Catalyst, method for producing catalyst, and method for producing bis (aminomethyl) cyclohexane

Abstract

The present invention provides a technology for exhibiting excellent reaction results in producing BAC. This catalyst is for producing bis (aminomethyl) cyclohexane and has hydrogenation ability. The CO adsorption amount measured for the catalyst by using a CO pulse measurement method is 0.20 cm3 / g-cat or more.

Description

Catalyst, method for producing the catalyst, and method for producing bis(aminomethyl)cyclohexane

[0001] The present invention relates to a catalyst, a method for producing the catalyst, and a method for producing bis(aminomethyl)cyclohexane.

[0002] Bis(aminomethyl)cyclohexane (hereinafter also referred to as "BAC") is an industrially important compound used as a raw material for polyamides and bis(isocyanatemethyl)cyclohexane. BAC can be obtained, for example, by catalytic hydrogenation of xylylenediamine. As a catalyst used in such catalytic hydrogenation, for example, Patent Document 1 discloses a catalyst prepared by adding an alkali metal modifier as an auxiliary agent to ruthenium / alumina, which is a catalyst component.

[0003] Chinese Patent Application Publication No. 112473663

[0004] Although the catalyst described in Patent Document 1 is said to improve BAC selectivity, there is still room for further improvement in terms of reaction performance in the reaction to produce BAC.

[0005] This invention has been made in view of the above-mentioned problems, and its purpose is to provide a technology that exhibits excellent reaction results in the production of BAC.

[0006] As a result of diligent research, the inventors of this invention have found that the above problems can be solved by a catalyst having predetermined physical properties, and have completed the present invention.

