JPWO2015178459A1 - Metal-supported catalyst, method for storing metal-supported catalyst, and method for producing alcohol - Google Patents

Abstract

An object of the present invention is to provide a metal-supported catalyst that has high catalytic activity and selectivity and can be handled in air. The present invention contains Ru and Sn, the half width of the peak at 2θ = 43 ° of powder X-ray diffraction analysis is 3.61 ° or less, and the oxidation rate represented by [X / Y] × 100 is 38%. The present invention relates to the above metal-supported catalyst. X represents the number of moles of oxygen required to oxidize the metal-supported catalyst when the metal-supported catalyst is subjected to temperature reduction and then oxidized at room temperature, and Y is supported on the metal-supported catalyst. Represents the total number of moles of metal formed.

Description

  The present invention relates to a metal-supported catalyst, a storage method thereof, and a method for producing an alcohol using the metal-supported catalyst.

  Conventionally, metal-supported catalysts have been widely studied and used in various catalytic reactions. For example, the use of various metal-supported catalysts has also been proposed in a method of directly hydrogenating (reducing) a carboxylic acid and / or a carboxylic acid ester to produce a corresponding alcohol. As a catalyst for reducing such a carboxylic acid and / or carboxylic acid ester to a corresponding alcohol, a catalyst in which ruthenium and tin are supported on a carrier and reduced with hydrogen or the like has been proposed (for example, Patent Documents 1 and 2). These catalysts exhibit high reaction activity and reaction selectivity in the reduction of carboxylic acid and / or carboxylic acid ester, and are good catalysts.

Japanese Unexamined Patent Publication No. 2000-007596 Japanese Unexamined Patent Publication No. 2001-157841

However, when the reduction reaction of carboxylic acid and / or carboxylic acid ester is carried out using the catalysts described in Patent Documents 1 and 2 prepared by a conventionally known production method, the raw material residue and the reaction selectivity are lowered. There has been a problem that the catalyst performance deteriorates. In addition, these catalysts have low stability, and thus have problems that they are deteriorated when the catalyst is stored or repeatedly used, and cannot be handled in the air.
In view of the above circumstances, the present invention provides a metal-supported catalyst having high catalytic activity and selectivity and capable of being handled in air, a method for storing the same, and a method for producing an alcohol using the metal-supported catalyst. Is an issue.

  The present inventors reduced a metal carrier (hereinafter also referred to as “metal carrier”) having ruthenium and tin supported on a carrier with hydrogen (hereinafter also referred to as “hydrogen reduction”) to carry the metal. The reaction behavior during the production of the catalyst was analyzed in detail. As a result, it was found that the metal support absorbs hydrogen during hydrogen reduction, but absorbs hydrogen rapidly at a relatively low temperature range, and the amount of hydrogen absorbed at that time is very large, accompanied by large heat generation. . The reason why the metal support exhibits such behavior at the time of hydrogen reduction is not yet clear, but since the metal support has the exothermic characteristics as described above, it is assumed that the catalyst performance is reduced as described above. did.

  Specifically, when the amount of hydrogen supplied is insufficient at the time of hydrogen reduction of the metal support, the metal support is in a hydrogen-deficient state due to rapid hydrogen absorption and rapid heat generation accompanying hydrogen absorption. When exposed to high temperature conditions, phenomena such as non-uniform heat storage, sintering, and particle size increase occur, and the metal-supported catalyst obtained by hydrogen reduction deteriorates, resulting in a significant decrease in performance. Therefore, in order to produce a highly active catalyst, it is necessary to control the heat generation behavior of the catalyst during hydrogen reduction and to avoid the occurrence of hot spots due to local heat generation. We thought that it was important in suppressing deterioration of In addition, since heat is also generated when the catalyst after hydrogen reduction is taken out into the air, it was considered that the catalyst deteriorates due to the same phenomenon as in the above reduction treatment.

  As a result of intensive studies based on the above knowledge, the present inventors, as a result, provided a metal carrier with a specific reduction treatment step and a specific oxidation stabilization step, thereby having a unique physical property that solved the above problems. The inventors have found that a supported catalyst can be obtained and have reached the present invention.

That is, the gist of the present invention is as follows.
[1] A metal-supported catalyst in which a metal is supported on a carrier,
Including ruthenium and tin as the metal,
A metal-supported catalyst having a half-width of a peak at 2θ = 43 ° of powder X-ray diffraction analysis of 3.61 ° or less and an oxidation rate represented by the following formula (1) of 38% or more .
Oxidation rate (%) = [X / Y] × 100 (1)
(In the above formula (1), X represents the number of moles of oxygen required to oxidize the metal-supported catalyst when the metal-supported catalyst is subjected to temperature reduction and subsequently oxidized at room temperature. .
Y represents the total number of moles of metal supported on the metal supported catalyst. )
[2] The metal-supported catalyst according to [1], wherein the half width is 3.60 ° or less.
[3] The metal-supported catalyst according to [1] or [2], wherein the halogen concentration in the metal-supported catalyst is 0.005 wt% or more and 0.8 wt% or less.
[4] The metal-supported catalyst according to any one of [1] to [3], further including platinum as the metal.
[5] The metal-supported catalyst according to any one of [1] to [4], wherein the support is a carbonaceous support.
[6] The metal-supported catalyst according to any one of [1] to [5], wherein the total supported amount of the metal in terms of metal atoms with respect to the total mass of the metal-supported catalyst is 5% by mass or more.
[7] The metal-supported catalyst according to any one of [1] to [6], wherein the metal-supported catalyst is prepared through an oxidation step.
[8] The method for storing a metal-supported catalyst according to any one of [1] to [7], wherein the metal-supported catalyst is stored in an atmosphere having an oxygen concentration of 15% by volume or less.
[9] Derived from the compound by reducing at least one compound selected from the group consisting of carboxylic acid and carboxylic acid ester, using the metal-supported catalyst according to any one of [1] to [7]. A method for producing alcohol, comprising the step of obtaining the alcohol to be produced.
[10] The method for producing alcohol according to [9], wherein the carboxylic acid forming the compound has 14 or less carbon atoms.
[11] The method for producing an alcohol according to [9] or [10], wherein the carboxylic acid forming the compound is a dicarboxylic acid.

  The metal-supported catalyst of the present invention has high activity and selectivity, and can be handled in air. Furthermore, the metal-supported catalyst of the present invention is a reduction catalyst, and is particularly useful for producing an alcohol by reducing a carboxylic acid and / or a carboxylic acid ester.

1 (a) and 1 (b) are powder X-ray diffraction diagrams of the metal-supported catalyst of the present invention, FIG. 1 (a) is an actual measurement diagram, and FIG. 1 (b) is a diagram after background treatment. . FIG. 2 is a graph showing the TPR measurement result of the metal support.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. 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 limited to these contents. Instead, various modifications can be made within the scope of the gist.
In the present application, metals (ruthenium, tin, and other metals such as platinum used as needed) used by being supported on a carrier may be collectively referred to as “metal component”. In addition, the metal component supported on a carrier may be referred to as a “metal-supported material”, and the metal-supported material may be referred to as a “metal-supported catalyst”. Further, “weight%” and “mass%” are synonymous.

[catalyst]
The catalyst of the present invention is a metal-supported catalyst in which a metal is supported on a carrier,
Including ruthenium and tin as the metal,
The full width at half maximum of the peak at 2θ = 43 ° of powder X-ray diffraction analysis is 3.61 ° or less, and the oxidation rate represented by the following formula (1) is 38% or more.
Oxidation rate (%) = [X / Y] × 100 (1)
(In the above formula (1), X represents the number of moles of oxygen required to oxidize the metal-supported catalyst when the metal-supported catalyst is subjected to temperature reduction and subsequently oxidized at room temperature. .
Y represents the total number of moles of metal supported on the metal supported catalyst. )

  The metal-supported catalyst of the present invention (hereinafter sometimes simply referred to as “the present catalyst”) is usually subjected to a reduction treatment with a reducing gas on a metal support on which the metal component is supported, followed by an oxidation stabilization treatment. Obtained.

(metal)
The metal supported on the metal-supported catalyst of the present invention contains ruthenium and tin as essential elements, and other than ruthenium and tin, as long as it does not adversely affect the reaction such as a reduction reaction using the catalyst, other The metal may be included. The other metal preferably includes at least one metal selected from metal species such as rhodium, platinum, gold, molybdenum, tungsten, rhenium, barium and boron, more preferably at least one selected from rhenium, platinum and gold. It contains a type of metal, more preferably platinum. Among them, a catalyst containing ruthenium, tin and platinum can obtain a high catalytic activity by a combination of these three metal components.

The amount of metal supported in the catalyst is not particularly limited, but the amount of supported ruthenium is usually 1% by mass or more, preferably 3% by mass or more, and usually 10% by mass ratio with respect to the total mass of the metal-supported catalyst. % Or less, preferably 8% by mass or less. The amount of tin supported is generally 1% by mass or more, preferably 2% by mass or more, and usually 15% by mass or less, preferably 10% by mass or less, as a mass ratio to the total mass of the metal-supported catalyst. The supported amount of other metals such as platinum used as necessary is generally 0.5% by mass or more, usually 7% by mass or less, preferably 5% by mass or less, in mass ratio to the total mass of the metal-supported catalyst. .
The total supported amount of ruthenium, tin and other metals with respect to the total mass of the metal-supported catalyst is not particularly limited, but is usually 5% by mass or more, preferably 8% by mass or more, more preferably 10% by mass or more, and usually 40%. It is at most mass%, preferably at most 30 mass%, more preferably at most 20 mass%.
The amount of metal supported is a value determined by converting all the supported metals are metal atoms. By satisfying these conditions, the oxidation rate of the metal-supported catalyst defined in the present invention can be controlled. The amount of metal supported is, for example, after elution of a metal component using an acid from a metal-supported catalyst and analyzing the concentration in the solution by atomic absorption analysis or inductively coupled plasma emission analysis, or after pulverizing the metal-supported catalyst to 50 μm or less. It can be measured using fluorescent X-ray analysis in the solid state.

