Method for manufacturing alcohol

Abstract

To provide a method for manufacturing alcohols capable of manufacturing a desired alcohol with high yield and high selectivity through the hydrogenation reaction of carbonyl compounds using a rhenium-containing metal catalyst molded article supported on a molded carrier in an industrially useful form.SOLUTION: In an alcohol manufacturing method for manufacturing alcohols from carbonyl compounds, a catalyst molded article in which a metal component containing rhenium is supported on a molded carrier is used as a catalyst. 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 method for producing alcohol, and more particularly to a method for producing alcohol by hydrogenating a carbonyl compound using a molded catalyst. [Background technology]

[0002] Methods for producing alcohols by hydrogenating carbonyl compounds have been known for a long time. For example, a commonly used method for producing alcohols from organic carboxylic acids is to first esterify the carboxylic acid with a lower alcohol and then reduce it with an Adkins catalyst (copper chromite catalyst). However, alcohol production using copper catalysts is generally carried out under harsh conditions, such as hydrogen pressures of 200 atmospheres or more, resulting in a wasteful process that consumes a great deal of energy during alcohol production and has many equipment limitations. Furthermore, copper catalysts cannot directly reduce organic carboxylic acids; instead, the carboxylic acid must first be converted to a carboxylic acid ester and then reduced. This makes the production of the target alcohol a complicated process involving multiple reaction steps. Furthermore, with such production methods, it is extremely difficult to selectively produce hydroxycarboxylic acids in which some of the carboxylic acid functional groups have been converted to alcohol functional groups, for example, when using polycarboxylic acids as raw materials.

[0003] On the other hand, a method for directly hydrogenating (reducing) a carboxylic acid in one step and producing the corresponding alcohol with high selectivity is an economically advantageous process. When using a polycarboxylic acid as a raw material, if the reaction conditions are appropriately controlled, it is also possible to selectively produce the corresponding hydroxycarboxylic acid. As catalysts for use in such processes, various metal-supported catalysts have been proposed, which contain a noble metal belonging to Groups 8 to 10 of the periodic table as the catalytically active component. For example, catalysts in which palladium and rhenium are supported on a carrier and then reduced with hydrogen or the like (e.g., Patent Document 1 and Non-Patent Document 1), and catalysts in which ruthenium and tin are supported on a carrier and then reduced with hydrogen or the like (e.g., Patent Documents 2 and 3) have been proposed. These catalysts are excellent catalysts that exhibit high reaction activity and reaction selectivity in the reduction of carboxylic acids and / or carboxylic acid esters. In addition, as this type of catalyst, a cobalt-based catalyst containing lanthanum and palladium (e.g., Patent Document 4) has also been proposed for the hydrogenation reaction of specific carboxylic acids.

[0004] In response to this, catalysts that do not use expensive noble metals belonging to Groups 8 to 10 of the periodic table have also been proposed. For example, catalysts using rhenium as a catalytic component have long been reported (e.g., Non-Patent Document 2). Furthermore, tin-containing rhenium-based catalysts have also been proposed for the hydrogenation reaction of specific carboxylic acids (e.g., Patent Document 5). Furthermore, as a method for selectively producing target alcohols under milder reaction conditions, a production method using a metal-supported catalyst containing rhenium as a catalytically active component has been reported (e.g., Non-Patent Documents 3 and 4). However, catalysts containing only rhenium as a catalytically active component have inferior catalytic activity compared to catalysts using noble metals. Therefore, methods for producing alcohol with high activity and selectivity by reducing carbonyl compounds have been reported, using one or more catalytically active components selected from the group consisting of silicon, gallium, germanium, and indium in addition to rhenium (see, for example, Patent Documents 6 and 7). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 63-218636 [Patent Document 2] Japanese Patent Application Laid-Open No. 2000-007596 [Patent Document 3] Japanese Patent Application Laid-Open No. 2001-157841 [Patent Document 4] Japanese Patent Application Publication No. 63-301845 [Patent Document 5] Japanese Patent Application Publication No. 4-99753 [Patent Document 6] WO2018 / 164193 [Patent Document 7] WO2020 / 022256 [Non-patent literature]

[0006] [Non-Patent Document 1] Topics in Catalysis 55 (2012) 466-473 [Non-patent document 2] Journal of Organic Chemistry 24 (1959) 1847-1854 [Non-patent document 3] Journal of Catalysis 328 (2015) 197-207 [Non-patent document 4] Chemistry A European Journal 23 (2017) 1001-1006 Summary of the Invention [Problem to be solved by the invention]