[0007] In other words, the present invention encompasses the following aspects: <1> A catalyst having hydrogenation ability for producing bis(aminomethyl)cyclohexane, wherein the amount of CO adsorbed to the catalyst, as measured by the CO pulse measurement method described below, is 0.20 cm³. ３A catalyst having a concentration of 1 / g-cat or higher. (CO pulse measurement method) (1) Contact 50 mg of the catalyst in a sample tube with He gas at a gas flow rate of 50 sccm for 20 minutes, raising the catalyst temperature to 260°C. (2) Contact the catalyst that has gone through (1) with He gas at a gas flow rate of 50 sccm for 15 minutes, maintaining the catalyst temperature at 260°C during this time. (3) Apply H to the catalyst that has gone through (2). ２ (1) Contact the catalyst with the gas at a gas flow rate of 50 sccm for 30 minutes, during which time the catalyst temperature is maintained at 260°C. (4) Contact the catalyst that has gone through (3) with He gas at a gas flow rate of 50 sccm for 15 minutes, during which time the catalyst temperature is maintained at 260°C. (5) Contact the catalyst that has gone through (4) with He gas at a gas flow rate of 50 sccm, during which time the catalyst temperature is lowered to 50°C. (6) Contact the catalyst that has gone through (5) with He gas at a gas flow rate of 50 sccm for 15 minutes, during which time the catalyst temperature is maintained at 50°C. (7) The catalyst that has undergone (6) above is brought into contact with He gas at a gas flow rate of 30 sccm, during which time the catalyst temperature is maintained at 50°C, and a CO / He mixed gas with a CO concentration of 10 volume% is flowed into the measuring tube at a gas flow rate of 50 sccm for 60 seconds, and then injected into the sample tube after 10 seconds. (8) Based on the results of (7) above, the amount of CO adsorbed is calculated from the amount of CO gas consumed. Here, pulse detection is based on a pulse detection judgment value of 0.001 mV / sec, and the amount of CO gas consumed is determined to have reached saturation when the error of the detection amount of the last 3 pulses becomes 2.0% or less, and is determined based on the pulse measurement results until saturation is reached. <2> The catalyst according to <1>, wherein the catalyst comprises a catalyst component and a carrier supporting the catalyst component, and the catalyst component comprises at least one selected from the group consisting of Ru, Rh, Ni, Pd and Co. <3> The amount of CO adsorbed by the CO pulse measurement method is 10.00 cm ３A catalyst according to <1> or <2>, wherein the amount of metal is 1 / g-metal or more. <4> A catalyst according to <2> or <3>, wherein the average particle size of the catalyst component is 15.00 nm or less. <5> A catalyst according to any one of <2> to <4>, wherein the Ru content in the catalyst is 0.1 to 10.0 mass% based on 100 mass% of the catalyst. <6> A catalyst according to any one of <1> to <5>, wherein the Cl content in the catalyst is 0.001 to 0.1 mass% based on 100 mass% of the catalyst. <7> A catalyst according to any one of <2> to <6>, wherein the support contains alumina. <8> A method for producing a catalyst according to any one of <1> to <7>, comprising: a supporting step (a) of reacting a catalyst component with a support to obtain a first reactant; and a base treatment step (b) of adding a basic aqueous solution to the first reactant to obtain a second reactant. <9> The method for producing a catalyst according to <8>, wherein the supporting step (a) includes reacting the chloride of the catalyst component with the support. <10> The method for producing a catalyst according to <8> or <9>, wherein the basic aqueous solution in the base treatment step (b) includes an aqueous sodium hydroxide solution. <11> The method for producing a catalyst according to <8> to <10>, wherein the base treatment step (b) is carried out at a temperature of 10 to 90°C. <12> The amount of CO adsorbed to the second reactant, as measured by the CO pulse measurement method, is 0.20 cm³. ３ A method for producing a catalyst according to any one of <7> to <11>, wherein the amount is 0.20 cm³ / g-cat or more. <13> A hydrogenation step to obtain bis(aminomethyl)cyclohexane by contacting xylylenediamine with hydrogen in the presence of a catalyst having hydrogenation ability, wherein the amount of CO adsorbed on the catalyst, as measured by the CO pulse measurement method described below, is 0.20 cm³. ３A method for producing bis(aminomethyl)cyclohexane having a concentration of 1 / g-cat or higher. (CO pulse measurement method) (1) Contact 50 mg of the catalyst in a sample tube with He gas at a gas flow rate of 50 sccm for 20 minutes, raising the catalyst temperature to 260°C. (2) Contact the catalyst that has gone through (1) with He gas at a gas flow rate of 50 sccm for 15 minutes, maintaining the catalyst temperature at 260°C during this time. (3) Apply H to the catalyst that has gone through (2). ２ (1) Contact the catalyst with the gas at a gas flow rate of 50 sccm for 30 minutes, during which time the catalyst temperature is maintained at 260°C. (4) Contact the catalyst that has gone through (3) with He gas at a gas flow rate of 50 sccm for 15 minutes, during which time the catalyst temperature is maintained at 260°C. (5) Contact the catalyst that has gone through (4) with He gas at a gas flow rate of 50 sccm, during which time the catalyst temperature is lowered to 50°C. (6) Contact the catalyst that has gone through (5) with He gas at a gas flow rate of 50 sccm for 15 minutes, during which time the catalyst temperature is maintained at 50°C. (7) The catalyst that has undergone (6) above is brought into contact with He gas at a gas flow rate of 30 sccm, during which time the catalyst temperature is maintained at 50°C, and a CO / He mixed gas with a CO concentration of 10 volume% is flowed into the measuring tube at a gas flow rate of 50 sccm for 60 seconds, and then injected into the sample tube after 10 seconds. (8) Based on the results of (7) above, the amount of CO adsorbed is calculated from the amount of CO gas consumed. Here, pulse detection is based on a pulse detection judgment value of 0.001 mV / sec, and the amount of CO gas consumed is determined to have reached saturation when the error of the detection amount of the last 3 pulses becomes 2.0% or less, and is determined based on the pulse measurement results until saturation is reached. <14> The method for producing bis(aminomethyl)cyclohexane according to <13>, wherein the catalyst comprises a catalyst component and a carrier supporting the catalyst component, and the catalyst component comprises at least one selected from the group consisting of Ru, Rh, Ni, Pd and Co. <15> The amount of CO adsorbed by the CO pulse measurement method of the catalyst is 10.00 cm ３ / g-metal or more, the process for producing bis(aminomethyl)cyclohexane according to <13> or <14>. <16> The process for producing bis(aminomethyl)cyclohexane according to <14> or <15>, wherein the average particle diameter of the catalyst component is 15.00 nm or less. <17> The process for producing bis(aminomethyl)cyclohexane according to any one of <14> to <16>, wherein the Ru content in the catalyst is 0.1 to 10.0 mass% relative to 100 mass% of the catalyst. <18> The process for producing bis(aminomethyl)cyclohexane according to any one of <14> to <17>, wherein the carrier comprises alumina. <19> The process for producing bis(aminomethyl)cyclohexane according to any one of <14> to <18>, further comprising a catalyst production step of producing the catalyst, wherein the catalyst production step comprises: a supporting step (a) of reacting the catalyst component with the carrier to obtain a first reactant; and a base treatment step (b) of adding a basic aqueous solution to the first reactant to obtain a second reactant. <20> The CO adsorption amount measured by the CO pulse measurement method for the second reactant is 0.20 cm ３ / g-cat or more, the process for producing bis(aminomethyl)cyclohexane according to <19>.

[0008] According to the present invention, a technique that exhibits excellent reaction performance in the production of BAC can be provided.

[0009] Hereinafter, a mode for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The following present embodiment is an illustration for describing the present invention, and is not intended to limit the present invention to the following content. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.