(Carrier)
The carrier used in the present invention is not particularly limited. For example, a carbonaceous carrier such as activated carbon and carbon black; an inorganic porous carrier such as alumina, silica, diatomaceous earth, zirconia, titania and hafnia; silicon carbide, Gallium nitride or the like is used. Among these, a carbonaceous carrier, titania and zirconia are preferable, a carbonaceous carrier is more preferable, and activated carbon is particularly preferable. One type of carrier may be used, or two or more types of carriers may be used in combination.

  The carrier may be used as it is or after being pretreated in a form suitable for loading. For example, when a carbonaceous carrier is used, it can be used after heat treating the carbonaceous carrier with nitric acid as described in Japanese Patent Application Laid-Open No. 10-71332. The above method is preferable because the dispersibility of the metal component on the support can be improved and the activity of the resulting catalyst is improved.

  The shape of the carrier and the size of the carrier used in the present invention are not particularly limited, but when the shape is converted into a sphere, the average particle diameter is usually 50 μm or more and 5 mm or less, preferably 4 mm or less. is there. The particle diameter is measured by a screening test method described in JIS standard JIS Z8815 (1994). By setting the average particle size within the above range, the catalyst has a high activity per unit weight and is easy to handle.

  When the reaction using this catalyst is a complete mixing type reaction, the particle size of the carrier is usually 50 μm or more, preferably 100 μm or more, usually 3 mm or less, preferably 2 mm or less. The smaller the particle size of the carrier, the higher the activity per unit mass of the resulting catalyst, which is preferable. However, if the particle size is too small, the separation of the reaction solution and the catalyst may be difficult. When the shape of the carrier is not spherical, the volume of the carrier is obtained and converted as the diameter of spherical particles having the same volume.

  When the reaction using the present catalyst is a fixed bed reaction, the particle size of the carrier is usually 0.5 mm or more and 5 mm or less, preferably 4 mm or less, more preferably 3 mm or less. This is because if the particle diameter is too small than the lower limit, the operation may be difficult due to the differential pressure, and if it is larger than the upper limit, the reaction activity may be lowered.

(Oxidation rate)
This catalyst has an oxidation rate represented by the following formula (1) of 38% or more.
Oxidation rate (%) = [X / Y] × 100 (1)
(In the above formula (1), X represents the number of moles of oxygen required to oxidize the metal-supported catalyst when the metal-supported catalyst is subjected to temperature reduction and subsequently oxidized at room temperature. .
Y represents the total number of moles of metal supported on the metal supported catalyst. )

<Measurement method of oxidation rate>
The oxidation rate and its measuring method will be described more specifically below.
(I) Temperature-programmed reduction In measuring the oxidation rate, the catalyst is first subjected to temperature-programmed reduction. Although the details of the method for producing the catalyst of the present invention will be described later, it is usually obtained by subjecting the metal support to a reduction treatment followed by an oxidation stabilization treatment. Although at least a part of the metal in the catalyst of the present invention is in an oxidized state, by subjecting the present catalyst to temperature reduction, the present catalyst is reduced again, and the metal component becomes a metallic state.
The temperature rising reduction method is not particularly limited, but is usually a method of adjusting the supply amount of hydrogen per unit time and performing the reduction while adjusting the temperature rising temperature per unit time, that is, Temperature Programmed Reduction. (Hereinafter referred to as TPR method). By using this method, the hydrogen absorption amount and absorption temperature of the catalyst can be accurately measured. Specifically, the catalyst to be measured is placed in a sealed container, the temperature of the sealed container is raised while flowing a constant flow of hydrogen, and the amounts of hydrogen at the inlet and outlet of the sealed container are continuously measured. By such a method, the reduction state of the metal-supported catalyst can be confirmed.
The amount of hydrogen consumed in the step of reducing the temperature of the catalyst is usually 40 to 130 ml, preferably 70 to 130 ml, per 1 g of the catalyst. The catalyst of the present invention showing hydrogen consumption in this range is stable in air and can be handled in air. Therefore, the operability at the time of catalyst introduction at the time of catalyst reaction and at the time of catalyst removal is improved, the catalyst can be used repeatedly, and the catalyst can be easily carried.

(Ii) Room temperature oxidation The catalyst that has been subjected to the temperature reduction is then oxidized at room temperature. From the measured oxygen absorption amount, the number of moles X of oxygen required to oxidize the metal-supported catalyst is determined.

As the oxidation method, a method of performing oxidation by adjusting the supply amount of oxygen per unit time is usually used. Specifically, the catalyst after temperature reduction and reduction is placed in the sealed container used in the TPR method, and the amount of oxygen at the inlet and outlet of the sealed container is continuously measured while flowing oxygen at room temperature. This is a method for measuring the amount of oxygen reacted to oxidize. A metal-supported catalyst reduced by temperature reduction under the flow of oxygen-containing gas is placed in the sealed container used in the TPR method, and the amount of oxygen at the inlet and outlet of the sealed container is adjusted while flowing oxygen at room temperature. Measure continuously. Thereby, the amount of oxygen absorbed by the metal-supported catalyst can be measured.
In this specification, the normal temperature means 25 ° C. This temperature is a temperature at which the present catalyst can be slowly oxidized, and is a temperature range in which portions other than the surface are not easily oxidized.

(Iii) Y
Y in the formula (1) represents the total number of moles of metal supported on the metal-supported catalyst. Specifically, it represents the total number of moles of metal when the metal components contained in the metal-supported catalyst are all converted to metal atoms.

The oxidation rate of this catalyst can be obtained by adjusting the hydrogen reduction method at the time of catalyst preparation and the oxidation stabilization method of the reduced catalyst.
(Iv) Specific Example of Oxidation Rate Measurement A method for measuring the oxidation rate defined in the present invention will be described below.
About 0.1 g of the dried evaluation catalyst is weighed and placed in a U-shaped quartz tube (hereinafter referred to as a reaction tube), and subjected to temperature reduction. After flowing 10 vol% hydrogen / helium through the reaction tube at a flow rate of 20 mL / min, the mass spectrometer confirmed that the detected amount of hydrogen in the outlet gas was low and stabilized from room temperature at 10 ° C./min. The temperature is raised to ° C and held at 550 ° C for 0.5 hour. The gas discharged from the outlet of the U-shaped quartz tube (hereinafter referred to as outlet gas) is continuously measured for hydrogen concentration with a mass spectrometer.
The reaction tube is cooled to 25 ° C. while keeping the composition of the gas passing through the reaction tube. Thereafter, the gas passing through the reaction tube is switched to helium, and the gas is circulated at a flow rate of 20 mL / min to confirm that the hydrogen in the reaction tube has been replaced with helium.
The catalyst is subsequently subjected to oxidation at 25 ° C. 2.5 volume% oxygen / helium is circulated through the reaction tube at a flow rate of 20 mL / min. At the beginning of the oxygen distribution start, most of the oxygen is consumed by the reaction, but after that, the detected amount of oxygen increases rapidly, and the rising behavior of the detected amount is observed. The apparent amount of oxygen absorbed from the start of switching to 2.5% by volume oxygen / helium is defined as Amol.
Thereafter, the helium is switched to 20 mL / min to replace oxygen in the system with helium.
After confirming that the oxygen is completely replaced with helium, the second oxygen detection amount rising behavior is observed for 20 minutes by switching to 2.5% oxygen / helium again. The apparent oxygen absorption amount until the second rising behavior is defined as Bmol, and the difference (AB) mol is defined as the actual oxygen absorption amount Cmol.
The absorbed oxygen absorption amount Cmol is divided by the number of moles of the supported metal in the catalyst weighed first and multiplied by 100 to calculate the oxidation rate.
As a mass spectrometer, M-400 manufactured by Canon Anelva is used.

<Significance of oxidation rate>
The reason why the reaction activity and selectivity are excellent when the oxidation rate defined in the present invention is 38% or more can be estimated as follows.
When the oxidation rate falls within the above range, ruthenium and tin are highly dispersed in the support. The highly-supported metal-supported catalyst can control the heat generated during the catalyst preparation and reaction in a homogeneous and mild manner. As a result, hot spots are not easily formed due to local heat generation due to the heterogeneity of the supported metal fine particles, and deterioration of the catalyst such as metal sintering and an increase in the diameter of the supported metal fine particles is avoided.

  The oxidation rate is preferably higher from the viewpoint of reaction activity, preferably 40% or more, more preferably 42% or more, and usually 100% or less, but from the viewpoint of selectivity, it is preferably 90%. Below, more preferably 80% or less. By making the said oxidation rate into the said range, it is excellent in reaction activity and selectivity.

<Oxidation rate control method>
Various Ru and tin-containing catalysts of the present invention have been reported so far. Among these catalysts, the value of the oxidation rate is adjusted and controlled mainly by combining the following methods described in detail later. .
(I ′) When the metal carrier is reduced with hydrogen, hydrogen absorption and temperature of the metal carrier are appropriately controlled, and the metal carrier is uniformly reduced.
(Ii ′) The metal-supported catalyst obtained by hydrogen reduction is appropriately treated under specific oxygen concentration conditions.
In addition to this, by controlling the halogen content in the catalyst after the reduction treatment, the method for loading the metal on the support in the metal loading step described later, the washing method during the dehalogenation treatment of the metal-supported catalyst, It can be controlled to a specified oxidation rate.

