of Groups 8 to 12 of the periodic table selected from the group consisting of iron, ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, and zinc, which are catalytically active metals.

[0043] A molded body carrier substantially free of the above metals means a molded body carrier that does not primarily contain the above metals, i.e., the content of these metals relative to the total mass of the molded body carrier is 5% by mass or less, preferably 1% by mass or less, and more preferably 0.1% by mass or less. The content of the metals in the molded body carrier can be measured and determined by known analytical methods such as ICP mass spectrometry (ICP-MS: Inductively Coupled Plasma Mass Spectrometry), ICP atomic emission spectrometry (ICP-AES: Inductively Coupled Plasma Atomic Emission Spectrometry), atomic absorption spectrometry (AAS: Atomic Absorption Spectrometry), or X-ray fluorescence analysis (XRF: X-ray Fluorescence Analysis).

[0044] The shaped support used in the present invention is not particularly limited, but is preferably composed mainly of an oxide of a metal of Group 4 of the periodic table. Here, "composed mainly of" means that the mass ratio of the oxide to the total mass of the support is usually 50 mass% or more, preferably 70 mass% or more, more preferably 90 mass% or more, even more preferably 95 mass% or more, still more preferably 98 mass% or more, and most preferably 99 mass% or more. When the support is mainly composed of an oxide of a metal of Group 4 of the periodic table, the support may use one metal oxide of Group 4 of the periodic table alone or a combination of two or more metal oxides of Group 4 of the periodic table. When two or more metal oxides are used in combination, there are no particular restrictions on the combination or mixing ratio, and the support may be used in the form of a mixture of individual compounds or a composite oxide.

[0045] The shaped body support used in the present invention preferably contains titanium oxide, zirconium oxide, or hafnium oxide, more preferably titanium oxide or zirconium oxide, even more preferably a shaped body support mainly composed of titanium oxide or zirconium oxide, and most preferably a titanium oxide shaped body support or a zirconium oxide shaped body support. By using a shaped body support containing titanium oxide, zirconium oxide, or hafnium oxide, a catalyst with high catalytic activity and selectivity can be obtained.

[0046] The shaped support used in the present invention may contain support components other than the metal oxides of Group 4 of the periodic table. Examples of other support components include one or more of graphite, activated carbon, silicon carbide, silicon nitride, aluminum nitride, boron nitride, boron oxide, aluminum oxide (alumina), silicon oxide (silica), lanthanum oxide, cerium oxide, yttrium oxide, niobium oxide, magnesium silicate, calcium silicate, magnesium aluminate, calcium aluminate, aluminosilicate, aluminosilicophosphate, aluminophosphate, magnesium phosphate, calcium phosphate, strontium phosphate, hydroxyapatite (calcium hydroxyphosphate), apatite chloride, apatite fluoride, calcium sulfate, barium sulfate, and barium carbonate.

[0047] The specific surface area of ​​the molded carrier used in the present invention is not particularly limited since it depends on the type of carrier used, but is usually 1 m 2 / g or more, preferably 10m 2 / g or more, more preferably 50m 2 / g or more, more preferably 80m 2 / g or more, usually 3000m 2 / g or less, preferably 2000m 2 / g or less, more preferably 500m 2 / g or less. By setting the specific surface area of ​​the shaped support within the above range, it is possible to suppress aggregation of the metal components of the catalyst shaped body and thereby achieve high catalytic activity. Furthermore, by setting the specific surface area of ​​the shaped support within the above range, it is possible to maintain the strength of the catalyst shaped body and suppress powdering of the catalyst shaped body. The specific surface area of ​​the shaped support is generally a value calculated using the BET equation by measuring the nitrogen adsorption isotherm at liquid nitrogen temperature.

[0048] The pore volume of the shaped support used in the present invention is not particularly limited, but is usually 0.01 mL / g or more, preferably 0.1 mL / g or more, more preferably 0.2 mL / g or more, and usually 10 mL / g or less, preferably 5 mL / g or less. The pore volume of the shaped support is generally calculated from the nitrogen adsorption amount at a relative pressure of 0.98 measured by measuring a nitrogen adsorption isotherm at liquid nitrogen temperature. By setting the pore volume of the shaped support within the above range, it is possible to suppress aggregation of the metal components of the catalyst molded body and to achieve high catalytic activity. Furthermore, by setting the pore volume of the shaped support within the above range, it is possible to maintain the strength of the catalyst molded body and suppress powdering of the catalyst molded body.

[0049] [Method of manufacturing a molded catalyst] The catalyst molded body according to the present invention is produced by supporting a metal component on a molded body support. Specifically, the method for producing a catalyst molded body of the present invention (hereinafter sometimes referred to as "the present production method") is a method for producing a catalyst molded body containing a metal component containing rhenium as the first component, and includes the following steps [2] to [4]. [2] A step of supporting a rhenium-containing compound on a molded support to obtain a metal-supported precursor (hereinafter referred to as the "first component supporting step"). [3] A step of calcining the obtained metal-supported precursor to obtain a metal-supported material (hereinafter referred to as the "calcination step"). [4] A step of reducing the obtained metal-supported material in a reducing gas to obtain a catalyst molded body containing a metal component containing rhenium (hereinafter referred to as the "reduction step").

[0050] In a method for producing a molded catalyst containing, in addition to a first component that is rhenium, one or more second components selected from the group consisting of elements belonging to Groups 13 to 15 of the third period or later and elements belonging to Groups 8 to 10 of the periodic table, it is preferable to include a step of supporting a compound containing the second component on a molded support before the step [2]. That is, it is preferable to include the following steps [1] to [4].

[0051] [1] A step of supporting, as a second component, one or more metals selected from elements belonging to Groups 13 to 15 of the third period or later and elements belonging to Groups 8 to 10 on a molded support (hereinafter referred to as the second component supporting step). [2] A step of supporting a rhenium-containing compound on a molded support to obtain a metal-supported precursor (first component supporting step) [3] A step of calcining the obtained metal-supported precursor to obtain a metal-supported material (calcination step) [4] A step of reducing the obtained metal-supported material with a reducing gas to obtain a catalyst molded body containing a metal component containing rhenium (reduction step). Each step will be explained below in order, but a preferred molded catalyst body of the present invention can be produced by combining the following steps in a preferred range. In order to produce the catalyst of the present invention in which rhenium is uniformly supported on the molded support at the center of the catalyst, it is important to appropriately combine the following preferable production conditions for the catalyst.