[0010] <Catalyst> The catalyst of the present embodiment is a catalyst for producing bis(aminomethyl)cyclohexane having hydrogenation ability, and the CO adsorption amount measured by the following CO pulse measurement method for the catalyst is 0.20 cm ３ / g-cat or higher. (CO pulse measurement method) (1) Contact 50 mg of the catalyst in the sample tube with He gas at a gas flow rate of 50 sccm for 20 minutes, raising the catalyst temperature to 260°C. (2) Contact the catalyst that has gone through (1) with He gas at a gas flow rate of 50 sccm for 15 minutes, maintaining the catalyst temperature at 260°C during this time. (3) Apply H to the catalyst that has gone through (2). ２ (1) Contact the catalyst with the gas at a gas flow rate of 50 sccm for 30 minutes, during which time the catalyst temperature is maintained at 260°C. (4) Contact the catalyst that has gone through (3) with He gas at a gas flow rate of 50 sccm for 15 minutes, during which time the catalyst temperature is maintained at 260°C. (5) Contact the catalyst that has gone through (4) with He gas at a gas flow rate of 50 sccm, during which time the catalyst temperature is lowered to 50°C. (6) Contact the catalyst that has gone through (5) with He gas at a gas flow rate of 50 sccm for 15 minutes, during which time the catalyst temperature is maintained at 50°C. (7) The catalyst that has gone through (6) above is brought into contact with He gas at a gas flow rate of 30 sccm, during which time the catalyst temperature is maintained at 50°C, and a CO / He mixed gas with a CO concentration of 10 volume% is flowed into the measuring tube at a gas flow rate of 50 sccm for 60 seconds, and then injected into the sample tube after 10 seconds. (8) Based on the results of (7) above, the amount of CO adsorbed is calculated from the amount of CO gas consumed. Here, pulse detection is based on a pulse detection judgment value of 0.001 mV / sec, and the amount of CO gas consumed is determined to have reached saturation when the error of the detection amount of the last 3 pulses becomes within 2.0%, and is determined based on the pulse measurement results until saturation is reached. Because the catalyst of this embodiment is configured as described above, it exhibits excellent reaction performance in the production of BAC.

[0011] (CO pulse measurement method) The catalyst of this embodiment has a CO adsorption amount of 0.20 cm³ measured by the CO pulse measurement method described above. ３Because the CO adsorption amount is greater than or equal to / g-cat, it exhibits excellent reaction performance in the production of BAC. The reason for this is not entirely clear, and this is not intended to limit the reason, but it is speculated as follows. The inventors speculated that there is a correlation between the amount of CO adsorption measured by the CO pulse measurement method of the catalyst and the reaction performance in the production of BAC, and focused on the above CO adsorption amount. That is, the inventors speculated that on the surface of a catalyst with a CO adsorption amount above a certain level, there are many adsorption sites for xylylenediamine, which is a raw material for BAC production, and the hydrogenation reaction can proceed more efficiently. Based on this speculation, the inventors conducted further investigations and found a tendency that the reaction performance in the production of BAC improves by using the amount of CO adsorption obtained by this measurement as an indicator and raising its value above a certain level. That is, when the CO adsorption amount is 0.20 cm ３ We found that catalysts with a CO adsorption capacity of 1 / g-cat or higher exhibit superior reaction performance in the production of BAC. However, the above only describes one possible factor contributing to the superior reaction performance of the catalyst in this embodiment in the production of BAC, and the mechanism of action of this embodiment is not limited to this. In addition to the above viewpoint, from the viewpoint of further improving the reaction performance in the production of BAC, the CO adsorption amount is set to 0.50 cm. ３ It is preferable that the amount of CO adsorbed by the CO pulse measurement method is 10.00 cm³ or more. ３ It is preferable that the amount of CO adsorption is 1 / g-metal or higher. More specifically, the amount of CO adsorption can be measured based on the method described in the examples below. The amount of CO adsorption can be adjusted to the above range by, for example, producing a catalyst based on the manufacturing method described below.

[0012] From the viewpoint of catalytic strength, the catalyst of this embodiment preferably includes a catalytic component and a carrier that supports the catalytic component.

[0013] (Catalyst Component) The catalyst component in this embodiment is not particularly limited, and various known catalyst components can be used. Examples of catalyst components in this embodiment include Ru, Rh, Ni, Pd, and Co, and these can be used individually or in combination of two or more. In this embodiment, from the viewpoint of hydrogenation capacity, the catalyst component preferably includes at least one selected from the group consisting of Ru, Rh, Ni, Pd, and Co, and more preferably includes Ru. The catalyst of this embodiment particularly includes a catalyst component and a carrier supporting the catalyst component, and the catalyst component preferably includes at least one selected from the group consisting of Ru, Rh, Ni, Pd, and Co, and more preferably includes Ru.

[0014] The average particle size of the catalyst component in this embodiment is not particularly limited, but from the viewpoint of hydrogenation capacity, it is preferably 15.00 nm or less, more preferably 10.00 nm or less, and even more preferably 5.00 nm or less. The lower limit of the average particle size of the catalyst component is not particularly limited and may be 0.1 nm or more. The average particle size of the catalyst component can be calculated from the amount of CO adsorbed measured by the CO pulse measurement method. The average particle size of the catalyst component can be adjusted to the above range, for example, by manufacturing the catalyst based on the manufacturing method described later.