(Half width)
In the metal-supported catalyst of the present invention, the half width of the peak at 2θ = 43 ° in powder X-ray diffraction analysis is 3.61 ° or less.
In this catalyst, a broad peak is detected in the vicinity of 2θ = 43 ° in the X-ray diffraction diagram obtained by powder X-ray diffraction analysis (see FIG. 1). In the present invention, the half width of this broad peak is measured. The full width at half maximum is the average of the upper and lower values including the standard deviation. The half width is preferably smaller, preferably 3.60 ° or less, more preferably 3.55 ° or less, and more preferably 3.50 ° or less, but is usually 2.0 ° or more.

<Significance of half-width>
In the present invention, it is preferable that the half width is small. In the catalyst of the present invention, “fine particles containing Ru and Sn” are supported on a carrier, and “crystallites containing Ru and Sn” are packed in the fine particles. The metal-supported catalyst (Ru—Sn-based catalyst) containing Ru and Sn as the metal of the present invention is characterized in that the larger the crystallite diameter, the smaller the half width, and the higher the catalytic activity. Conventionally, it is considered that the catalyst activity is higher when the crystallite diameter of the catalyst is smaller, that is, when the half width is larger, but the Ru—Sn catalyst of the present invention showed the opposite tendency.
In general, the peak width widens due to crystal imperfection, and when the catalyst is a multi-component system, the peak shifts due to the difference in composition, but the diffraction result overlaps them, so the peak width apparently widens. . From this, it is considered that the Ru—Sn-based catalyst should have high crystallinity and a uniform composition.

<Half width control method>
The value of the half width of this catalyst is the pretreatment method of the carrier at the time of preparing the catalyst, the type of metal compound, the type and amount of the solvent in which the metal compound is dissolved, the method of supporting the metal compound, the drying method, the type of alkali And the amount thereof, the type and amount of the solvent in which the alkali dissolves, the alkali treatment method, the amount of hydrogen during hydrogen reduction, the hydrogen reduction method, and the oxidation stabilization method of the reduced catalyst can be adjusted. .

[Method for producing catalyst]
The method for producing a catalyst of the present invention usually has the following steps, but is preferably prepared through an oxidation step shown in (iii '').
(I ″) Step of supporting the metal component on a carrier (hereinafter referred to as “metal supporting step”)
(Ii '') A step of reducing the obtained metal support with a reducing gas (hereinafter referred to as “reduction treatment step”))
(Iii ″) Step of oxidizing after reduction treatment (hereinafter referred to as “oxidation stabilization step”))
Hereinafter, it demonstrates in order for every process.

(I '' metal loading process)
The metal supporting step is a step of obtaining the metal supporting material by supporting the above-described metal component on the above-described carrier. The method for supporting the metal component is not particularly limited, and a known method can be used. In carrying, a solution or dispersion of various metal compounds that are raw materials for the metal component can be used.

<Metal loading method>
The method for supporting the metal component on the carrier is not particularly limited, but various impregnation methods are usually applicable. For example, an adsorption method that adsorbs metal ions below the saturated adsorption amount using the adsorption force of metal ions on the carrier, an equilibrium adsorption method that immerses a solution above the saturated adsorption amount to remove excess solution, and the pore volume of the carrier The pore filling method in which the same solution is added and all are adsorbed on the carrier, the solution is added until the amount of water absorbed by the carrier is met, and the incipient wetness method in which the carrier surface is uniformly wetted and no excess solution is present, the carrier There are evaporative drying methods in which the solvent is evaporated while being impregnated and spraying methods in which the carrier is dried and sprayed with the solution. Among these, there are the pore filling method, the incipient wetness method, the evaporative drying method, and the spraying method. The pore filling method, the incipient wetness method, and the evaporation to dryness method are more preferable. This is because the above method is advantageous in that ruthenium, tin, and other metal components such as platinum used as necessary can be supported after being relatively uniformly dispersed.

  The metal compound to be used is not particularly limited and can be appropriately selected depending on the supporting method. For example, halides such as chloride, bromide and iodide; mineral salts such as nitrate and sulfate; acetates An organic acid salt such as a metal hydroxide, a metal oxide, an organometallic compound, or a metal complex can be used. Among these, halides, mineral acid salts, organic acid salts and the like are preferable, halides and mineral acid salts are more preferable, halides are more preferable, and chlorides such as hydrochlorides are particularly preferable among the halides. . Moreover, it is preferable that at least 1 sort (s) of the said metal compound is a chloride, and it is more preferable that all that is a chloride. By using chloride, it is considered that the metal is complexed in a solution state, and the dispersion state of each metal on the supported carrier becomes uniform, which is preferable because it is stably supported. In addition, growth of alloy particles due to ruthenium, tin in the obtained catalyst, and other metal components such as platinum used as needed is suppressed, improving activity and selectivity, and improving the stability of the catalyst during the reaction. To do. By satisfying these conditions, the oxidation rate of the metal-supported catalyst defined in the present invention can be controlled.

<Solvent>
When the metal compound is supported on a carrier, the metal compound can be dissolved or dispersed using various solvents and used in various support methods. The type of the solvent used at this time is not particularly limited as long as it does not adversely affect the subsequent calcination of the metal support and hydrogen reduction, and further the hydrogenation reaction using this catalyst, which can dissolve or disperse the metal compound. For example, ketone solvents such as acetone; alcohol solvents such as methanol and ethanol; ether solvents such as tetrahydrofuran and ethylene glycol dimethyl ether; water and the like are used. These may be used singly or as a mixed solvent, and are inexpensive, and water is preferably used because the metal compound, preferably a halide, more preferably a chloride, has high solubility.

  Moreover, when dissolving or dispersing the metal compound, various additives may be added in addition to the solvent. For example, as described in Japanese Patent Application Laid-Open No. 10-15388, by adding a carboxylic acid and / or carbonyl compound solution, the dispersibility of each metal component on the carrier is improved when it is supported on the carrier. can do.

The metal carrier can be used by drying as necessary, and is preferably used after drying. When the subsequent reduction treatment is performed on the metal support in an undried state, the reaction activity may be lowered, and in particular, when the subsequent dehalogenation treatment described below is performed, in the presence of an alkali usually used for the dehalogenation treatment. Drying is preferable in that elution of the metal salt can be suppressed.
The drying method is not particularly limited as long as the solvent used at the time of loading is removed, and the drying is usually performed under an inert gas flow.
The drying pressure is not particularly limited, but is usually performed under normal pressure or reduced pressure.
The drying temperature is not particularly limited, but is usually 300 ° C. or lower, preferably 250 ° C. or lower, more preferably 200 ° C. or lower, and usually 80 ° C. or higher. By satisfying these conditions, the oxidation rate of the metal-supported catalyst defined in the present invention can be controlled.

<Dehalogenation treatment>
The metal carrier can be subjected to a dehalogenation treatment, if necessary, before a reduction step described later. In the above-described metal loading step, particularly when a halide such as chloride is used as a raw material for the metal component, a halogen compound may be generated in the reduction device in the reduction step described later. Although there is no problem with laboratory-scale throughput, particularly when industrial reduction is carried out in large quantities, a large amount of halogen compounds may be generated in the reduction device, and exhaust gas treatment may be required. Corrosion may occur. Therefore, it is preferable to dehalogenate before carrying out the reduction step.
The method of dehalogenation treatment is not particularly limited, but usually, the metal support is contacted with an alkaline compound in a gas phase or a liquid phase, and the halide in the metal support is reacted, followed by the gas phase treatment. Alternatively, it can be removed by washing. Among these, from the viewpoint of ease of operation and efficiency in removing halide from the metal support, it is preferable to perform the treatment by contacting with an alkaline compound in a liquid phase and then removing by washing. Specifically, it is more preferable to wash with water after contacting with an alkaline aqueous solution. By satisfying these conditions, the oxidation rate of the metal-supported catalyst defined in the present invention can be controlled.

The dehalogenation temperature is not particularly limited, but is usually 10 ° C. or higher, preferably 20 ° C. or higher, usually 150 ° C. or lower, preferably 100 ° C. or lower, more preferably 80 ° C. or lower. If it is lower than the lower limit value, a cooling operation may be required. If it is higher than the upper limit value, volatilization of the solvent and alkali compounds used in the treatment, thermal decomposition, etc. may occur.
When an alkaline aqueous solution is used for the dehalogenation treatment, the pH of the alkaline aqueous solution is not particularly limited, but the normal pH is 7.5 or more, preferably 8.0 or more, usually 13.0 or less, preferably 12.5 or less. It is. When an alkali whose pH is too higher than the above upper limit value is used, the supported metal may be altered or the eluted of the supported metal may be caused by washing described later. If the pH is too lower than the lower limit, dehalogenation may not be performed sufficiently.

  As the type of the alkali compound, for example, alkali metal carbonate, bicarbonate, ammonia or ammonium carbonate, ammonium bicarbonate, or the like is used. These may be used alone or in combination of two or more. Preferably, the use of a weakly basic alkali compound such as ammonia or ammonium salt tends to provide a more active catalyst than the use of a strongly basic alkali compound.

  The amount of the alkali compound is usually 0.1 to 50 equivalents, preferably 1 to 20 equivalents, more preferably 1 to 10 equivalents, relative to the halogen ions contained in the carrier. The alkaline compound is usually used as an aqueous solution, but a water-soluble solvent such as methanol, ethanol, acetone, ethylene glycol dimethyl ether, or a mixed solvent of these with water may be used. The alkaline aqueous solution is preferably used in an amount that completely fills the pores of the carrier carrying the metal component of the metal carrier, that is, more than the pore volume of the carrier. The amount of the alkaline aqueous solution used is not particularly limited because it depends on the concentration of the alkaline aqueous solution, but is usually 0.8 to 20 times, preferably 1 times the pore volume of the metal carrier used. It is 10 times or less, more preferably 1 time or more and 5 times or less.