[0007] When carrying out the reduction reaction of a carbonyl compound, for example, a batch-type or flow-type reactor can be used. In either type of reactor, the catalyst is preferably in the form of a structure having a size of approximately 0.1 mm or more, rather than a powder, from the viewpoint of operability in adding and separating the catalyst, and in the case of a flow-type reactor, reduction of pressure loss. However, compared to supporting a metal component on a powder support, supporting a metal component on a compact support generally tends to result in non-uniformity of the supported metal component, which poses a problem of reduced catalytic activity. Even with a rhenium-containing metal catalyst supported on a molded support, there is a problem in that the catalytic activity for the reaction of producing alcohol from a carbonyl compound is significantly lower than that of a powder catalyst. The present invention aims to solve the problem of the decline in activity of the catalyst shaped body and to provide a method for producing an alcohol, which can produce a target alcohol in high yield and with high selectivity by a hydrogenation reaction of a carbonyl compound using a rhenium-containing metal catalyst shaped body supported on a shaped body support, which is an industrially useful form. [Means for solving the problem]

[0008] The present inventors have found that a molded catalyst in which rhenium is supported on a molded support in a specific distribution can solve the above-mentioned problems, and have completed the present invention. [1] A method for producing alcohol from a carbonyl compound, using a catalyst molded body in which a metal component containing rhenium is supported on a molded body support as a catalyst, 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 both sides 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 method for producing an alcohol according to the above [1], wherein the catalyst molded body is spherical. [3] The method for producing an alcohol according to the above [1], wherein the catalyst molded body is columnar. [4] The method for producing an alcohol according to any one of the above [1] to [3], wherein the first quartile of the distribution of the amount of rhenium supported in the region is 70% or more of the third quartile. [5] The method for producing an alcohol 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. [6] The method for producing an alcohol according to [5] above, wherein the coefficient of variation of the amount of the second component supported in the region is 0.25 or less. [7] The method for producing an alcohol 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 method for producing an alcohol according to any one of the above [1] to [7], wherein the shaped support contains an oxide of a metal of Group 4 of the periodic table. [9] The method for producing an alcohol according to any one of [1] to [8] above, wherein the shaped carrier 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 method for producing the alcohol according to any one of the above [1] to [9], wherein the alcohol is produced in a flow reactor. [Effects of the Invention]

[0009] According to the present invention, there can be provided a method for producing a target alcohol in high yield and with high selectivity by a hydrogenation reaction of a carbonyl compound using a rhenium-containing metal catalyst shaped body supported on a shaped body support, which is an industrially useful form. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 2 is a schematic diagram showing a cross section of a catalyst molded body. [Figure 2] FIG. 2 is a schematic diagram showing a cross-sectional view of a catalyst molded body having a hollow structure. [Figure 3] 1 shows line profiles of the intensities of rhenium Lα line and germanium L line in rectangular regions of 100 μm on both sides of a line segment dividing the cross section in half in Example 1. [Figure 4] 1 is a histogram of the intensity distribution of rhenium Lα rays in Example 1. [Figure 5] 1 is a histogram of the intensity distribution of germanium L lines in Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0011] 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 and one or more elements selected from the group of elements belonging to Groups 13 to 15 of the third period or later 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," and a metal-supported material that has been subjected to reduction treatment is sometimes called a "metal-supported catalyst."

[0012] [Alcohol production method] The alcohol production method of the present invention is a method for producing an alcohol from a carbonyl compound, and uses a catalyst molded body in which a metal component containing rhenium is supported on a molded body support as a catalyst, and in the cross section of the catalyst molded body, 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 both sides of the line segment has a coefficient of variation of 0.25 or less in the amount of rhenium supported. The molded catalyst body produced in the production method of the present invention will now be described.

[0013] [Catalyst molding] The molded catalyst according to 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.

[0014] 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.

[0015] 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 cylindrical, spherical, hollow spherical, honeycomb, or shapes lacking a portion thereof or having an uneven structure such as protrusions can be used. This also includes a cylindrical shape. Furthermore, the cross-sectional shape of the columnar catalyst molded body can be any of circular, polygonal, hollow circular, trilobal, and quadrolobal shapes. Of these, spherical and cylindrical shapes are preferred in terms of ease of handling. Below, spherical and cylindrical shapes will be described as examples.

[0016] 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.

[0017] 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.

[0018] 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.

[0019] <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 carried in the center of the catalyst within the above range, aggregation of the carried rhenium can be suppressed.

[0020] 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.

[0021] Furthermore, 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 reaction selectivity 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.

[0022] When the rhenium-containing catalyst contains the 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. In other words, the catalytic activity and selectivity for the hydrogenation reaction of carbonyl compounds can be improved.