[0015] The surface area of ​​the catalyst component in this embodiment is not particularly limited, but from the viewpoint of hydrogenation capacity, it is 10 m². 2 Preferably, the amount is 40mg or more. 2 It is more preferable that the amount be 70 mg or more. 2 It is even more preferable that the amount be 1 / g-metal or higher, and 100m 2 It is even more preferable that the concentration be 120m or higher, with a concentration of 1 / g-metal. 2 It is particularly preferable that the amount is 1 / g-metal or more. The upper limit of the surface area of ​​the catalyst component is not particularly limited, but is 1000 m 2 / g-metal or less. The surface area of the catalyst component can be calculated from the CO adsorption amount measured by the CO pulse measurement method. The surface area of the catalyst component can be adjusted to the above range, for example, by producing the catalyst according to the production method described later.

[0016] The dispersity of the catalyst component in the present embodiment is not particularly limited, but from the viewpoint of hydrogenation ability, it is preferably 10% or more, more preferably 30% or more, and still more preferably 50% or more. The upper limit of the dispersity of the catalyst component is not particularly limited, and may be 100% or less. In the present specification, the dispersity of a catalyst component is an index representing how uniformly the catalyst components present on the catalyst surface are dispersed. The closer the dispersity of the catalyst component is to 100%, the more uniformly the catalyst component is dispersed on the catalyst surface, which means that the hydrogenation ability of the catalyst is higher. The dispersity of the catalyst component can be calculated from the CO adsorption amount measured by the CO pulse measurement method. The dispersity of the catalyst component can be adjusted to the above range, for example, by producing the catalyst according to the production method described later.

[0017] The content of the catalyst component in the present embodiment is not particularly limited, but from the viewpoint of hydrogenation ability, it is preferably 0.1 to 10.0% by mass based on 100% by mass of the catalyst. When the catalyst of the present embodiment contains Ru, from the viewpoint of excellent BAC yield, the content of Ru is preferably 0.1 to 10.0% by mass based on 100% by mass of the catalyst. The content of the above catalyst component can be measured by X-ray fluorescence analysis (XRF). In addition, the above content can also be specified as the raw material charging ratio during catalyst production.

[0018] (Support) The support in the present embodiment is not particularly limited as long as it can support a catalyst component, and various known supports can be employed. Examples of the support in the present embodiment include alumina, diatomaceous earth, carbon, etc. One of these may be used alone, or two or more thereof may be used in combination. In the present embodiment, from the viewpoint of catalyst strength, the support preferably contains alumina.

[0019] The catalyst of this embodiment may further contain alkali metals. The alkali metals in this embodiment are distinct from the catalyst components described above and are not particularly limited in type; for example, Li, Na, K, Rb, and Cs can be cited. These can be used individually or in combination of two or more. The alkali metals in this embodiment preferably include at least one selected from the group consisting of Na, K, and Li. More preferably, the alkali metals in this embodiment include at least one selected from the group consisting of Na and K. When the catalyst of this embodiment contains alkali metals, from the viewpoint of further improving the BAC yield, the alkali metal content is preferably 0.1 to 10.0% by mass relative to 100% by mass of the catalyst. In particular, when the catalyst of this embodiment contains Na, from the viewpoint of further improving the BAC yield, the Na content is preferably 0.1 to 10.0% by mass relative to 100% by mass of the catalyst. The Na content and the content of other alkali metals can be measured by X-ray fluorescence analysis (XRF). Furthermore, the Na content and other alkali metal content can also be specified as the raw material charge ratio during catalyst production.

[0020] The catalyst of the present embodiment may further contain an alkaline earth metal. The alkaline earth metal in the present embodiment is distinguished from the aforementioned catalyst components, and the type thereof is not particularly limited, and examples thereof include Be, Mg, Ca, Sr, and Ba. One of these may be used alone, or two or more thereof may be used in combination. The alkaline earth metal in the present embodiment preferably contains at least one selected from the group consisting of Be, Mg and Ca. The alkaline earth metal in the present embodiment more preferably contains Mg. When the catalyst of the present embodiment contains an alkaline earth metal, from the viewpoint of further improving the BAC yield, the content of the alkaline earth metal is preferably 0.1 to 10.0 mass% based on 100 mass% of the catalyst. In particular, when the catalyst of the present embodiment contains Mg, from the viewpoint of further improving the BAC yield, the content of Mg is preferably 0.1 to 10.0 mass% based on 100 mass% of the catalyst. The content of Mg described above and the content of other alkaline earth metals can be measured by X-ray fluorescence analysis (XRF). In addition, the content of Mg described above and the content of other alkaline earth metals can also be specified as the raw material charging ratio during catalyst production.

[0021] The catalyst of the present embodiment may contain Cl, and the content thereof is not particularly limited, but the lower the content is, the more preferable it is. Based on 100 mass% of the catalyst, the content is preferably 0.001 to 0.1 mass%, more preferably 0.001 to 0.07 mass%, still more preferably 0.001 to 0.05 mass%, and even more preferably 0.001 to 0.03 mass%. When the Cl content in the catalyst is within the above range, the BAC yield tends to be further improved. The content of Cl in the catalyst can be measured by X-ray fluorescence analysis (XRF).

[0022] Cl contained in the catalyst of the present embodiment is, for example, derived from raw materials used in producing the catalyst, and the content of Cl can be adjusted by adjusting the Cl concentration in the raw material solution during catalyst production, or by passing through the base treatment step (b) described later, or the like.