<Washing>
The metal-carrying material that has been treated with the alkali compound is washed away to remove excess alkali compound and generated halide. For the washing, any solution that dissolves an excess alkali compound and the produced halide can be used, but water is preferred among them. In that case, the washing temperature is not particularly limited, and the washing is usually carried out at 10 ° C. or more and 100 ° C. or less, preferably 40 ° C. or more, more preferably 50 ° C. or more because of good washing efficiency with warm water. .

After the alkali treatment, further drying may be performed as necessary. As drying conditions, the same conditions as those for drying the metal support are used.
By satisfying these conditions, the oxidation rate of the metal-supported catalyst defined in the present invention can be controlled.

(Ii '' Reduction process)
The metal carrier is subjected to reduction treatment with a reducing gas.
The reduction treatment step usually has the following first reduction treatment step and second reduction treatment step.
<Reducing gas>
The reducing gas used in the reduction treatment step is not particularly limited as long as it has reducing properties. For example, hydrogen, methanol, hydrazine and the like are used, and preferably hydrogen.
In the reduction treatment in the present invention, a reduction reaction occurs regardless of the type of reducing gas, which becomes a metal-supported catalyst. Even if a reducing gas other than hydrogen is used, the gas that is actually consumed and absorbed by the catalyst is Hydrogen. Therefore, the amount of reducing gas necessary for the reduction treatment is expressed as “hydrogen absorption amount”.

<First reduction treatment process>
The metal carrier is first subjected to a first reduction treatment in a reducing gas atmosphere. The first reduction treatment is a treatment to be performed in order that the metal support suddenly absorbs a large amount of hydrogen in a relatively low temperature range and generates a large amount of heat. That is, the object is to sufficiently absorb hydrogen in a relatively low temperature range in order to prevent hydrogen deficiency due to rapid hydrogen absorption of the metal support. The reduction treatment may be performed in the presence of a reducing gas, but it is usually preferable to perform the reduction treatment by circulating a reducing gas.

The first reduction treatment temperature is a temperature range corresponding to a temperature range in which abrupt hydrogen absorption of the metal support is observed, and is usually a temperature showing a maximum absorption amount in a hydrogen absorption measurement by TPR analysis of the metal support. When the peak temperature is set, the measurement is performed within the range of the peak temperature ± 100 ° C. The peak temperature is preferably in the range of ± 50 ° C, more preferably in the range of the peak temperature ± 30 ° C.
Specifically, it is usually at least 80 ° C, preferably at least 100 ° C, more preferably at least 150 ° C, usually less than 350 ° C, preferably at most 300 ° C, more preferably at most 250 ° C.

  In the vicinity of the peak temperature, the largest amount of hydrogen is absorbed, so the amount of heat generated during the reduction treatment is the largest. Therefore, if the first reduction treatment is performed around this peak temperature, a large amount of heat is generated, and the reduction treatment is smoothly performed by the heat. If the temperature is too lower than the lower limit, the reduction reaction may not proceed sufficiently. On the other hand, when the temperature is too high above the upper limit, the metal support is placed in the rapid heat generation region, which causes more intense heat generation, resulting in a deficient state of reducing gas, and the sintering of the catalyst proceeds. As a result, the activity may decrease.

  Further, the first reduction treatment temperature may be a constant temperature or may be changed. Specifically, the first reduction treatment may be performed while maintaining a specific temperature within the above-mentioned preferable temperature range for a certain period of time, or the first reduction while raising the above-mentioned preferable temperature range for a certain period of time. Processing may be performed. From the viewpoint of improving the reaction time efficiency, the reduction treatment raises the temperature of the reaction system with the heat generation of the metal support, and therefore it is preferable to carry out the reduction treatment while raising the temperature for a certain time. On the other hand, since intense heat generation is involved, it is preferable to keep the temperature constant for the purpose of accurately controlling the reaction.

<Second reduction process>
The metal support subjected to the first reduction treatment is subjected to a second reduction treatment. The reduction treatment may be performed in the presence of a reducing gas, but it is usually preferable to perform the reduction treatment by circulating a reducing gas.
In the second reduction treatment, hydrogen absorption generated at a temperature higher than the temperature at which hydrogen absorption is caused by the first reduction treatment is sufficiently performed. When the hydrogen absorption behavior of the metal support in the present invention is observed in the TPR analysis described later, a large amount of hydrogen absorption is observed around 100 ° C., but the second reduction treatment is observed at a higher temperature. This process is performed to cope with the hydrogen absorption behavior.

The second reduction treatment temperature is higher than the first reduction treatment temperature. The second reduction treatment temperature is not particularly limited as long as it is higher than the first reduction treatment temperature, but is usually 350 ° C or higher, preferably 400 ° C or higher, more preferably 450 ° C or higher, usually 650 ° C or lower, preferably Is 600 ° C. or lower, more preferably 580 ° C. or lower. This is because if the reduction treatment temperature is too higher than the upper limit temperature, there is a concern about the sintering of the resulting catalyst and the adverse effect on the support.
The second reduction treatment temperature may be a constant temperature or may change.
By satisfying these conditions, the oxidation rate of the metal-supported catalyst specified in the present invention can be controlled.

<Reduction treatment time>
The time required for the first reduction treatment and the second reduction treatment varies depending on the amount of the metal carrier to be treated and the apparatus used, but each is usually 7 minutes or more, preferably 15 minutes or more, more preferably 30 minutes or more, more preferably 1 hour or more, most preferably 3 hours or more, usually 40 hours or less, preferably 30 hours or less, more preferably 10 hours or less.

<Hydrogen concentration in reducing gas>
The concentration of the reducing gas during the first reduction treatment and the second reduction treatment of the catalyst is not particularly limited, but even if it is 100% by volume of reducing gas, it is diluted with an inert gas. Also good. The inert gas referred to here is a gas that does not react with the metal carrier or the reducing gas, and nitrogen, water vapor, etc. are raised, but nitrogen is usually used.
The reducing gas concentration when 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 more preferably 50% by volume, based on the total gas components. The above is preferably used, but low concentration hydrogen may be used at the initial stage of reduction, and then the concentration may be gradually increased. By satisfying these conditions, the oxidation rate of the metal-supported catalyst defined in the present invention can be controlled.

<Flow of reducing gas>
At the time of the first reduction treatment and the second reduction treatment of the catalyst, the reducing gas may be used in a sealed state in the reactor or may be used by circulating in the reactor. Preferably it is. Since a local hydrogen-deficient state can be avoided by flowing, water, ammonium chloride, and the like are by-produced in the reactor by the reduction treatment, and these by-products are metal supports before the reduction treatment, There is a case where the metal support subjected to the reduction treatment and the obtained catalyst are adversely affected. This is because by-products can be discharged out of the reaction system by flowing a reducing gas in order to prevent this.

<Amount of reducing gas>
The total amount of reducing gas required for the first reduction treatment and the second reduction treatment is not particularly limited as long as the object of the present invention is satisfied, and the size of the reducing device and the size of the reactor during the reduction are not limited. It can be set as appropriate according to the method of flowing the sheath, the method of flowing the catalyst, and the like. Usually, the amount of hydrogen absorbed by the TPR method is 1.5 times or more, preferably 2 times the amount of hydrogen required for each reduction treatment under conditions where the contact efficiency is high such that hydrogen flows through the catalyst layer. The flow rate is at least twice, more preferably at least 3 times, and even more preferably at least 5 times. When the amount is less than the lower limit, particularly when the contact efficiency with hydrogen is low, the reduction may not be sufficiently performed. The upper limit is not particularly limited, but if it is too much, there is a problem of exhaust gas treatment, and further, the metal support and the produced catalyst may be scattered by the reducing gas, which is a waste of the reducing gas, Usually 500 times or less, preferably 200 times or less. By satisfying these conditions, the oxidation rate of the metal-supported catalyst defined in the present invention can be controlled.

<Degree of reduction of metal support>
The degree of reduction of the metal-supported product can be determined by the halogen concentration in the metal-supported catalyst that has been oxidized and stabilized after the reduction treatment. The halogen concentration is not particularly limited, but the halogen concentration in the metal-supported catalyst is usually 0.8% by mass or less, more preferably 0.7% by mass or less, and further preferably 0.5% by mass or less. A lower halogen concentration is preferable because the elution of halogen into the reaction solution is suppressed in the reduction reaction using the present catalyst, and the lower limit is not particularly limited, but is usually 0.005% by mass or more, preferably Is 0.01% by mass or more. When the halogen concentration is within the above range, the metal support is sufficiently reduced, elution of the halogen into the reaction solution is kept low, and the activity of the reduction reaction using the catalyst is improved. This is preferable because the selectivity is improved and the stability of the catalyst is improved.
By satisfying these conditions, the oxidation rate of the metal-supported catalyst defined in the present invention can be controlled.

  The size of the metal-supported catalyst after the reduction according to the present invention is not particularly limited, but is basically the same as the size of the carrier described above.

<Preferred embodiment of reduction treatment>
Preferred embodiments of the reduction treatment include a method in which a reducing gas is passed through a metal support on a fixed bed, a method in which the reducing gas is circulated through a metal support that is stationary on a tray or belt, and a fluidized metal. There is a method in which a reducing gas is circulated in the support. Among them, it is preferable to perform the reduction treatment while flowing the metal support in the reduction treatment. This is because by performing the reduction treatment while flowing, the surface area of contact between the metal carrier during the reduction treatment and the reducing gas is increased, so that the efficiency of the reduction treatment is improved.

The method for causing the fluid to flow is not particularly limited, and it is sufficient that the metal support to be reduced is accompanied by a movement that increases the contact surface area with the reducing gas. There are a method of rotating a reactor containing a support and the like, and a method of incorporating an apparatus configuration in which the metal support in the reactor is stirred or moved up and down.
Specific examples of the flow method include a method of treating using various kilns (heating furnaces).
Specific preferred production methods include, for example, a mode using a continuous kiln or a batch kiln.