[0052] Each step will be explained below in order. [1] Second component loading step In the second component supporting step, various metals can be supported using solutions or dispersions of various metal-containing compounds that serve as raw materials for the various metal components. The supporting method is not particularly limited and known methods can be used, and various impregnation methods are preferred. Details of the impregnation method are as described below in the first component supporting step, and the preferred ranges are also the same.

[0053] When a metal-containing compound of a metal component is supported on a molded support, the metal-containing compound can be dissolved or dispersed in various solvents and used in various supporting methods. The type of solvent used in this case is not particularly limited as long as it can dissolve or disperse the metal-containing compound and does not adversely affect the subsequent calcination and hydrogen reduction of the metal-supported material, or the hydrogenation reaction using the present catalyst. Examples of solvents that can be used include ketone solvents such as acetone, alcohol solvents such as methanol and ethanol, ether solvents such as tetrahydrofuran and ethylene glycol dimethyl ether, and water. These may be used alone or as a mixed solvent. Among these, water is preferred because it is inexpensive and generally has a high solubility for metal-containing compounds.

[0054] The second component-containing compound is not particularly limited and can be appropriately selected depending on the loading method. For example, halides such as chlorides, bromides, and iodides; mineral acid salts such as nitrates and sulfates; metal hydroxides, metal oxides, metal-containing ammonium salts, acetates, metal alkoxides, and other organic group-containing compounds; and metal complexes can be used. Among these, halides, mineral acid salts, metal hydroxides, metal oxides, metal-containing ammonium salts, and organic group-containing compounds are preferred, and halides, mineral acid salts, metal oxides, metal-containing ammonium salts, and organic group-containing compounds are more preferred. These can be used alone or in combination of two or more in the required amounts.

[0055] When the second component is a metal containing germanium, the metal-containing compound is not particularly limited, and examples of metal complexes that can be used include germanium, germanium oxide, germanium halides such as germanium chloride, and germanium alkoxide compounds such as germanium methoxide and germanium ethoxide. Among these, germanium, germanium oxide, and germanium alkoxide compounds are preferred, with germanium oxide, germanium methoxide, and germanium ethoxide being more preferred, and germanium oxide being particularly preferred. When the second component is a metal containing iron, cobalt, or nickel, the metal-containing compound is not particularly limited, and examples thereof include the simple metals iron, cobalt, and nickel, and alloys thereof, oxides such as iron oxide, cobalt oxide, and nickel oxide, halides such as iron chloride, cobalt chloride, nickel chloride, iron bromide, cobalt bromide, and nickel bromide, metal complexes such as iron carbonyl, cobalt carbonyl, and nickel carbonyl, and metal salts such as iron nitrate, cobalt nitrate, nickel nitrate, iron sulfate, cobalt sulfate, and nickel sulfate. Among these, oxides, chlorides, and nitrates are preferred, chlorides and nitrates are more preferred, and nitrates are particularly preferred. When the second component is a metal containing ruthenium, rhodium, palladium, platinum, or iridium, the metal-containing compound is not particularly limited, but may include, for example, the metals ruthenium, rhodium, palladium, platinum, and iridium, and their alloys; oxides such as ruthenium oxide, rhodium oxide, palladium oxide, platinum oxide, and iridium oxide; metal halides such as ruthenium chloride, rhodium chloride, palladium chloride, chloropalladic acid, chloroplatinic acid, iridium chloride, and chloroiridic acid; nitrates such as ruthenium nitrosylnitrate, rhodium nitrate, palladium nitrate, iridium nitrate, and platinum nitrate; and metal complexes such as tetraamminepalladium hydroxide, hexaneammineiridium hydroxide, and tetraammineplatinum hydroxide. Among these, metal halides, nitrates, and ammine complexes are preferred, with metal halides being particularly preferred.

[0056] In the step of loading the compound of the second component, the compound of the third component may also be loaded. The loading method can be the same as the method for loading the second component, and the loading of the second component and the third component can be carried out simultaneously or sequentially.

[0057] The second component-supported material is preferably dried to a moisture content of 25% or less before the subsequent first component-supporting step (step [2]). The moisture content is more preferably 20% or less, even more preferably 10% or less, even more preferably 5% or less, and particularly preferably 2% or less. By keeping the moisture content below the above upper limit, the rhenium-containing compound can be uniformly supported in the rhenium-containing compound-supporting step. The drying method for the second component-supported material is not particularly limited as long as the solvent used during support is removed. The pressure during drying is not particularly limited, but drying is usually carried out under normal pressure or reduced pressure. The temperature during drying is not particularly limited, but drying is usually carried out at 300°C or lower, preferably 250°C or lower, more preferably 200°C or lower, and usually 80°C or higher. The method for measuring the moisture content is not particularly limited, but for example, a known heat-drying moisture meter may be used to heat a sample to 150°C and measure the moisture content from the change in mass before and after heating.

[0058] [2] First component loading step The first component supporting step is a step of supporting a rhenium-containing compound on a molded support or a second component-supported material that has supported the second component-containing compound in the above step [1].

[0059] When a second component is supported on a molded support in addition to rhenium, by supporting a rhenium-containing compound on the second component-supported material as described above, it is possible to prevent the second component and rhenium from being unevenly supported at different positions in the center of the molded support, and to ensure uniform loading.

[0060] Examples of rhenium-containing compounds that can be supported on a shaped support include perrhenates, halides such as chlorides, bromides, and iodides, mineral acid salts such as nitrates and sulfates, metal hydroxides, metal oxides, metal-containing ammonium salts, acetates, and metal alkoxides, and other organic group-containing compounds, and metal complexes. Among these, when a rhenium-containing compound containing halogens or a metal other than rhenium is used as a precursor, these elements generally remain in the catalyst and may affect catalytic performance, so rhenium-containing compounds that do not contain these elements are preferred. Furthermore, from the viewpoints of solubility in water, economic efficiency, and industrial applicability, rhenium(VII) oxide, perrhenic acid, and ammonium perrhenate are preferred, with ammonium perrhenate being particularly preferred. Alternatively, rhenium metal may be used in place of the rhenium-containing compound supported on the compact support.