[0023] 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 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 coefficient of variation of the amount of the second component supported to the coefficient of variation of the amount of rhenium supported at 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 at the catalyst center within the above range, rhenium and the second component can be mixed uniformly, and the effect of adding the second component can be enhanced. In other words, the catalytic activity and selectivity for the hydrogenation reaction of carbonyl compounds can be improved.

[0025] <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).

[0026] 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.

[0027] 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.

[0028]

number

[0029] 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.

[0030] 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 periodic table from the third period onward. 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. In the present invention, the periodic table refers to the long-form periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005).

[0031] (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. In addition, the reaction selectivity is high and catalyst costs can be reduced. 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.

[0032] 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 the second component to be combined with rhenium and / or the ratio of the amount carried thereon within the above range, the effect of adding the second component can be enhanced.

[0033] 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 the latter stage of the reaction, in particular. 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.

[0034] (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 metals in Groups 8 to 10 of the periodic table excluding iron and nickel, silver, gold, molybdenum, tungsten, aluminum, and boron.

[0035] In addition, when metals such as iron and nickel are dissolved and mixed into the catalyst molded body due to corrosion of a reaction vessel made of SS, SUS, etc., in the present invention, the content of metal components in the catalyst molded body can be the amount excluding the iron content and the above-mentioned metal content in a specific ratio determined depending on the material of the reaction vessel, and it is preferable to calculate the content of metal components in the catalyst molded body excluding these contents.

[0036] For example, if contamination occurs from SUS201, nickel, chromium, and manganese are detected in specific quantitative ratios along with iron. If contamination occurs from SUS202, nickel, chromium, and manganese are detected in specific quantitative ratios along with iron. If contamination occurs from SUS301, nickel and chromium are detected in specific quantitative ratios along with iron. If contamination occurs from SUS302, nickel and chromium are detected in specific quantitative ratios along with iron. If contamination occurs from SUS303, nickel, chromium, and molybdenum are detected in specific quantitative ratios along with iron. If contamination occurs from SUS304, nickel and chromium are detected in specific quantitative ratios along with iron. If contamination occurs from SUS305, nickel and chromium are detected in specific quantitative ratios along with iron. If contamination occurs from SUS316, nickel, chromium, and molybdenum are detected in specific quantitative ratios along with iron. If contamination occurs from SUS317, nickel, chromium, and molybdenum are detected in specific quantitative ratios along with iron. If the contamination is from SUS329J1, nickel, chromium, and molybdenum will be detected in specific ratios along with iron. If the contamination is from SUS403, chromium will be detected in specific ratios along with iron. If the contamination is from SUS405, chromium and aluminum will be detected in specific ratios along with iron. If the contamination is from SUS420, chromium will be detected in specific ratios along with iron. If the contamination is from SUS430, chromium will be detected in specific ratios along with iron. If the contamination is from SUS430LX, chromium, titanium, or niobium will be detected in specific ratios along with iron. If the contamination is from SUS630, nickel, chromium, copper, and niobium will be detected in specific ratios along with iron.

[0037] Of these third components, at least one metal selected from ruthenium, cobalt, rhodium, iridium, palladium, platinum, gold, molybdenum, and tungsten is preferred, and among these, at least one metal selected from ruthenium, cobalt, rhodium, iridium, palladium, platinum, molybdenum, and tungsten is more preferred, and further, at least one metal selected from ruthenium, iridium, palladium, and platinum is particularly preferred, and among these, ruthenium is particularly preferred.

[0038] (Amount of the third component supported) The content of these third components contained in the present catalyst molded body, in terms of the element mass ratio to rhenium, for rare and expensive metals in Groups 8 to 10 of the periodic table excluding iron and nickel, is usually less than 0.2, preferably 0.15 or less, more preferably 0.1 or less, even more preferably less than 0.1, and most preferably 0, for reasons of improving reaction selectivity and reducing the cost of producing the catalyst molded body. In other words, it is preferable that the present catalyst molded body is substantially free of rare and expensive metals in Groups 8 to 10 of the periodic table excluding iron and nickel.

[0039] In the case of the third metal component other than the noble metals of Groups 8 to 10 of the periodic table, the mass ratio of the element to rhenium is usually 10 or less, preferably 5 or less, more preferably 1 or less, and even more preferably 0.5 or less. By selecting an appropriate combination and appropriate contents of these additional metal components, high catalytic activity can be obtained while maintaining high selectivity.

[0040] 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.

[0041] <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.

[0042] 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.

[0043] 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.

[0044] 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 than 2 mm, even more preferably 3 More than 5 × 10 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.

[0045] 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.

[0046] 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).