[0023] <Method for Manufacturing the Catalyst> The method for manufacturing the catalyst of this embodiment is not particularly limited as long as the catalyst of this embodiment can be obtained, but it is preferable to obtain it by the following method. That is, the preferred method for manufacturing the catalyst of this embodiment (hereinafter also referred to as "method (A)") includes a loading step (a) in which a catalyst component is reacted with a support to obtain a first reactant, and a base treatment step (b) in which a basic aqueous solution is added to the first reactant to obtain a second reactant. Since method (A) is configured as described above, a catalyst that exhibits excellent reaction performance in the production of BAC can be efficiently manufactured.

[0024] (Supporting step (a)) In supporting step (a), the catalyst component and the support are reacted to obtain a first reactant. In supporting step (a), it is preferable to obtain the first reactant by reacting a chloride of the catalyst component, as exemplified below, with the support. The catalyst component and support can be those exemplified in <Catalyst> as appropriate. That is, the chloride of the catalyst component can be the chloride of the catalyst component described above. The reaction between the catalyst component and the support is not limited to the following, but can be carried out by employing various known conditions, for example, the spontaneous wetness (IW) method or the equilibrium adsorption method. In this embodiment, from the viewpoint of improving the hydrogenation ability of the obtained catalyst, step (a) preferably includes adsorbing the raw material solution onto the support and then drying it. The raw material solution is not limited to the following, but preferably contains at least one chloride selected from the group consisting of ruthenium-n chloride hydrate, rhodium chloride trihydrate, nickel chloride hexahydrate, sodium palladium chloride trihydrate, and cobalt chloride hexahydrate.

[0025] (Base treatment step (b)) In base treatment step (b), a basic aqueous solution is added to the first reactant to obtain a second reactant. The second reactant can be used as the catalyst of this embodiment. The catalyst of this embodiment, obtained through base treatment step (b), has a CO adsorption amount of 0.20 cm³ as measured by the CO pulse measurement method. ３The concentration can be controlled to above / g-cat, resulting in excellent reaction performance in the production of BAC. Furthermore, the average particle size, surface area, and dispersion of the catalyst component can be appropriately controlled by going through the base treatment step (b). Specifically, by going through the base treatment step (b), aggregation of the catalyst component in the second reactant can be suppressed, and as a result, the amount of CO adsorbed measured by the CO pulse measurement method is 0.20 cm³. ３ The amount can be set to 1 / g-cat or more. Furthermore, the Cl content in the resulting second reactant can be reduced. The Cl content in the second reactant is preferably 0.001 to 0.1% by mass, more preferably 0.001 to 0.07% by mass, even more preferably 0.001 to 0.05% by mass, and even more preferably 0.001 to 0.03% by mass, based on 100% by mass of the second reactant.

[0026] In this embodiment, from the viewpoint of improving the hydrogenation capacity of the obtained catalyst, the base treatment step (b) preferably includes adding a basic aqueous solution to the first reactant to obtain a second reactant, and then drying it. The basic aqueous solution is not limited to the following, but preferably includes, for example, an aqueous sodium hydroxide solution. From the viewpoint of hydrogenation capacity, in the manufacturing method (A), the amount of CO adsorbed to the second reactant, as measured by the CO pulse measurement method, is 0.20 cm. ３ Preferably, the value is 0.50 cm or more, and the concentration is 0.50 cm. ３ It is more preferable that the CO adsorption amount is 10.00 cm³ or more. ３ It is preferable that the value is 1 / g-metal or higher.

[0027] In the base treatment step (b), the temperature conditions under which the base treatment is carried out are not particularly limited, but from the viewpoint of further suppressing the aggregation of catalyst components in the second reaction product and improving the hydrogenation ability of the resulting catalyst, 10 to 90°C is preferred, 10 to 70°C is more preferred, 15 to 50°C is even more preferred, and 20 to 30°C is particularly preferred.

[0028] In the base treatment step (b), the treatment time for the base treatment is not particularly limited, but from the viewpoint of improving the hydrogenation ability of the resulting catalyst, 1 to 96 hours is preferred, 12 to 84 hours is more preferred, 24 to 72 hours is even more preferred, and 36 to 60 hours is particularly preferred.

[0029] (Step (c)) The manufacturing method (A) may further include, after the loading step (a), step (c) of adding an alkali metal and / or alkaline earth metal to the first reactant to obtain a third reactant. The third reactant can be used as the catalyst of this embodiment by adding a basic aqueous solution in the base treatment step (b) described above to obtain a fourth reactant, or it can be used as the catalyst of this embodiment after further adjusting its properties such as hydrogenation ability through step (d) described later. The alkali metals and alkaline earth metals can be those exemplified in <Catalyst> as appropriate. The addition of alkali metals and / or alkaline earth metals is not limited to the following, but can be carried out by employing various known conditions, for example, in the spontaneous wetness (IW) method. The alkali metals and alkaline earth metals are not limited to the following, but may be added as carbonates, bicarbonates, nitrates, hydroxides, etc. In this embodiment, the alkaline earth metal preferably contains Mg from the viewpoint of the hydrogenation ability of the resulting catalyst.