<Continuous kiln>
A continuous kiln refers to an apparatus that can continuously supply a metal support and carry out the reduction, and discharge the continuously reduced catalyst. Specifically, there are continuous rotary kilns, roller hearth kilns, belt kilns, tunnel kilns, etc.In particular, in the production method of the present invention, the metal support has high fluidity and high contact efficiency with reducing gas. Therefore, a continuous rotary kiln is preferable.

(A) Operation condition of continuous kiln The operation condition of the continuous kiln is not particularly limited as long as the conditions of the above-described reduction treatment and oxidation stabilization treatment are satisfied, and may be appropriately set according to the apparatus to be used. it can. Usually, if it is in a continuous kiln, it can drive | operate so that the said reduction process conditions may be satisfied by the flow volume and temperature control of the reducing gas.

  Since the continuous kiln can continuously supply the metal support and the reducing gas, the method for supplying the metal support into the continuous kiln and the flow rate of the reducing gas can be controlled.

The flow rate of the reducing gas in the continuous kiln is not particularly limited, but the hydrogen amount required for reduction calculated by TPR measurement of the metal support is “hydrogen absorption A (m ³ / kg)”. When the input amount of the metal support to be charged into the kiln is B (kg / hour), the hydrogen flow rate is usually (1.5 × A × B) m ³ / hour or more, preferably (2 × A × B) m ³ / hour or more, more preferably (5 × A × B) m ³ / hour or more. When the hydrogen flow rate is lower than the lower limit, hydrogen deficiency may occur in the first reduction treatment, and the performance of the resulting catalyst may be reduced.
The upper limit is not particularly limited, but (1000 × A × B) m ³ / hour or less, preferably (500 × A × B) m ³ / hour or less, more preferably, in order to reduce the amount of wasted hydrogen. (300 × A × B) m ³ / hour or less.

The flow direction of the metal support to be subjected to the reduction treatment in the continuous kiln and the flow direction of the reducing gas such as hydrogen can be adjusted as appropriate depending on the state of the reduction treatment. Although it is possible to carry out both parallel flow and counterflow with respect to the flow direction, the catalyst that has reached the outlet of the continuous kiln can come into contact with fresh hydrogen. It is preferable that the flow is countercurrent (opposite directions).
The rotation speed of the continuous rotary kiln is not particularly limited. The contact efficiency between the metal support and hydrogen is improved as soon as possible, but since the catalyst is worn, it is usually 0.5 rpm or more and 10 rpm or less, preferably 5 rpm or less.

<Batch kiln>
A batch type kiln is a device that can charge a predetermined amount of metal support in the kiln in advance, increase the temperature sequentially to the target reduction temperature under the flow of reducing gas, and perform reduction at the predetermined temperature. Specifically, a fixed-bed heating furnace that is filled with a metal support and processed, a shelf-type heating furnace that is heated on a shelf, a shuttle kiln in which a baking cart enters and exits the electric furnace, and a batch rotary kiln Etc.

  Considering the contact efficiency of the metal support with the reducing gas, a fixed bed heating furnace and a batch type rotary kiln for filling and processing the metal support are preferable, and a device for flowing the catalyst is used for uniform reduction. It is preferable to use a batch rotary kiln.

  The continuous kiln is usually operated at a constant flow rate when introducing the reducing gas due to restrictions on the equipment, whereas the batch kiln has a reaction tank for each batch. The flow rate and concentration of the reducing gas can be changed for each batch.

(B) Operation condition of batch kiln The operation condition of the batch kiln is not particularly limited, and can be appropriately set according to the configuration of the apparatus.

  Since the batch type rotary kiln used in the present invention starts the temperature rise after charging a predetermined amount of metal support beforehand, the temperature rise time to the final reduction temperature can be controlled in more detail than the continuous type rotary kiln. Is possible. Although the time for the reduction treatment is not particularly limited, it is usually 1 hour or longer, preferably 2 hours or longer, usually 40 hours or shorter, preferably 30 hours or shorter, more preferably 10 hours or shorter.

If it is too short than the above lower limit, when rapid hydrogen absorption occurs, a large amount of metal support is reduced at a time, so with intense heat generation, enormous hydrogen absorption occurs and catalyst sintering proceeds. , Stable operation may be difficult. In addition, the reduction may be insufficient, and the reaction activity and selectivity may be adversely affected.
If it is longer than the upper limit, the productivity of the catalyst deteriorates and hydrogen loss occurs, which may be industrially disadvantageous.

When a batch type rotary kiln is used, the concentration, flow rate, etc. of the reducing gas can be appropriately changed depending on the state of the reduction treatment for each batch.
The preferred reducing gas concentration in the operation of the batch rotary kiln is the same as described above.

The flow rate of the reducing gas is not particularly limited and can be appropriately set according to the state of the reduction reaction. However, the amount of hydrogen required until the end of the reduction is calculated by TPR analysis of the unreduced catalyst, and usually the amount of hydrogen required. 5 times or more, preferably 10 times or more, more preferably 20 times or more. Also, it is usually 5000 times or less, preferably 1000 times or less. If the amount is less than the lower limit value, hydrogen deficiency may occur. If the amount is more than the upper limit value, excessive reducing gas is consumed.
The rotation speed of the batch type rotary kiln is not particularly limited. However, the higher the speed, the better the contact efficiency with hydrogen, but the catalyst wears out. Therefore, the rotation speed is usually 0.5 to 10 rpm, preferably 0.5 to 5 rpm. .

(Iii '' oxidation stabilization process)
In the production of the metal supported product of the present invention, the oxidation state (hereinafter referred to as “oxidation stabilization”) is usually performed on the metal supported catalyst obtained by reducing the metal supported product. By performing oxidation stabilization, it is possible to produce a catalyst that is excellent in activity and selectivity and that can be handled in air. Since this catalyst can be handled in air, it is convenient for carrying a large amount of catalyst.

  The oxidation stabilization method is not particularly limited, but a method of adding water or a method of adding it to water, a method of oxidizing and stabilizing with a low oxygen concentration gas diluted with an inert gas, and stabilization with carbon dioxide Among them, a method of adding water, a method of adding water, a method of stabilizing by oxidation with a gas having a low oxygen concentration is preferable, and a method of stabilizing oxidation (gradual oxidation) with a gas having a low oxygen concentration ( Hereinafter, it is referred to as “gradual oxidation method”). Furthermore, it is preferable to stabilize the oxidation under the flow of a low oxygen concentration gas.

The initial oxygen concentration when oxidizing and stabilizing with a gas having a low oxygen concentration is not particularly limited, but the oxygen concentration at the start of gradual oxidation is usually 0.2% by volume or more, preferably 0.5% by volume or more, usually It is 10 volume% or less, preferably 8 volume% or less, more preferably 7 volume% or less. When the oxygen concentration is too lower than the lower limit, not only the time for complete oxidation stabilization becomes very long but also stabilization may be insufficient. If the oxygen concentration is too higher than the upper limit, the catalyst may become hot and deactivate.
In order to produce a gas having a low oxygen concentration, it is preferable to dilute air with an inert gas, and nitrogen is preferable as the inert gas.

The oxygen concentration at the time of gradual oxidation may be the same as the oxygen concentration at the start of gradual oxidation. However, if the catalyst internal temperature becomes high and the catalyst does not deteriorate, The oxygen concentration may be increased. Finally, it may be gradually oxidized with air.
At the time of stable oxidation stabilization with a low oxygen concentration gas, the oxygen concentration is such that the temperature of the catalyst does not normally exceed 130 ° C, preferably does not exceed 120 ° C, more preferably does not exceed 110 ° C. The flow rate is controlled, and this control is carried out until the heat generation has subsided.
When the temperature of the catalyst exceeds 130 ° C., rapid oxidation proceeds, the sintering of the catalyst proceeds, and the strength of the support may decrease.
The oxidation stabilization condition is one of the factors that control the oxidation rate of the metal-supported catalyst defined in the present invention.

  As a method of stabilizing the oxidation with a low oxygen concentration gas, a method of passing a low oxygen concentration gas through a catalyst in a fixed bed, a method of circulating a low oxygen concentration gas through a catalyst standing on a tray or a belt, There is a method in which a gas having a low oxygen concentration is circulated in a fluidized catalyst.

The better the dispersibility of the supported metal on the metal-supported catalyst, the more rapidly the oxidation stabilization proceeds, and a large amount of oxygen reacts. Therefore, a method of passing a low oxygen concentration gas through the catalyst in a fixed bed, a fluidized catalyst A method in which a gas having a low oxygen concentration is circulated is preferable.
In addition, the manufacturing method of the catalyst of this invention is not limited to said manufacturing method, as long as the catalyst of this invention can be manufactured. For example, as long as the catalyst of this invention can be manufactured, you may combine another process.

[Catalyst preservation method]
When storing the metal-supported catalyst of the present invention, it is preferable to store it in an atmosphere having an oxygen concentration of 15% by volume or less. By storing in the above atmosphere, if the oxidation proceeds slowly even after the stabilization of oxidation, the oxidation can proceed slowly in the sealed container. The lower limit of the oxygen concentration is not particularly limited, but it is usually preferably 0.2% by volume or more in order to promote oxidation.

  In addition, the gas-stabilized catalyst is very hygroscopic and is a major problem in non-aqueous reactions. Therefore, it is preferably stored in a closed container.

[Reduction reaction using catalyst / use]
The catalyst of the present invention is suitable as a catalyst for reduction reaction. As a preferred embodiment of the reduction reaction using the present catalyst, for example, production of alcohol having a step of obtaining at least one compound selected from the group consisting of carboxylic acid and carboxylic acid ester to obtain alcohol derived from the compound A method is mentioned.