[0061] The method for supporting the rhenium-containing compound on the molded support is not particularly limited, and known methods can be used. Typically, various impregnation methods can be used. Examples include the adsorption method, which utilizes the adsorption force of metal ions on the support to adsorb metal ions up to the saturated adsorption amount; the equilibrium adsorption method, which immerses the support in a solution exceeding the saturated adsorption amount and removes excess solution; the pore-filling method, which adds a solution equivalent to the pore volume of the support and adsorbs it all onto the support; the incipient wetness method, which adds a solution until it matches the water absorption amount of the support and terminates when the support surface is uniformly wet and no excess solution is present; the evaporation-to-dryness method, which impregnates the support and then evaporates the solvent by heating or reducing the pressure; and the spray method, which drys the support and sprays the solution. Among these, the pore-filling method, the incipient wetness method, the evaporation-to-dryness method, and the spray method are preferred, with the pore-filling method, the incipient wetness method, and the evaporation-to-dryness method being more preferred.

[0062] When the rhenium-containing compound is supported on the molded support, the supporting method preferably includes a step of dissolving the rhenium-containing compound in a solvent to form a solution or a dispersion to form a dispersion in a solvent, and mixing the solution with the molded support. As a method for supporting the required amount of rhenium-containing compound on the molded support, the entire required amount may be supported in one loading, or the required amount may be supported by carrying out two or more loadings.

[0063] The lower limit of the volume of the solvent used for loading is preferably 10% or more of the pore volume of the shaped support, more preferably 50% or more, even more preferably 75% or more, and particularly preferably 80% or more. The upper limit of the volume of the solvent used for loading is preferably 1000% or less, more preferably 500% or less, even more preferably 300% or less, and particularly preferably 150% or less. By satisfying these conditions, the aqueous solution or dispersion of the rhenium-containing compound can be absorbed into the pores of the shaped support and can penetrate into the center of the shaped support, allowing the rhenium-containing compound to be uniformly loaded on the shaped support.

[0064] The rhenium concentration of the solution or dispersion in which the rhenium-containing compound is dissolved and used for loading is not particularly limited, but is usually 0.1 g / L or more, preferably 1 g / L or more, more preferably 10 g / L or more, and particularly preferably 100 g / L or more, and is usually 10,000 g / L or less, preferably 5,000 g / L or less, more preferably 1,000 g / L or less, and particularly preferably 500 g / L or less. By setting the rhenium concentration of the solution or dispersion in which the rhenium-containing compound is dissolved within the above range, an excessive increase in the number of steps in the rhenium loading step can be prevented, and the catalyst production cost can be reduced. Furthermore, it is possible to prevent the solution from becoming supersaturated, which would otherwise cause the rhenium-containing compound to segregate on the outer surface of the molded support when the solution and the molded support are mixed.

[0065] When a rhenium-containing compound is supported on a molded support, the temperature of the solution or dispersion in which the rhenium-containing compound is dissolved is usually 10° C. or higher, preferably 20° C. or higher, more preferably 40° C. or higher, even more preferably 50° C. or higher, particularly preferably 60° C. or higher, and most preferably 70° C. or higher. The temperature is usually 100° C. or lower, preferably 98° C. or lower, more preferably 90° C. or lower. By keeping the temperature of the solution or dispersion in which the rhenium-containing compound is dissolved within the above range, it is possible to prevent the rhenium-containing compound from being strongly adsorbed to the outer surface of the molded support and segregating, and also to promote diffusion of the rhenium-containing compound into the pores.

[0066] When a rhenium-containing compound is supported on a molded support, the temperature difference between the solution or dispersion in which the rhenium-containing compound is dissolved and the molded support when they are mixed is preferably 50° C. or less, more preferably 30° C. or less, even more preferably 20° C. or less, and particularly preferably 10° C. or less. By keeping the temperature difference between the solution or dispersion in which the rhenium-containing compound is dissolved and the molded support within the above range when they are mixed, it is possible to prevent a temperature gradient from occurring within the molded support due to the temperature difference between the molded support and the solution, and thus prevent the rhenium-containing compound from segregating on the molded support. Here, the "temperature difference during mixing" refers to the temperature difference immediately before the dispersion liquid and the molded carrier are mixed, and does not specify the temperature difference between the two thereafter.

[0067] When dissolving or dispersing a metal-containing compound, various additives may be added in addition to a solvent. For example, as described in JP-A-10-15388, by adding a carboxylic acid and / or carbonyl compound solution, the dispersibility of each metal component on the support can be improved when the metal component is supported on the support.

[0068] The metal-supported material after supporting the rhenium-containing compound may be dried as needed, and is preferably subjected to the calcination and reduction treatment steps after drying. If the metal-supported material is subjected to the subsequent calcination and reduction treatment without being dried, the reaction activity of the resulting catalyst may be reduced. The method for drying the metal-supported material after supporting the rhenium-containing compound is not particularly limited, as long as the solvent used during the support is removed. The pressure during drying is not particularly limited, but drying is usually carried out under normal pressure or reduced pressure. The temperature during drying is not particularly limited, but drying is usually carried out at 300°C or lower, preferably 250°C or lower, more preferably 200°C or lower, and usually 80°C or higher.

[0069] [3] Firing process The calcination step is a step of calcining the molded body support on which the first component compound is supported by the above step [2], or the molded body support on which the first component compound and the second component compound are supported by the above steps [1] and [2]. The calcination conditions are not particularly limited as long as they allow the rhenium compound supported on the compact carrier to be converted into a sublimable rhenium compound, and the oxygen concentration may be 100% or the mixture may be diluted with an inert gas. The calcination treatment is preferably carried out in an oxygen-containing gas. The oxygen concentration of the calcination atmosphere is preferably 0.1% or more, more preferably 1% or more, and particularly preferably 18% or more. The inert gas here is defined as a gas that does not react with the metal support at the calcination temperature, and examples thereof include nitrogen, argon, and helium. In addition to oxygen and the inert gas, any other component may be included as long as it does not adversely affect the hydrogenation reaction using the catalyst. However, air is most preferably used because it can reduce the cost of catalyst production. By calcining in an oxygen-containing atmosphere, the rhenium-containing compound supported on the compact support can be oxidized to produce a sublimable, high-value rhenium species (e.g., rhenium(VII) oxide (dirhenium heptoxide)). This sublimable rhenium species repeatedly sublimates and re-adsorbs within the support during calcination, allowing the rhenium-containing compound to be highly dispersed on the compact support.