[0030] Furthermore, step (c) may be included after the base treatment step (b). In that case, an alkali metal and / or alkaline earth metal can be added to the second reactant to obtain a third reactant. The third reactant itself can be used as the catalyst of this embodiment, or it can be used as the catalyst of this embodiment after further adjusting its properties such as hydrogenation capacity through step (d) described later.

[0031] (Step (d)) The manufacturing method (A) may further include step (d) of reducing the second reactant, the third reactant, or the fourth reactant to obtain a fifth reactant. When the fifth reactant is used as the catalyst of this embodiment, the hydrogenation capacity tends to be higher. The temperature conditions for step (d) are not particularly limited, but from the viewpoint of the hydrogenation capacity of the obtained catalyst, it is preferable that step (d) be carried out at a temperature of 160 to 360°C.

[0032] <Method for Producing Bis(aminomethyl)cyclohexane> The method for producing bis(aminomethyl)cyclohexane according to this embodiment (hereinafter also referred to as "the method of this embodiment") includes a hydrogenation step in which xylylenediamine and hydrogen are brought into contact in the presence of a catalyst having hydrogenation ability to obtain bis(aminomethyl)cyclohexane, wherein the amount of CO adsorbed onto the catalyst, as measured by the CO pulse measurement method described below, is 0.20 cm³. ３ / g-cat or higher. (CO pulse measurement method) (1) Contact 50 mg of the catalyst in the sample tube with He gas at a gas flow rate of 50 sccm for 20 minutes, raising the catalyst temperature to 260°C. (2) Contact the catalyst that has gone through (1) with He gas at a gas flow rate of 50 sccm for 15 minutes, maintaining the catalyst temperature at 260°C during this time. (3) Apply H to the catalyst that has gone through (2). ２(1) Contact the catalyst with the gas at a gas flow rate of 50 sccm for 30 minutes, during which time the catalyst temperature is maintained at 260°C. (4) Contact the catalyst that has gone through (3) with He gas at a gas flow rate of 50 sccm for 15 minutes, during which time the catalyst temperature is maintained at 260°C. (5) Contact the catalyst that has gone through (4) with He gas at a gas flow rate of 50 sccm, during which time the catalyst temperature is lowered to 50°C. (6) Contact the catalyst that has gone through (5) with He gas at a gas flow rate of 50 sccm for 15 minutes, during which time the catalyst temperature is maintained at 50°C. (7) The catalyst that has gone through (6) above is brought into contact with He gas at a gas flow rate of 30 sccm, during which time the catalyst temperature is maintained at 50°C, and a CO / He mixed gas with a CO concentration of 10 volume% is flowed into the measuring tube at a gas flow rate of 50 sccm for 60 seconds, and then injected into the sample tube after 10 seconds. (8) Based on the results of (7) above, the amount of CO adsorbed is calculated from the amount of CO gas consumed. Here, pulse detection is based on a pulse detection judgment value of 0.001 mV / sec, and the amount of CO gas consumed is determined to have reached saturation when the error of the detection amount of the last 3 pulses becomes within 2.0%, and is determined based on the pulse measurement results until saturation is reached. Because the manufacturing method of this embodiment is configured as described above, BAC can be manufactured with high reaction performance.

[0033] (Hydrogenation Step) In the hydrogenation step of this embodiment, bis(aminomethyl)cyclohexane is obtained by contacting xylylenediamine with hydrogen in the presence of a catalyst having hydrogenation ability. The reaction method of xylylenediamine and hydrogen is not particularly limited and may be a batch reaction or a reaction method in which xylylenediamine and hydrogen are continuously contacted.

[0034] In the manufacturing method of this embodiment, xylylenediamine, one of the raw materials, has three isomers: ortho, meta, and para, and any of these, either individually or in mixtures, can be used as raw materials. In the manufacturing method of this embodiment, the meta and para isomers are preferably used, and it is more preferable that the xylylenediamine contains meta-xylylenediamine (hereinafter also referred to as "MXDA") and / or para-xylylenediamine (hereinafter also referred to as "PXDA").

[0035] In the manufacturing method of this embodiment, the solvent that can be used is not particularly limited, and various known solvents can be employed. Examples of solvents in this embodiment, but not limited to the following, include water, alkylamines, and alkylenediamines. These can be used individually or in combination of two or more. When alkylamines and alkylenediamines are included as solvents, they are separated by distillation from the reaction product and recycled. Therefore, to facilitate recycling in continuous manufacturing methods in industrialization, it is preferable to select those with 1 to 18 carbon atoms that are liquid at room temperature. In this case, the generation of by-products is further suppressed, and the yield of the target product tends to increase. Examples of alkylamines in this embodiment, but not limited to the following, include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, isopropylamine, diisopropylamine, butylamine, dibutylamine, tributylamine, hexylamine, cyclohexylamine, and 2-ethylhexylamine. These can be used individually or in combination of two or more. The alkylenediamines in this embodiment are not limited to the following, but examples include ethylenediamine, propylenediamine, 1,4-butylenediamine, hexamethylenediamine, and bis(aminomethyl)cyclohexane. These can be used individually or in combination of two or more. In this embodiment, since bis(aminomethyl)cyclohexane obtained by catalytic reduction can be recycled, the solvent in this embodiment preferably contains bis(aminomethyl)cyclohexane.