As the carboxylic acid or carboxylic acid ester to be subjected to the reduction reaction, any industrially easily available carboxylic acid or carboxylic acid ester can be used.
Examples of carboxylic acids and / or carboxylic acid esters that can be used in the reduction reaction using the catalyst of the present invention include acetic acid, butyric acid, lauric acid, oleic acid, linoleic acid, linolenic acid, stearic acid, and palmitic acid. Aliphatic chain carboxylic acids; aliphatic cyclic carboxylic acids such as cyclohexane carboxylic acid, naphthenic acid, cyclopentane carboxylic acid; oxalic acid, malonic acid, succinic acid, methyl succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, Aliphatic polycarboxylic acids such as sebacic acid, cyclohexanedicarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,3,4-cyclohexanetricarboxylic acid, bicyclohexyldicarboxylic acid, decahydronaphthalenedicarboxylic acid; phthalic acid, isophthalic acid , Terephthalic acid, trimesic acid, etc. Aromatic carboxylic acids, and the like.

The carboxylic acid forming the carboxylic acid and / or carboxylic acid ester is not particularly limited, but is preferably a chain or cyclic saturated aliphatic carboxylic acid, more preferably a carboxylic acid having 20 or less carbon atoms other than the carboxyl group. It is an acid and it is more preferable that carbon number which carboxylic acid has is 14 or less. The carboxylic acid is preferably a dicarboxylic acid, more preferably a dicarboxylic acid having 20 or less carbon atoms other than the carboxyl group and represented by the following formula (2).
HOOC-R ₁ -COOH (2)
(In the formula, R ₁ represents an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms other than the substituent, which may have a substituent.)

The carboxylic acid and / or carboxylic acid ester is particularly preferably an aliphatic or alicyclic polycarboxylic acid having 4 to 14 carbon atoms or an ester thereof having high activity and high selectivity in the reduction reaction. Therefore, it is preferable.
When these carboxylic acid esters are used, examples of the alcohol component include lower alcohols such as methanol, ethanol, i-propanol, and n-butanol.
It can also be esterified with alcohol obtained by reduction.

The reduction reaction using the catalyst of the present invention can be carried out in the absence of a solvent or in the presence of a solvent, but is usually carried out in the presence of a solvent.
As the solvent, solvents such as water, lower alcohols such as methanol and ethanol, alcohols of reaction products, ethers such as tetrahydrofuran, dioxane and ethylene glycol dimethyl ether, and hydrocarbons such as hexane and decalin can be used. . These solvents can be used alone or in combination of two or more.
In particular, when reducing carboxylic acid and / or carboxylic acid ester, it is preferable to use a mixed solvent containing water for reasons such as solubility. Although the usage-amount of a solvent is not specifically limited, It is about 0.1-20 weight times amount with respect to the carboxylic acid and / or carboxylic acid ester which are normal raw materials, Preferably it is 0.5-10 weight times amount, More preferably Is preferably used in an amount of about 1 to 10 times by weight.

The reduction reaction using the catalyst of the present invention is usually performed under hydrogen gas pressurization. The reaction is usually carried out at 100 to 300 ° C, preferably 150 to 300 ° C. The reaction pressure is 1 to 30 MPa, preferably 1 to 25 MPa, and more preferably 5 to 25 MPa.
The reduction reaction using the catalyst of the present invention can be carried out in both the liquid phase and the gas phase, but is preferably carried out in the liquid phase.

  EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

<Calculation method of catalyst oxidation rate>
(Mass spectrometer): Canon Anelva M-400
About 0.1 g of the dried evaluation catalyst was weighed and placed in a U-shaped quartz tube (hereinafter referred to as reaction tube), and subjected to temperature reduction. After flowing 10 vol% hydrogen / helium through the reaction tube at a flow rate of 20 mL / min, the mass spectrometer confirmed that the detected amount of hydrogen in the outlet gas was low and stabilized from room temperature at 10 ° C./min. The temperature was raised to 50 ° C. and held at 550 ° C. for 0.5 hour. The gas discharged from the outlet of the U-shaped quartz tube (hereinafter referred to as outlet gas) was continuously measured for hydrogen concentration with a mass spectrometer.
The reaction tube was cooled to 25 ° C. while keeping the composition of the gas passing through the reaction tube. Thereafter, the gas passing through the reaction tube was switched to helium and circulated at a flow rate of 20 mL / min, and it was confirmed that the hydrogen in the reaction tube was replaced with helium.
The catalyst was subsequently subjected to oxidation at 25 ° C. 2.5 vol% oxygen / helium was passed through the reaction tube at a flow rate of 20 mL / min. At the beginning of the oxygen distribution start, most of the oxygen is consumed by the reaction, but after that, the detected amount of oxygen increases rapidly, and the rising behavior of the detected amount is observed. The apparent amount of oxygen absorbed from the start of switching to 2.5% by volume oxygen / helium is defined as Amol.
Thereafter, the helium was switched to 20 mL / min to replace the oxygen in the system with helium.
After confirming that oxygen was completely replaced with helium, the volume was switched to 2.5% oxygen / helium again, and the rising behavior of the second oxygen detection amount was observed for 20 minutes. The apparent oxygen absorption amount until the second rising behavior was defined as Bmol, and the difference (AB) mol was defined as the actual oxygen absorption amount Cmol.
The absorbed oxygen absorption Cmol was divided by the number of moles of the supported metal in the catalyst weighed first and multiplied by 100 to calculate the oxidation rate.

<Measurement method of powder X-ray diffraction half width>
(Measurement equipment specifications)
Device name: X'Pert Pro MPD manufactured by PANalytical
Optical system: Concentrated optical system Optical system specifications Incident side: Enclosed X-ray tube (CuKα)
Soller Slit (0.04 rad)
Divergence Slit (Variable Slit)
Sample stage: Rotating sample stage (Spinner)
Light receiving side: Semiconductor array detector (X'Celerator)
Gonio radius: 243nm
(Measurement condition)
X-ray output: 40kV 30mA
Operation axis: θ / 2θ
Operating range: 10 to 70 degrees Measurement mode: Continuous
Reading width: 0.016 degrees Counting time: 59.7 seconds Automatic variable slit: 10 nm (irradiation width)
Horizontal divergence mask: 10 nm (irradiation width)
(X-ray diffraction pattern processing method)
A profile fitting method using a Peason-VII function was used for background processing of the X-ray diffraction diagram and measurement of the half-width.

Based on the above measurement conditions, powder X-ray diffraction is measured, and an X-ray diffraction diagram in which the X axis is the diffraction angle and the Y axis is the diffraction intensity is obtained. From the obtained X-ray diffraction diagram, the half width is obtained by the following procedure.
In the obtained X-ray diffraction diagram, a peak top of a broad peak detected near the diffraction angle 2θ = 43 ° is determined, and a baseline is drawn. Next, the background is subtracted from the diffraction intensity so that the baseline is parallel to the X axis. Then, a perpendicular line is drawn from the peak top of 2θ = 43 ° determined in advance to the base line. At this time, the length of the perpendicular line connecting the peak top and the base line is defined as the peak height. Then, a line parallel to the base line passing through the position having a length of ½ of the peak height is drawn on the perpendicular, and the distance between the two points intersecting the broad peak is obtained as a half width.

<Method for confirming catalyst reaction activity>
The reaction activity of the catalyst obtained in the present invention was confirmed by using a production reaction of 1,4-cyclohexanedimethanol (CHDM) by the following hydrogenation reaction of 1,4-cyclohexanedicarboxylic acid.
In a 200 mL induction stirring autoclave (hereinafter referred to as “reactor”) manufactured by Hastelloy C (registered trademark), 40 g of water, 10 g of 1,4-cyclohexanedicarboxylic acid (mixture of cis- and trans-isomers: manufactured by Tokyo Chemical Industry Co., Ltd.), After charging 2 g of the catalyst to be evaluated and replacing the inside of the reactor with hydrogen, the partial pressure of hydrogen was set to 1 MPa, the reactor was heated with stirring at 1000 rpm, the reaction pressure was set to 8.5 MPa at a predetermined temperature, and the reaction was started at 240 ° C. did. Hydrogen was continuously supplied from the pressure accumulator into the reactor, and the reaction was carried out at 240 ° C. with a constant reaction pressure for 3 hours. After completion of the reaction, the presence or absence of cracking of the catalyst was visually confirmed. At this point, the reaction that becomes too fast agitation or becomes a catalyst in which cracking becomes apparent due to poor agitation is excluded from the evaluation because the apparent reaction rate becomes high and the activity cannot be compared.
The conversion rate of the carboxyl group was calculated | required by carrying out NaOH neutralization titration of the obtained product. The primary rate constant k (h ⁻¹ ) for the first hour of the reaction was calculated from the gas absorption curve of the pressure accumulator.
In all of the examples and comparative examples, the conversion rate of the carboxyl groups was 99% or more.
The product was analyzed using a gas chromatograph. The main product was 1,4-cyclohexanedimethanol (CHDM), which was the target product, and the main by-products were two types, cyclohexanemethanol (CHM) and 4-methylcyclohexanemethanol (MCHM). Except for the two types of by-products, the total amount was CHDM, so the catalyst performance was compared based on the yield of the two types of by-products and the reaction rate constant.

<Measurement of ratio of catalyst activity to reference activity>
Even if the same reduction treatment and oxidation treatment are performed depending on the metal support as the raw material, the performance of the produced catalyst differs.
Therefore, the standard activity (rate constant (h ⁻¹ )) of the metal support as the raw material of the example and the comparative example is measured by the following “standard activity measurement method 1” or “reference activity measurement method 2”. did.
The ratio of “catalytic activity of Examples or Comparative Examples” to the standard activity was calculated.
In the following “reference activity measurement method 1” and “reference activity measurement method 2”, the reduction treatment conditions are slightly different, but from the present inventors' experience, this difference does not affect the catalyst performance. I understand that.