[0070] In the present invention, the shape of the container used for calcination is not particularly limited, but in order to prevent sublimable rhenium species from detaching from the molded body support and moving outside the catalyst molded body, a method of calcining in a sealed container such as a container with a lid is preferred. Among these, a container with a structure that does not excessively overlap the catalyst particles is more preferred in order to prevent uneven metal loading between the catalyst particles, and a container in which the ratio of the height to the positive square root of the bottom area of ​​the container is 20 times or less, more preferably 10 times or less, even more preferably 5 times or less, even more preferably 1 time or less, and particularly preferably 0.2 times or less. By setting the ratio of the height to the positive square root of the bottom area of ​​the container to the above upper limit or less, calcination can be performed without causing unevenness between the particles of the metal support.

[0071] The firing temperature is usually 200° C. or higher, preferably 250° C. or higher, more preferably 300° C. or higher, and usually 500° C. or lower, preferably 450° C. or lower, more preferably 400° C. or lower, particularly preferably 350° C. or lower. The firing time varies depending on the firing temperature, but is usually 30 minutes or longer, preferably 1 hour or longer, more preferably 2 hours or longer, and usually 40 hours or shorter, preferably 30 hours or shorter, more preferably 10 hours or shorter. By setting the calcination temperature within the above range, the rhenium-containing compound can be dispersed on the molded support without being desorbed from the molded support. That is, by calcining at or above the lower limit temperature, the sublimation of the sublimable rhenium species is not kinetically suppressed, and the dispersion of the rhenium component on the support is sufficiently promoted. Furthermore, by calcining at or below the upper limit temperature, the generated sublimable rhenium species can be prevented from desorbing from the molded support and moving out of the catalyst molded body. Therefore, the catalytic activity for the hydrogenation reaction of carbonyl compounds is maintained.

[0072] The rate of temperature rise required to reach the above temperature is not particularly limited, but is usually 0.01°C / min or more, preferably 0.1°C / min or more, more preferably 0.5°C / min or more, and particularly preferably 1°C / min or more, and is usually 200°C / min or less, preferably 100°C / min or less, more preferably 50°C / min or less, and particularly preferably 10°C / min or less. By setting the rate of temperature rise at or above the lower limit above, the time required for calcination can be reduced, thereby reducing the costs associated with catalyst production. By setting the rate of temperature rise at or below the upper limit above, it is possible to prevent temperature distribution within the calcined body and unevenness in the catalyst composition. The temperature may be increased at a constant rate or may be increased at a varying rate. When the temperature is increased at a varying rate, the average rate may be calculated by dividing the difference between the maximum temperature reached and the temperature at which the temperature increase starts (room temperature) by the total time required for the temperature increase.

[0073] In the present invention, as described above, by appropriately combining the calcination conditions, it is possible to suppress desorption of the rhenium-containing compound from the compacted support while promoting re-adsorption onto the support of the sublimable high-valent rhenium species that are partially produced, thereby achieving high dispersion of the rhenium-containing compound within the compacted support.

[0074] [4] Reduction process The reduction step is a step in which the molded support that has undergone the calcination step [3] is reduced in a hydrogen-containing gas. The hydrogen concentration of the hydrogen gas is not particularly limited, and the hydrogen gas may be 100% by volume or may be diluted with an inert gas. The inert gas referred to here is a gas that does not react with the metal support or hydrogen gas, and examples thereof include nitrogen and water vapor, but nitrogen is usually used. The hydrogen concentration of the hydrogen-containing gas diluted with an inert gas is usually 5% by volume or more, preferably 15% by volume or more, more preferably 30% by volume or more, and even more preferably 50% by volume or more, based on the total gas components. However, a hydrogen-containing gas with a low hydrogen concentration may be used at the beginning of the reduction, and then the hydrogen concentration may be gradually increased.

[0075] The time required for the reduction treatment varies depending on the amount of metal-supported material to be treated, the apparatus used, etc., but is usually 7 minutes or more, preferably 15 minutes or more, more preferably 30 minutes or more, and usually 40 hours or less, preferably 30 hours or less, more preferably 10 hours or less. The temperature during the reduction treatment is usually 100°C or more, preferably 200°C or more, more preferably 250°C or more, even more preferably 300°C or more, particularly preferably 350°C or more, and most preferably 400°C or more, and usually 700°C or less, preferably 600°C or less, more preferably 500°C or less. If the temperature during the reduction treatment is too high, sintering of the supported metal may occur, which may reduce the activity of the resulting catalyst.

[0076] The reducing gas used during the reduction treatment may be sealed in the reactor or circulated through the reactor, but circulating through the reactor is preferred. This is because circulating the gas can avoid local hydrogen deficiency. Depending on the raw material used, the reduction treatment may produce by-products such as water or ammonium chloride in the reactor, and these by-products may adversely affect the metal-supported material before the reduction treatment and the reduced metal-supported catalyst. However, circulating the reducing gas allows these by-products to be discharged outside the reaction system. The amount of reducing gas required for the reduction treatment is not particularly limited as long as the object of the present invention is satisfied, and can be appropriately set depending on the apparatus used, the size of the reactor during reduction, the method of flowing the reducing gas, the method of fluidizing the catalyst, etc.

[0077] The size of the metal-supported catalyst after reduction treatment is not particularly limited, but is basically the same as the size of the molded support described above. Preferred modes of the reduction treatment include a method in which a reducing gas is passed through a metal-supported material in a fixed bed, a method in which a reducing gas is passed through a metal-supported material placed stationary on a tray or belt, and a method in which a reducing gas is passed through a flowing metal-supported material.