[0036] In the manufacturing method of this embodiment, the weight ratio of water to the raw material xylylenediamine (amount of xylylenediamine:amount of water) is not particularly limited, but is preferably 1:30 to 1:1.

[0037] In the manufacturing method of this embodiment, the mixed weight ratio of alkylamines and alkylenediamines to the raw material xylylenediamine (amount of xylylenediamine: total amount of alkylamines and alkylenediamines) is not particularly limited, but is preferably 1:30 to 1:1.

[0038] The alkylamines and alkylenediamines mentioned above may be used individually, as mixtures of amines and alkylenediamines, or as mixtures with other organic solvents. Examples of organic solvents that can be mixed include, but are not limited to, methanol, ethanol, isopropyl alcohol, n-propyl alcohol, and other alcohols.

[0039] In the hydrogenation step of this embodiment, the hydrogen supply conditions are not particularly limited, but it is preferable that the hydrogen pressure be 5 MPa or more and 15 MPa or less. In a reaction format in which xylylenediamine and hydrogen are continuously brought into contact, it is preferable that the hydrogen supply amount per 1 mL of catalyst be 0.5 N mL / min or more and 2.5 N mL / min or less. The above hydrogen pressure can be specified as gauge pressure.

[0040] In the manufacturing method of this embodiment, the catalyst has a CO adsorption amount of 0.20 cm, as measured by the CO pulse measurement method, from the viewpoint of hydrogenation capacity. ３ / g-cat or higher, and 0.50 cm ３ It is preferable that the amount of CO adsorbed by the CO pulse measurement method described above is 10 cm³ or more. As the catalyst, the catalyst described in <Catalyst> can be appropriately used. Furthermore, from the viewpoint of hydrogenation capacity, the catalyst in the manufacturing method of this embodiment should have a CO adsorption amount of 10 cm³ or more as measured by the CO pulse measurement method described above. ３ It is preferable that the value is 1 / g-metal or higher.

[0041] The catalyst in the manufacturing method of this embodiment may include a catalyst component and a carrier supporting the catalyst component, and the catalyst component and carrier may be those exemplified in <Catalyst> as appropriate.

[0042] The catalyst in the manufacturing method of this embodiment comprises a catalyst component and a carrier supporting the catalyst component, and it is preferable that the catalyst component contains at least one selected from the group consisting of Ru, Rh, Ni, Pd, and Co, and more preferably Ru. In the manufacturing method of this embodiment, it is preferable that the carrier contains alumina.

[0043] The catalyst in the manufacturing method of this embodiment may contain alkali metals in addition to the catalyst components and support. The alkali metals exemplified in the section on catalysts can be used as appropriate, and from the viewpoint of hydrogenation ability, it is preferable to include at least one selected from the group consisting of Na, K, and Li.

[0044] In the manufacturing method of this embodiment, the catalyst preferably contains 0.1 to 10.0% by mass of catalyst components relative to 100% by mass of catalyst. If the catalyst components include Ru, the Ru content in the catalyst preferably contains 0.1 to 10.0% by mass relative to 100% by mass of catalyst.

[0045] In the manufacturing method of this embodiment, from the viewpoint of hydrogenation capacity, the average particle size of the catalyst components in the catalyst is preferably 15.00 nm or less, more preferably 10.00 nm or less, and even more preferably 5.00 nm or less. The lower limit of the average particle size of the catalyst components is not particularly limited and may be 0.1 nm or more.

[0046] In the manufacturing method of this embodiment, from the viewpoint of hydrogenation capacity, the catalyst has a surface area of ​​10 m² of catalyst components. 2 Preferably, the amount is 40mg or more. 2 It is more preferable that the amount be 70 mg or more. 2 It is even more preferable that the amount be 1 / g-metal or higher, and 100m 2 It is even more preferable that the concentration be 120m or higher, with a concentration of 1 / g-metal. 2 It is particularly preferable that the amount is 1 / g-metal or more. The upper limit of the surface area of ​​the catalyst component is not particularly limited, but is 1000 m 2 It may be less than or equal to / g-metal.

[0047] In the manufacturing method of this embodiment, from the viewpoint of hydrogenation capacity, the degree of dispersion of the catalyst components in the catalyst is not particularly limited, but is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more. The upper limit of the degree of dispersion of the catalyst components is not particularly limited and may be 100% or less.