(Measurement method 1 of reference activity)
2.5 g of metal support was charged into a glass tube having an inner diameter of 25 mm, set in an electric furnace, purged with argon, and then flowed at 100% hydrogen at 5 L / min. The temperature of the electric furnace was raised, and the temperature of the metal-supported material was raised to 100 ° C. in 9 minutes, and the temperature was raised from 100 ° C. to 450 ° C. at a constant rate for 31 minutes. The reduction treatment was carried out at 450 ° C. for 2 hours as it was, and after 2 hours, cooling was performed under argon flow, and stabilization was carried out by flowing at room temperature with 6% O ₂ / N ₂ , 2.1 L / hour for 1 hour. Using the stabilized catalyst, the reference activity was confirmed by the above-described <Method for confirming reaction activity of catalyst>.

(Measurement method 2 of reference activity)
2.5 g of metal support was charged into a glass tube having an inner diameter of 25 mm, set in an electric furnace, purged with argon, and then flowed at 100% hydrogen at 5 L / min. The temperature of the electric furnace was raised, and the metal support was heated to 100 ° C. in 11 minutes, and the temperature was raised from 100 ° C. to 550 ° C. at a constant rate for 47 minutes. The reduction treatment was carried out at 550 ° C. for 2 hours as it was, and after 2 hours, the mixture was cooled under argon flow and stabilized by flowing at 6% O ₂ / N ₂ , 2.1 L / hour for 1 hour at room temperature. Using the stabilized catalyst, the reference activity was confirmed by the above-described <Method for confirming reaction activity of catalyst>.

(Calculation method of the ratio of the amount of supplied hydrogen to the amount of hydrogen required for reduction of the metal support)
For the metal support prepared by the same method as in Example 1, the same operation as the temperature reduction in <Calculation method of catalyst oxidation rate> was performed, and the hydrogen concentration in the outlet gas from the reaction tube was continuously changed. Measured and detected hydrogen absorption as a peak. The detection result is shown in FIG. In FIG. 2, three peaks were observed. From the total area of these three peaks, the amount of hydrogen necessary for the reduction of the metal support was calculated to be 111 ml / g (metal support).
In the examples or comparative examples, the amount of hydrogen circulated in the rotary kiln within the time that the metal support stays in the heating zone is determined as the amount of hydrogen necessary for the reduction of the metal support (111 ml / g). The value divided by the value was defined as the ratio of the amount of supplied hydrogen to the amount of hydrogen required for reduction of the metal support.

Example 1
A 1 mm cylindrical activated carbon (R1 EXTRA manufactured by NORIT) carrier was used as the carrier, and the ruthenium chloride hydrate and chloroplatinic acid (IV) -6 were used in accordance with Example 4 of Japanese Patent Application Laid-Open No. 2001-9277. Using a hydrate, tin (II) chloride dihydrate, ruthenium, platinum, and tin were supported on activated carbon to prepare a metal support (hereinafter, metal support 1). In the preparation method of the metal carrier 1, the dissolved water of the metal chloride was the same as the pore volume of the activated carbon used. The amount of metal chloride charged is such that when the total amount charged is supported, reduced by hydrogen, and stabilized by oxidation, the content in the metal-supported catalyst is 6 mass% Ru, 3 mass% Pt, 7 mass% Sn. did. In addition, the ammonium bicarbonate used was used as a 12% strength aqueous solution in an amount twice as much as the metal chloride chlorine.

The metal support 1 was subjected to a reduction treatment using a continuous rotary kiln. The continuous rotary kiln has a furnace length of 2m, a heating zone installed in the center of the furnace, a heating zone length of 0.95m, an inner diameter of 0.25m, and a rotation speed of 0.5rpm. The temperature at the center of the direction was 480 ° C to 530 ° C.
Using a screw feeder, the metal carrier 1 having a bulk specific gravity of about 0.5 kg / L was continuously fed into the kiln for 3 hours from the continuous rotary kiln inlet at a feed rate of 0.5 kg / hour. The temperature at the inlet of the continuous rotary kiln was 120 ° C. The tilt angle of the rotary kiln is adjusted to 1%, and the metal carrier 1 is about 30 minutes from the kiln inlet to the heating zone (corresponding to the first reduction step when a part of this is reduced in two steps, The time in the temperature range from ℃ to 300 ℃ was about 14 minutes.), The residence time in the heating zone is 1 hour (this is the second reduction step when reducing in a two-step process) ), And was fed from the heating zone to the kiln outlet for about 40 minutes. The hydrogen concentration was 100%, and it was continuously supplied at a rate of 50 L / min countercurrently to the metal support from the kiln outlet side.
The amount of hydrogen circulated in the rotary kiln during the time when the metal support 1 stayed in the heating zone was 55 times that required for reduction.

The catalyst obtained by the above reduction treatment was collected in three at the outlet of the rotary kiln. The first one hour recovery (referred to as “front part”), the subsequent one hour recovery (referred to as “central part”), and the remaining catalyst after that (hereinafter referred to as “rear part”) were recovered.
420 g of the front portion thus obtained was subjected to oxidation stabilization for 2 hours under a flow of 1.9 vol% oxygen / nitrogen 4.4 L / min, and 6.1 wt% Ru-2.9 wt% Pt. -6.7 mass% Sn / activated carbon supported catalyst was obtained. Further, the chlorine content in the obtained catalyst was 0.38% by mass. The temperature inside the catalyst during the oxidation stabilization operation was 60 ° C. or lower.

This catalyst was subjected to powder X-ray diffraction analysis by the above analysis method, and the half width of a broad peak at 2θ = 43 ° was measured from the obtained X-ray diffraction diagram by the above-described calculation method. Met. Further, when the oxygen absorption amount of this catalyst was measured by the above measuring method, it was 0.55 mmol oxygen / g-catalyst, and the oxidation rate of the catalyst was 41%.
The reaction activity of the obtained catalyst was confirmed by the above method.
Further, for the metal carrier 1 prepared in Example 1, the reference activity was measured by the above <Reference Activity Measurement Method 1>, and the ratio of the catalyst activity to the reference activity was calculated. The results are shown in Table 1. In the table, M.M. B. (Material balance) is a value obtained by dividing the total number of moles of raw materials and products detected after reaction by the number of moles of charged raw materials and multiplying by 100. This M.I. B. The detected amounts of 1,4-cyclohexanedimethanol (CHDM), cyclohexanemethanol (CHM) and 4-methylcyclohexanemethanol (MCHM) are converted to 100%, divided by the number of moles of the charged raw material, and multiplied by 100. The yield was calculated.

(Example 2)
297 g of the central portion recovered in Example 1 was oxidized and stabilized under the same conditions as in Example 1 to obtain 6.2 mass% Ru-3.0 mass% Pt-7.1 mass% Sn / activated carbon supported catalyst. It was. Further, the chlorine content in the obtained catalyst was 0.06% by mass. The temperature inside the catalyst during the oxidation stabilization operation was 60 ° C. or lower.
This catalyst was analyzed in the same manner as in Example 1. As a result of powder X-ray diffraction analysis, the half-width of the broad peak at 2θ = 43 ° was 3.36 °, and the oxygen absorption was 0.57 mmol oxygen / g-catalyst. The oxidation rate was 42%.
The reaction activity of the obtained catalyst was confirmed by the above method.
Further, for the metal carrier 1 prepared in Example 1, the reference activity was measured by the above <Reference Activity Measurement Method 1>, and the ratio of the catalyst activity to the reference activity was calculated. The results are shown in Table 1.

(Example 3)
The rear portion 139 g recovered in Example 1 was subjected to oxidation stabilization under the same conditions as in Example 1 except that the oxidation stabilization time was 73 minutes, and 6.2 mass% Ru-3.0 mass% Pt-7. 3 mass% Sn / activated carbon supported catalyst was obtained. The chlorine content in the obtained catalyst was 0.07% by mass. The temperature inside the catalyst during the oxidation stabilization operation was 60 ° C. or lower.
This catalyst was analyzed in the same manner as in Example 1. As a result of powder X-ray diffraction analysis, the half width of the broad peak at 2θ = 43 ° was 3.19 °, and the oxygen absorption was 0.62 mmol oxygen / g-catalyst. The oxidation rate was 45%.
The reaction activity of the obtained catalyst was confirmed by the above method.
Further, for the metal carrier 1 prepared in Example 1, the reference activity was measured by the above <Reference Activity Measurement Method 1>, and the ratio of the catalyst activity to the reference activity was calculated. The results are shown in Table 1.

Example 4
A metal support was prepared in the same manner as in Example 1. Using the obtained metal support, except that the metal support supply rate was 2.6 kg / hour, the rotation speed of the continuous rotary kiln was 1.6 rpm, and the residence time in the heating zone of the continuous rotary kiln was 0.5 hours. Was reduced in the same manner as in Example 1 (at this time, it took about 15 minutes from the kiln inlet to the heating zone).
The amount of hydrogen circulated in the rotary kiln during the time that the metal support stayed in the heating zone was 10.5 times that required for reduction.
2591 g of the middle part obtained by the above reduction treatment was subjected to oxidation stabilization for 3 hours and 55 minutes under a flow of 7 vol% oxygen / nitrogen 36 L / min, and 6.1 mass% Ru-2.6 mass% Pt-6. .9 mass% Sn / activated carbon supported catalyst was obtained. Moreover, the chlorine content in the obtained catalyst was 0.23 mass%. The temperature inside the catalyst during the oxidation stabilization operation was 110 ° C. or lower.
This catalyst was analyzed in the same manner as in Example 1. As a result of powder X-ray diffraction analysis, the half-width of the broad peak at 2θ = 43 ° was 3.50 °, and the oxygen absorption was 0.57 mmol oxygen / g-catalyst. The oxidation rate was 43%.
Further, for the metal support used in Example 4, the reference activity was measured by the above <Method for measuring reference activity 2>, and the ratio of the catalyst activity to the reference activity was calculated. The results are shown in Table 1.