[0078] <Applicable reaction examples> The reaction to which the present catalyst molded body is applied is not particularly limited, and the catalyst molded body can be suitably used for various hydrogenation reactions, such as the hydrogenation of carbonyl compounds, the hydrogenation of carbon dioxide, the hydrogenation of olefins, the hydrogenation of nitro compounds, and the hydrogenolysis of alcohols. As an example, the reduction reaction (hydrogenation) of a carbonyl compound will be explained below. The molded catalyst of the present invention is suitable as a reduction catalyst for carbonyl compounds, and by treating a carbonyl compound with the molded catalyst of the present invention, the corresponding alcohol can be produced. In the present invention, a carbonyl compound is defined as a compound having a carbon-oxygen double bond (C=O), and an alcohol is defined as a compound in which the carbonyl compound is converted into an alcohol functional group (OH). Therefore, in the present invention, when the carbonyl compound used as the raw material has a plurality of carbon-oxygen double bonds, a compound in which at least one of the double bonds has been converted into an alcohol functional group is defined as an alcohol. In the reduction reaction (hydrogenation) of the carbonyl compound, it is preferable to use a flow reactor from the viewpoint of productivity, for example, a method of producing alcohol in a flow reactor. In particular, by using the present catalyst molded body, it is possible to improve operability in the introduction and separation of the catalyst and reduce pressure loss.

[0079] A preferred embodiment of the reduction reaction using the present molded catalyst is, for example, a method for producing an alcohol, comprising a step of reducing at least one carbonyl compound selected from the group consisting of ketones, aldehydes, carboxylic acids, carboxylic acid esters, carboxylic acid amides, carboxylic acid halides, and carboxylic acid anhydrides to obtain an alcohol derived from the compound. The present molded catalyst is particularly characterized by its ability to directly reduce carboxylic acids, among these compounds, to produce an alcohol. Any carbonyl compound that is easily available industrially can be used as the target of the reduction reaction. Specifically, the carboxylic acid and / or carboxylic acid ester may be an aliphatic chain monocarboxylic acid such as acetic acid, butyric acid, decanoic acid, lauric acid, oleic acid, linoleic acid, linolenic acid, stearic acid, or palmitic acid, an aliphatic cyclic monocarboxylic acid such as cyclohexanecarboxylic acid, naphthenic acid, or cyclopentanecarboxylic acid, an oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, 1,2,4-butanetricarboxylic acid, or 1,3,4-cyclohexanetricarboxylic acid. Examples of suitable carboxylic acids include aliphatic polycarboxylic acids such as carboxylic acid, bicyclohexyldicarboxylic acid, and decahydronaphthalenedicarboxylic acid; aromatic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and trimesic acid; carboxylic acids having a furan skeleton such as furancarboxylic acid and furandicarboxylic acid; and carboxylic acid esters such as methyl esters, ethyl esters, propyl esters, and butyl esters of these carboxylic acids, and esters with alcohols obtained by reduction of the carboxylic acids; and lactones such as γ-butyrolactone, δ-valerolactone, and ε-caprolactone.

[0080] Examples of the carboxylic acid amide include methylamides and ethylamides of the above-mentioned carboxylic acids. Examples of the carboxylic acid halides include chlorides and bromides of the above-mentioned carboxylic acids. Examples of the carboxylic acid anhydride include acetic anhydride, succinic anhydride, maleic anhydride, and phthalic anhydride. Examples of aldehydes and ketones include benzaldehyde, propionaldehyde, acetaldehyde, 3-hydroxypropionaldehyde, furfural, hydroxymethylfurfural, acetone, benzophenone, glucose, xylose, lactose, and fructose.

[0081] The carboxylic acid forming these carboxylic acids, carboxylic acid esters, carboxylic acid amides, carboxylic acid halides, and / or carboxylic acid anhydrides is not particularly limited, but is preferably a linear or cyclic saturated aliphatic carboxylic acid, more preferably a carboxylic acid having 20 or less carbon atoms other than the carboxyl group, and even more preferably a carboxylic acid having 14 or less carbon atoms.

[0082] In the present invention, among the carbonyl compounds to be subjected to the reduction reaction, carboxylic acids, carboxylic acid esters, carboxylic acid anhydrides, and aldehydes are preferred because of their ease of availability as raw materials, and among these, carboxylic acids, carboxylic acid esters, carboxylic acid anhydrides, and aldehydes are more preferred, with carboxylic acids and carboxylic acid esters being particularly preferred.

[0083] The carboxylic acid is preferably a dicarboxylic acid, and more preferably a dicarboxylic acid having 20 or less carbon atoms other than the carboxyl group and represented by the following formula (2). HOOC-R1-COOH···(2) (In the formula, R1 represents an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms other than the substituent, which may have a substituent.)

[0084] The present molded catalyst has the characteristic of being able to convert polycarboxylic acids such as the above-mentioned dicarboxylic acids into the corresponding hydroxycarboxylic acids, lactones, and polyhydric alcohols with high selectivity and high yield. In this case, it is possible to control the production ratio of hydroxycarboxylic acids or lactones to polyhydric alcohols by appropriately selecting the production conditions, such as the catalyst used, reaction pressure, reaction temperature, and residence time of the raw materials.

[0085] Other particularly preferred carbonyl compounds include carboxylic acids having a furan skeleton derived from biomass resources, such as furandicarboxylic acid, and aldehydes, such as hydroxymethylfurfural.

[0086] The reduction reaction of carbonyl compounds using the present molded catalyst can be carried out in either a liquid or gas phase, but is preferably carried out in a liquid phase. The reduction reaction in the liquid phase using the present molded catalyst can be carried out either without a solvent or in the presence of a solvent, but is usually carried out in the presence of a solvent. As the solvent, typically, solvents such as water, lower alcohols such as methanol and ethanol, alcohols of the reaction product, ethers such as tetrahydrofuran, dioxane, and ethylene glycol dimethyl ether, hydrocarbons such as hexane, decalin, and methylcyclohexane can be used. These solvents can be used alone or in combination of two or more. The amount of the solvent used is not particularly limited, but is usually about 0.1 to 20 times by mass, preferably 0.5 to 10 times by mass, and more preferably 1 to 10 times by mass relative to the carbonyl compound used as the raw material.