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] <Alcohol production method> The present molded catalyst is suitable as a catalyst for the reduction reaction (hydrogenation) of carbonyl compounds, and alcohols can be produced by treating carbonyl compounds with the present molded catalyst. 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.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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.)

[0058] 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.

[0059] 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.

[0060] The reduction reaction using the present molded catalyst can be carried out in either a liquid phase or a 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.

[0061] The reduction reaction using the present catalyst molded body 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.

[0062] In the alcohol production method of the present invention, it is preferable to use a flow reactor from the viewpoint of productivity, and for example, a method of producing alcohol in a flow reactor is preferred. In particular, by using the present catalyst molded body, operability in catalyst introduction and separation can be improved and pressure loss can be reduced.

[0063] [Method of manufacturing a molded catalyst] The method for producing a molded catalyst according to the present invention preferably includes the following steps [1] to [4]. [1] A step of supporting a compound containing a second component on a molded body carrier (a step of supporting the second component) [2] A step of supporting a first component-containing compound on a molded body carrier supporting a second component-containing compound (first component supporting step) [3] A step of firing the molded support carrying the first component-containing compound and the second component-containing compound in an oxygen-containing gas atmosphere (firing step). [4] A step of reducing the molded support that has undergone the calcination step in a hydrogen-containing gas (reduction step).

[0064] Each step will be explained below in order. [1] Second component loading step The second component supporting step is a step of supporting a necessary amount of a second component-containing compound on the above-mentioned molded support to produce a second component-supported material. As described above, the second component contains 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 preferably contains one or more elements selected from the group consisting of silicon, germanium, and indium. More preferably, the second component contains one or more elements including germanium, and particularly preferably contains germanium.

[0065] In the second component supporting step, a solution or dispersion of various metal-containing compounds that serve as raw materials for the metal components can be used to support the above-mentioned elements (metals). 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 in the first component supporting step below, and the preferred ranges are also the same.

[0066] 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.

[0067] 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.

[0068] When the second component is a metal containing germanium, which is particularly preferred, the metal-containing compound is not particularly limited, and examples of the metal-containing compound that can be used include metal complexes such as 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] [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].

[0074] 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.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] [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.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] [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.

[0090] 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.

[0091] 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.

[0092] 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. [Example]

[0093] 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.

[0094] <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.

[0095] <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.

[0096] 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).

[0097] <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.

[0098] 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.

[0099] 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.

[0100] <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).

[0101] <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.

[0102] The results of Examples 1 to 4 and Comparative Examples 1 and 2 are summarized in Table 1.

[0103] [Table 1]

[0104] 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, revealed that catalyst molded bodies in which the coefficient of variation of the amount of rhenium supported at the center of the catalyst was 0.25 or less solved the problem of reduced activity in the catalyst molded body 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 and provides an industrially useful catalyst molded body in which rhenium is uniformly supported on a molded body support, as well as a method for producing alcohol by hydrogenating a carbonyl compound using the catalyst molded body, thereby contributing to the development of industrial alcohol production technology. [Industrial Applicability]

[0105] The present invention provides an industrially useful rhenium-containing shaped catalyst supported on a shaped support, which is an industrially useful catalyst for directly synthesizing alcohols from carbonyl compounds, and is therefore of great industrial value. 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]

[0106] 1. Cross section of catalyst compact 2 Hollow part 3, 3' area 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 method for producing alcohol from a carbonyl compound, the method using a catalyst molded body in which a metal component containing rhenium is supported on a molded body support as a catalyst, wherein in a cross section of the catalyst molded body, in a rectangular region that is 10 to 90% in length from one end of a line segment that divides the cross section into two and has a width of 100 μm on both sides 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 method for producing alcohol according to claim 1 , wherein the catalyst molded body is spherical.

3. The method for producing an alcohol according to claim 1 , wherein the catalyst molded body has a columnar shape.

4. 2. The method for producing an alcohol according to claim 1, wherein the first quartile of the distribution of the amount of rhenium supported in the region is 70% or more of the third quartile.

5. 2. The method for producing an alcohol 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.

6. The method for producing an alcohol 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. The method for producing an alcohol 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. The method for producing an alcohol according to claim 1 , wherein the shaped support contains an oxide of a metal of Group 4 of the periodic table.

9. 2. The method for producing an alcohol according to claim 1, wherein the shaped carrier is spherical and has a diameter of 0.34 mm to 10 mm, or cylindrical and has a circumscribed circle having a diameter of 0.34 mm to 10 mm in cross section and a length of 0.5 mm to 50 mm.

10. The method for producing alcohol according to claim 1, wherein the alcohol is produced in a flow reactor.

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