(Example 5)
A metal support was prepared in the same manner as in Example 1.
2.5 g of the obtained metal support was charged into a glass tube having an inner diameter of 25 mm, set in an electric furnace, and after argon substitution, the flow was performed at 5 L / hour of 100% hydrogen. The electric furnace was heated to raise the temperature of the metal carrier to 110 ° C. in 11 minutes and from 100 ° C. to 550 ° C. for 47 minutes at a constant rate. The reduction treatment was carried out at 550 ° C. for 2 hours as it was, followed by cooling under argon flow, stabilization at a flow rate of 6% oxygen / nitrogen at room temperature for 1 hour at 2.1 L / hour, and 5.9% by weight Ru. -2.2 mass% Pt-6.8 mass% Sn / activated carbon supported catalyst was obtained. The temperature inside the catalyst during the oxidation stabilization operation was 60 ° C. or lower.
This catalyst was analyzed in the same manner as in Example 1. As a result of powder X-ray diffraction analysis, the half width of the broad peak at 2θ = 43 ° was 3.46 °, and the oxygen absorption was 0.71 mmol oxygen / g-catalyst. The oxidation rate was 56%.
Further, for the metal support used in Example 5, the reference activity was measured by the above <Reference Activity Measurement Method 2>, and the ratio of the catalyst activity to the reference activity was calculated. The results are shown in Table 1.

(Example 6)
A metal support was prepared in the same manner as in Example 1.
Reduction was performed in the same manner as in Example 1 except that the obtained metal support was used and the metal support supply rate was 1.5 kg / hour. The amount of hydrogen circulated in the rotary kiln during the time when the metal support stayed in the heating zone was 18 times that required for reduction.
The rear part 949 g obtained by the above reduction treatment was subjected to oxidative stabilization for 77 minutes under a flow of 6.6 vol% oxygen / nitrogen 18.2 L / min, and 5.8 wt% Ru-2.2 wt% Pt. -6.7 mass% Sn / activated carbon supported catalyst was obtained. Further, the chlorine content in the obtained catalyst was 0.17% by mass.
This catalyst was analyzed in the same manner as in Example 1. As a result of powder X-ray diffraction analysis, the half width of the broad peak at 2θ = 43 ° was 3.61 °, and the oxygen absorption was 0.49 mmol oxygen / g-catalyst. The oxidation rate was 39%.
Further, for the metal support used in Example 6, the standard activity was measured by the above <Method for measuring standard activity 1>, and the ratio of the catalyst activity to the standard activity was calculated. The results are shown in Table 1.

(Comparative Example 1)
Reduction was carried out in the same manner as in Example 1 except that the metal carrier 1 used in Example 1 was used, and 50 volume% hydrogen / nitrogen was changed to 4.4 L / min. The amount of hydrogen circulated in the rotary kiln during the time when the metal support 1 stayed in the heating zone was 2.4 times that required for reduction.
411 g of the catalyst obtained by the above reduction treatment was subjected to oxidation stabilization for 2 hours under a flow of 1.9% volume% oxygen / nitrogen 4.4 L / min, and 5.8 mass% Ru-2.9 mass%. Pt-6.7 mass% Sn / activated carbon catalyst was obtained. Moreover, the chlorine content in the obtained catalyst was 0.26 mass%.
In this oxidation stabilization operation, the temperature inside the catalyst was 60 ° C. or lower.
This catalyst was analyzed in the same manner as in Example 1. As a result of powder X-ray diffraction analysis, the half-width of the broad peak at 2θ = 43 ° was 3.64 °, and the oxygen absorption was 0.46 mmol oxygen / g-catalyst. The oxidation rate was 36%.
Further, with respect to the metal support 1 used in Comparative Example 1, the reference activity was measured by the above <Method for measuring reference activity 1>, and the ratio of the catalyst activity to the reference activity was calculated. The results are shown in Table 1.

(Comparative Example 2)
A metal support was prepared in the same manner as in Example 1.
Reduction was performed in the same manner as in Example 1 except that the obtained metal support was used and the metal support supply rate was 2.5 kg / hour. The amount of hydrogen circulated in the rotary kiln during the time when the metal support stayed in the heating zone was 11 times that required for reduction.
The rear part 2412 g obtained by the above reduction treatment was subjected to oxidation stabilization for 4 hours and 9 minutes under a flow of 7 vol% oxygen / nitrogen 36 L / min. 6.2 wt% Ru-2.9 wt% Pt-7 2 mass% Sn / activated carbon supported catalyst was obtained. The chlorine content in the obtained catalyst was 0.98% by mass.
This catalyst was analyzed in the same manner as in Example 1. As a result of powder X-ray diffraction analysis, the half-width of the broad peak at 2θ = 43 ° was 3.67 °, and the oxygen absorption was 0.48 mmol oxygen / g-catalyst. The oxidation rate was 35%.
Further, for the metal support used in Comparative Example 2, the standard activity was measured by the above <Standard Activity Measurement Method 1>, and the ratio of the catalyst activity to the standard activity was calculated. The results are shown in Table 1.

From Examples 1 to 6 and Comparative Examples 1 and 2, it can be seen that the catalyst of the present invention has a high ratio of the catalytic activity to the standard activity and is highly active. It was also found that the target product, CHDM, was obtained in high yield and purity when the catalyst of the present invention was used.
In Examples 1 to 6, the reaction activity was confirmed after the catalyst was once taken out into the air after the oxidation stabilization operation. This shows that the catalyst of the present invention can be handled in air.

(Example 7)
A metal support was prepared in the same manner as in Example 1.
5 g of the obtained metal carrier was charged into a glass tube having an inner diameter of 25 mm, set in an electric furnace, and after argon substitution, it was allowed to flow at 10 L / hour of 100% hydrogen. The electric furnace was heated to raise the temperature of the metal carrier to 100 ° C. in 9 minutes and from 100 ° C. to 550 ° C. for 36 minutes at a constant rate. The reduction treatment was carried out at 500 ° C. for 2 hours as it was, followed by cooling under argon flow, stabilization at 6% oxygen / nitrogen, 2.1 L / hour at room temperature for 1.5 hours to stabilize the activated carbon supported catalyst. Obtained. The temperature inside the catalyst during the oxidation stabilization operation was 60 ° C. or lower.
This catalyst was analyzed in the same manner as in Example 1. As a result of powder X-ray diffraction analysis, the half width of the broad peak at 2θ = 43 ° was 3.46 °, and the oxygen absorption was 0.60 mmol oxygen / g-catalyst. The oxidation rate was 46%.
2 g of this catalyst was sealed in a 10 ml sample bottle in an atmosphere of 10% oxygen / nitrogen and stored at room temperature.
After 37 days, the reaction was carried out in the same manner as in <Method for confirming reaction activity of catalyst> except that the reaction pressure was 10 MPa and the reaction temperature was 200 ° C. did. The results are shown in Table 2.

(Reference Example 1)
Of the catalyst stabilized by oxidation in Example 7, 2 g was stored at room temperature in the atmosphere (21% oxygen concentration).
After 36 days, the reaction was carried out under the same conditions as in Example 7 using the stored catalyst, and the rate constant was calculated. The results are shown in Table 2.

  From Example 7 and Reference Example 1, it was found that the catalyst of the present invention can maintain a high catalytic activity after storage by storing it in an atmosphere having a low oxygen concentration.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on May 23, 2014 (Japanese Patent Application No. 2014-107283), the contents of which are incorporated herein by reference.

  According to the present invention, a highly active catalyst can be obtained even when the metal-supported catalyst is produced on an industrial scale.

Claims (11)

A metal-supported catalyst in which a metal is supported on a carrier,
Including ruthenium and tin as the metal,
A metal-supported catalyst having a half-width of a peak at 2θ = 43 ° of powder X-ray diffraction analysis of 3.61 ° or less and an oxidation rate represented by the following formula (1) of 38% or more .
Oxidation rate (%) = [X / Y] × 100 (1)
(In the above formula (1), X represents the number of moles of oxygen required to oxidize the metal-supported catalyst when the metal-supported catalyst is subjected to temperature reduction and subsequently oxidized at room temperature. .
Y represents the total number of moles of metal supported on the metal supported catalyst. )   The metal-supported catalyst according to claim 1, wherein the half width is 3.60 ° or less.   The metal-supported catalyst according to claim 1 or 2, wherein the halogen concentration in the metal-supported catalyst is 0.005 wt% or more and 0.8 wt% or less.   The metal-supported catalyst according to any one of claims 1 to 3, further comprising platinum as the metal.   The metal-supported catalyst according to any one of claims 1 to 4, wherein the support is a carbonaceous support.   The metal-supported catalyst according to any one of claims 1 to 5, wherein a total supported amount of the metal in terms of metal atoms with respect to a total mass of the metal-supported catalyst is 5% by mass or more.   The metal-supported catalyst according to any one of claims 1 to 6, wherein the metal-supported catalyst is prepared through an oxidation step.   The method for storing a metal-supported catalyst according to any one of claims 1 to 7, wherein the metal-supported catalyst is stored in an atmosphere having an oxygen concentration of 15% by volume or less.   Using the metal-supported catalyst according to any one of claims 1 to 7, at least one compound selected from the group consisting of a carboxylic acid and a carboxylic acid ester is reduced to obtain an alcohol derived from the compound. A method for producing alcohol, comprising a step.   The method for producing alcohol according to claim 9, wherein the carboxylic acid forming the compound has 14 or less carbon atoms.   The method for producing an alcohol according to claim 9 or 10, wherein the carboxylic acid forming the compound is a dicarboxylic acid.

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