[0087] The reduction reaction of a carbonyl compound using the present molded catalyst is usually carried out under pressurized hydrogen gas. The reaction is usually carried out at 100 to 300°C, preferably 120 to 250°C. The reaction pressure is usually 1 to 30 MPaG, preferably 1 to 25 MPaG, and more preferably 5 to 25 MPaG. The product obtained in the reduction reaction using the present catalyst molded body can be recovered after the reaction is completed, depending on the physical properties of the product, but can usually be recovered by solvent distillation, solvent distillation followed by extraction with an organic solvent, distillation, sublimation, crystallization, chromatography, etc. If the product is liquid under the handling temperature conditions, a method of recovering the product while purifying it by distillation is preferred. If the product is solid under the handling temperature conditions, a method of recovering the product while purifying it by crystallization is preferred. A preferred embodiment is a method of purifying the obtained solid product by washing. [Example]

[0088] The present invention will be explained in more detail below by way of examples, but the present invention is not limited to the following examples as long as it does not depart from the gist of the invention.

[0089] <Measurement of loading distribution> The substrate was cut along the plane where it was divided so that the volume ratio after division was approximately 1:1, and then subjected to a conductive treatment using carbon. SEM-EDS observations were performed using a Hitachi High-Technologies SU5000 Schottky scanning electron microscope equipped with a Bruker AXS QUANTAX FlatQUAD direct-top EDS detector, and line profiles of the rhenium Lα line and germanium L line intensities in the cross section of the molded catalyst were obtained using analysis software Bruker AXS Esprit 2.3. From the obtained line profiles, the coefficient of variation of the amount of metal component loaded within the molded catalyst and the first quartile relative to the third quartile of the amount loaded were calculated. The measurement conditions were: accelerating voltage 15 kV, spot intensity 50.0, working distance 11.0 mm, measurement magnification 70x, image pixel count 512 x 384, pulse input 130 kcps, acquisition time 300 seconds, and dwell time 16 μs for EDS measurements. Furthermore, intensity quantification for line profiles was performed using count values ​​without background subtraction or peak separation. The counts for each element were calculated based on an energy range encompassing 87% of the main peak value for the rhenium Lα and germanium L lines. Line profiles were acquired at 3.56 μm intervals to obtain the intensity distribution. At least three specimens were measured for each sample.

[0090] <Catalyst reaction activity> A 70 mL high-pressure reactor was charged with 40 mg of the catalyst prepared in each Example and Comparative Example, 500 mg of decanoic acid, 4.5 mL of methylcyclohexane, and a stirrer chip. After purging with nitrogen, hydrogen gas was introduced at room temperature at 4.3 MPaG, and the hydrogenation reaction was carried out at 200°C for 1 hour. The reaction pressure at 200°C was 7.0 MPaG. After the reaction, the reaction mixture was cooled to room temperature and depressurized, and the reaction mixture was analyzed using a gas chromatograph.

[0091] Example 1 4.70 g of germanium oxide was dissolved in 400 g of room-temperature water, and 100 g of titanium oxide spherical bodies (CS-300S-12, manufactured by Sakai Chemical Industry Co., Ltd., pore volume 0.4 mL / g, spheres with diameters of 1–2 mm (average diameter 1.6 mm)) was added. The water was removed using an evaporator, and the mixture was then dried under vacuum at 80°C for 1 hour (germanium oxide / titanium oxide). 7.83 g of ammonium perrhenate was added to 40 mL of water equal to the pore volume of the titanium oxide bodies and heated to 80°C. The germanium oxide / titanium oxide heated to 80°C was then added to the mixture, and the mixture was then heated to 120°C and dried. The resulting metal-supported product was placed in a petri dish with a height-to-square-root-of-base-area ratio of 0.11 and calcined in air (oxygen concentration 21%) at 300°C for 3 hours in a muffle furnace. The obtained solid was placed in a vertical calcination tube and reduced at 500°C for 30 minutes while passing hydrogen gas through it. After that, it was cooled to 30°C, and the rhenium / germanium / titanium oxide catalyst molded body (spheres with a diameter of 1 to 2 mm (average diameter 1.6 mm)) was stored under argon. Figure 3 shows line profiles of the rhenium Lα and germanium L line intensities in rectangular regions 100 μm on either side of the line dividing the cross section of a rhenium / germanium / titanium oxide catalyst molded body into two halves at a volume ratio of approximately 1:1. From these profiles, histograms of the rhenium Lα and germanium L line intensities in the above regions are shown in Figures 4 and 5, respectively. From Figures 4 and 5, the coefficients of variation of the rhenium and germanium loading amounts at the center of the catalyst were calculated to be 0.06 and 0.07, respectively. Furthermore, the first quartile of the rhenium and germanium loading amounts relative to the third quartile were calculated to be 92% and 91%, respectively. Similar analysis was performed on three samples of catalyst compact particles, and the average values ​​were calculated. The coefficients of variation for the rhenium and germanium loadings were 0.08 and 0.09, respectively, and the first quartile relative to the third quartile was 90% and 90%, respectively. The catalytic activity was evaluated using the above method. The molar yield of the reaction was 58.4% for 1-decanol and 12.1% for decyl decanoate, resulting in a yield of 70.5% for the target components (decanol and decyl decanoate). The molar ratio of by-products (nonane and decane) to target components (decanol and decyl decanoate) was below the detection limit (<0.001).

[0092] <Example 2> A rhenium / germanium / titanium oxide catalyst molded body (spheres with diameters of 1 to 2 mm (average diameter 1.6 mm)) was prepared in the same manner as in Example 1, except that germanium oxide / titanium oxide at room temperature (25°C) was added to an aqueous solution of ammonium perrhenate instead of germanium oxide / titanium oxide heated to 80°C. Analysis was performed in the same manner as in Example 1, and the coefficients of variation of the rhenium and germanium loading amounts at the center of the catalyst were 0.15 and 0.18, respectively, and the first quartile relative to the third quartile of the loading amount was 81% and 79%, respectively. The catalytic activity was evaluated by the same method as in Example 1. The molar yields of the reaction were 33.4% for 1-decanol and 13.0% for decyl decanoate, and the yield of the target components (decanol, decyl decanoate) was 46.4%. The molar ratio of by-products (nonane, decane) to target components (decanol, decyl decanoate) was 0.0015.

[0093] Example 3 A rhenium / germanium / titanium oxide catalyst molded body (spherical, 1 to 2 mm in diameter (average diameter 1.6 mm)) was prepared in the same manner as in Example 1, except that instead of performing calcination treatment in air at 300°C for 3 hours, calcination treatment was performed in air (oxygen concentration 21%) at 500°C for 3 hours. Analysis was performed in the same manner as in Example 1, and the coefficients of variation of the rhenium and germanium loading amounts at the catalyst center were 0.18 and 0.15, respectively, and the first quartile relative to the third quartile of the loading amount was 79% and 82%, respectively. The catalytic activity was evaluated by the same method as in Example 1. The molar yields of the reaction were 31.6% for 1-decanol and 14.3% for decyl decanoate, and the yield of the target components (decanol, decyl decanoate) was 45.9%. The molar ratio of by-products (nonane, decane) to target components (decanol, decyl decanoate) was 0.0016.

[0094] Example 4 0.783 g of ammonium perrhenate was added to 40 mL of water with the same volume as the pore volume of the titanium oxide molded body and heated to 80°C. 10 g of titanium oxide spherical molded body (CS-300S-12, Sakai Chemical Industry Co., Ltd., pore volume 0.4 mL / g, 1-2 mm diameter spheres (average diameter 1.6 mm)) heated to 80°C was added thereto, and the mixture was heated to 120°C and dried. The resulting metal-supported product was placed in a vertical calcination tube and calcined at 300°C for 3 hours while flowing air (oxygen concentration 21%). The resulting solid was then placed in a vertical calcination tube and reduced at 500°C for 30 minutes while flowing hydrogen gas. The mixture was then cooled to 30°C, and the rhenium / titanium oxide catalyst molded body (1-2 mm diameter spheres (average diameter 1.6 mm)) was stored under argon. As a result of carrying out the same analysis as in Example 1, the coefficient of variation of the amount of supported rhenium in the center of the catalyst was 0.23, and the first quartile of the supported amount relative to the third quartile was 73%. The reaction activity of the catalyst was evaluated by the same method as in Example 1. The molar yield of the reaction was 20.1% for 1-decanol and 7.9% for decyl decanoate, and the yield of the target components (decanol, decyl decanoate) was 28.0%. The molar ratio of by-products (nonane, decane) to target components (decanol, decyl decanoate) was 0.0100.

[0095] <Comparative Example 1> 0.783 g of ammonium perrhenate and 0.470 g of germanium oxide were dissolved in 40 g of water, and 10 g of titanium oxide spherical bodies (CS-300S-12, Sakai Chemical Industry Co., Ltd., pore volume 0.4 mL / g, 1-2 mm diameter spheres (average diameter 1.6 mm)) were added. Water was removed using an evaporator under reduced pressure at 80°C. The metal support was placed in a vertical calcination tube and calcined for 3 hours at 300°C while flowing air (oxygen concentration 21%). The resulting solid was placed in a vertical calcination tube and reduced for 30 minutes at 500°C while flowing hydrogen. The mixture was then cooled to 30°C, and the rhenium-germanium / titanium oxide catalyst bodies (1-2 mm diameter spheres (average diameter 1.6 mm)) were stored under argon. As a result of the same analysis as in Example 1, the coefficients of variation of the amounts of rhenium and germanium supported at the center of the catalyst were 0.27 and 0.18, respectively, and the first quartile relative to the third quartile of the supported amount was 68% and 78%, respectively. The reaction activity of the catalyst was evaluated by the same method as in Example 1. The molar yield of the reaction was 23.3% for 1-decanol and 12.8% for decyl decanoate, resulting in a yield of 36.1% for the target components (decanol, decyl decanoate). The molar ratio of by-products (nonane, decane) to target components (decanol, decyl decanoate) was below the detection limit (<0.001).

[0096] <Comparative Example 2> 0.783 g of ammonium perrhenate was dissolved in 40 g of water, and 10 g of titanium oxide spherical bodies (CS-300S-12, manufactured by Sakai Chemical Industry Co., Ltd., 1-2 mm diameter spheres (average diameter 1.6 mm)) was added. Water was removed using an evaporator under reduced pressure at 80°C. The metal support was placed in a vertical calcination tube and calcined for 3 hours at 300°C while flowing air (oxygen concentration 21%). The resulting solid was placed in a vertical calcination tube and reduced for 30 minutes at 500°C while flowing hydrogen. The mixture was then cooled to 30°C, and the rhenium / titanium oxide (evaporated to dryness) catalyst bodies (1-2 mm diameter spheres (average diameter 1.6 mm)) were stored under argon. As a result of carrying out the same analysis as in Example 1, the coefficient of variation of the amount of supported rhenium in the center of the catalyst was 0.27, and the first quartile of the supported amount relative to the third quartile was 70%. The reaction activity of the catalyst was evaluated by the same method as in Example 1. The molar yield of the reaction was 9.2% for 1-decanol and 4.9% for decyl decanoate, and the yield of the target components (decanol, decyl decanoate) was 14.1%. The molar ratio of by-products (nonane, decane) to target components (decanol, decyl decanoate) was 0.0160.

[0097] The results of Examples 1 to 4 and Comparative Examples 1 and 2 are summarized in Table 1.

[0098] [Table 1]

[0099] A comparison of Examples 1 to 4, which used a rhenium catalyst supported on a titanium oxide molded body, with Comparative Examples 1 and 2 revealed that the catalyst molded body produced by the production method of the present invention exhibits high catalytic activity for the reaction of producing alcohol from a carbonyl compound. As described above, the present invention solves the problem of reduced activity in molded catalyst bodies, provides a method for producing industrially useful molded catalyst bodies, and contributes to the development of industrial chemical production technology.

[0100] A comparison of Examples 1 to 4 and Comparative Examples 1 and 2, which used the above rhenium catalyst supported on a titanium oxide molded body, showed that catalyst molded bodies in which the coefficient of variation of the rhenium loading at the catalyst center was 0.25 or less solved the problem of reduced activity in catalyst molded bodies and showed high catalytic activity for the reaction of producing alcohol from carbonyl compounds. More specifically, as is clear from the comparison results between Example 4 and Comparative Example 2, it was confirmed that when the coefficient of variation of rhenium is 0.25 or less, the yield of the target component is improved, the ratio of by-products to the target component is reduced, and selectivity is improved. Furthermore, a comparison between Examples 1 to 3 and Comparative Example 1 showed that when the metal component of the catalyst molding contains germanium as a second component in addition to rhenium, catalyst moldings in which the coefficients of variation of the rhenium and germanium loadings at the catalyst center were both 0.25 or less exhibited high catalytic activity for the reaction of producing alcohol from a carbonyl compound. As described above, the present invention solves the problem of reduced activity in catalyst molded bodies, provides a catalyst molded body that is industrially useful, in which rhenium is uniformly supported on a molded body support, and contributes to the development of industrial chemical production technology. [Industrial Applicability]

[0101] The present invention provides an industrially useful rhenium-containing shaped catalyst supported on a shaped support, and a method for producing the same. The shaped catalyst is industrially useful as a catalyst for various hydrogenation reactions, and its industrial value is extremely high. Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention. [Explanation of symbols]

[0102] 1. Cross section of catalyst compact 2 Hollow part 3, 3' region a Line segment when the cross-sectional area ratio is 1:1 b A line segment drawn so that the cross-sectional area ratio (top:bottom) is 1:2 c A line segment drawn so that the cross-sectional area ratio (bottom:top) is 1:2 X, Y, X', Y' Ends of line segments X1, X1': points 10% of the length from the ends X and X' X2, X2' 90% of the length from the ends X and X'

Claims

1. A catalyst molded body in which a metal component containing rhenium is supported on a molded body support, wherein in a cross section of the catalyst molded body, in a rectangular region extending 10 to 90% in length from one end of a line segment dividing the cross section into two and having a width of 100 μm on each side of the line segment, the coefficient of variation of the amount of rhenium supported in a direction parallel to the line segment is 0.25 or less.

2. The catalyst molded body according to claim 1 , wherein the catalyst molded body is spherical.

3. The catalyst molded article according to claim 1 , wherein the catalyst molded article is columnar.

4. 2. The catalyst molded body according to claim 1, wherein the first quartile of the distribution of the amount of rhenium loaded in said region is 70% or more of the third quartile.

5. 2. The catalyst molded body according to claim 1, wherein the metal component contains, as a second component, one or more elements selected from the group consisting of elements belonging to Groups 13 to 15 of the third period or later and elements belonging to Groups 8 to 10.

6. 6. The molded catalyst body according to claim 5, wherein a coefficient of variation of the amount of the second component supported in the region is 0.25 or less.

7. 6. The catalyst molded article according to claim 5, wherein a first quartile of the distribution of the supported amount of the second component in the region is 70% or more of a third quartile.

8. 2. The catalyst shaped body according to claim 1, wherein the shaped body support comprises an oxide of a metal of Group 4 of the periodic table.

9. 2. The catalyst molded body according to claim 1, wherein the molded body support is spherical and has a diameter of 0.34 mm or more and 10 mm or less, or cylindrical and has a circumscribed circle diameter of 0.34 mm or more and 10 mm or less and a length of 0.5 mm or more and 50 mm or less.

10. 2. The catalyst shaped body according to claim 1, which is used as a catalyst for producing an alcohol from a carbonyl compound.

11. A method for producing an alcohol, comprising bringing a carbonyl compound into contact with the shaped catalyst according to any one of claims 1 to 10 in the presence of the shaped catalyst to produce a corresponding alcohol.

12. The method for producing alcohol according to claim 11, wherein the alcohol is produced in a flow reactor.

13. A method for producing a catalyst molded body including a metal component containing rhenium as a first component, the method comprising sequentially carrying out the following steps [2] to [4]: Step [2]: A first component supporting step, which comprises supporting a rhenium-containing compound on a molded support to obtain a metal-supported precursor. Step [3]: A calcination step comprising calcining the metal-supported precursor to obtain a metal-supported material. Step [4]: ​​A reduction step, which includes reducing the metal-supported material in a reducing gas to obtain a catalyst molded body containing a metal component containing rhenium.

14. The method for producing a catalyst molded body according to claim 13, comprising the following step [1] before the step [2]: Step [1]: A second component supporting step in which one or more metals selected from elements belonging to Groups 13 to 15 of the third period or later and elements belonging to Groups 8 to 10 are supported on a molded support as a second component.

15. The method for producing a molded catalyst body according to claim 13 or 14, wherein in the step [3], the calcination treatment is carried out in an oxygen-containing gas.

16. The method for producing a molded catalyst body according to claim 13 or 14, further comprising a drying step after the step [1] and before the step [2].

17. 15. The method for producing a catalyst molded body according to claim 13 or 14, wherein the step [2] is a step of supporting a rhenium-containing compound on a molded body support, and the temperature of the solution or dispersion is 10°C or higher when the solution or dispersion is mixed with the molded body support.

18. The method for producing a molded catalyst body according to claim 17, wherein the temperature difference between the solution or dispersion and the molded support is controlled to be 50°C or less.

19. The method for producing a molded catalyst according to claim 18, wherein the temperature difference between the solution or dispersion and the molded support is controlled to be 20°C or less.

20. The method for producing a molded catalyst body according to claim 13 or 14, wherein the molded body support comprises an oxide of a metal of Group 4 of the periodic table.

21. The method for producing a molded catalyst body according to claim 14, wherein the second component contains germanium.

22. The method for producing a molded catalyst body according to claim 17, wherein the rhenium-containing compound comprises at least one selected from perrhenic acid and perrhenates.

23. The method for producing a molded catalyst according to claim 13 or 14, wherein the molded catalyst is used as a catalyst for producing a corresponding alcohol from a carbonyl compound.

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