[0048] The catalyst in the manufacturing method of this embodiment is obtained by manufacturing method (A), and it is preferable that manufacturing method (A) includes a loading step (a) in which the catalyst component and the support are reacted to obtain a first reactant, and a base treatment step (b) in which a basic aqueous solution is added to the first reactant to obtain a second reactant. The second reactant can also be used as the catalyst in the manufacturing method of this embodiment. Here, manufacturing method (A) can be any method described in <Method for Manufacturing a Catalyst>. In manufacturing method (A), from the viewpoint of the hydrogenation capacity of the obtained catalyst, the amount of CO adsorbed on the second reactant, as measured by the CO pulse measurement method, is 0.20 cm³. ３ Preferably, the value is 0.50 cm or more, and the concentration is 0.50 cm. ３ It is more preferable that the amount is 1 / g-cat or more. The loading step (a) preferably includes adsorbing the raw material solution onto the support and then drying it, from the viewpoint of the hydrogenation ability of the obtained catalyst. The basic aqueous solution in the base treatment step (b) preferably includes an aqueous sodium hydroxide solution. In the base treatment step (b), the temperature conditions in which the base treatment is carried out are not particularly limited, but from the viewpoint of improving the BAC yield of the obtained catalyst, 10 to 90°C is preferred, 10 to 70°C is more preferred, 15 to 50°C is even more preferred, and 20 to 30°C is particularly preferred. In the base treatment step (b), the treatment time for the base treatment is not particularly limited, but from the viewpoint of improving the BAC yield of the obtained catalyst, 1 to 96 hours is preferred, 12 to 84 hours is more preferred, 24 to 72 hours is even more preferred, and 36 to 60 hours is particularly preferred.

[0049] The reactor for carrying out the hydrogenation process in this embodiment is not particularly limited, but for example, an autoclave batch reactor or a fixed-bed reactor can be used. In this embodiment, when the process is carried out continuously using a solvent, the reactor may have a configuration that allows for the separation of dissolved gas from the reaction product using a gas-liquid separator, and then the separation of BAC obtained by catalytic hydrogenation, which can then be recycled. Alternatively, the reactor may have a configuration that allows for the separation of the solvent from the reaction product after gas-liquid separation using a solvent recovery facility and then the recycling of the BAC. In this embodiment, the BAC obtained by catalytic hydrogenation can also be used as a solvent, in which case it is preferable to separate the dissolved gas from the reaction product using a gas-liquid separator and then recycle it directly.

[0050] (Optional Steps) The manufacturing method of this embodiment may include optional steps other than the hydrogenation step. The manufacturing method of this embodiment is not limited to the following, but may further include, for example, a purification step. Examples of purification steps include distilling off alkylamines, alkylenediamines and organic solvents at atmospheric pressure and then vacuum distillation, thereby allowing for the preferred separation of the target product (BAC) from the reaction product.

[0051] The embodiments will be described in more detail below with reference to examples, but the scope of these embodiments is not limited by these examples.

[0052] [Example 1] (Catalyst production) 20 g of alumina (NeoBead® GB-13, specific surface area: 180 m²) was prepared at a temperature of 25°C. ２ Using 1 g of ruthenium-n chloride hydrate and 9 g of water, the catalyst components were supported on alumina by the inspirient wetness (IW) method, and then dried at 120°C for 2 hours to obtain support 1. Support 1 was subjected to a basic treatment using 60 g of 1 M sodium hydroxide and 300 g of water (temperature conditions: 25°C, treatment time: 48 hours) (i.e., support 1 was in contact with sodium hydroxide and water for 48 hours), and then dried at 110°C for 2 hours to obtain the catalyst of Example 1. X-ray fluorescence analysis (XRF) was performed on the catalyst of Example 1, and the Cl content in the catalyst was measured to be 0.011 mass%.

[0053] (Measurement by CO pulse measurement method) The amount of CO adsorbed on the obtained catalyst was measured using a catalyst analyzer ("BELCAT-B", manufactured by Microtrac-Bel) by the following method: (1) He gas was brought into contact with 50 mg of catalyst in a sample tube at a gas flow rate of 50 sccm for 20 minutes, and the catalyst temperature was raised to 260°C. (2) He gas was brought into contact with the catalyst after (1) at a gas flow rate of 50 sccm for 15 minutes, and the catalyst temperature was maintained at 260°C during this time. (3) H ２(4) The catalyst was brought into contact with the gas at a gas flow rate of 50 sccm for 30 minutes, during which time the catalyst temperature was maintained at 260°C. (5) The catalyst that went through (4) was brought into contact with He gas at a gas flow rate of 50 sccm for 15 minutes, during which time the catalyst temperature was maintained at 260°C. (6) The catalyst that went through (5) was brought into contact with He gas at a gas flow rate of 50 sccm for 15 minutes, during which time the catalyst temperature was lowered to 50°C. (7) The catalyst that has undergone the procedure in (6) above was brought into contact with He gas at a gas flow rate of 30 sccm, during which time the catalyst temperature was maintained at 50°C, and a CO / He mixed gas with a CO concentration of 10 volume% was flowed into the measuring tube at a gas flow rate of 50 sccm for 60 seconds, and then injected into the sample tube after 10 seconds. (8) Based on the results of (7) above, the amount of CO adsorbed was calculated from the amount of CO gas consumed. Here, pulse detection was based on a pulse detection judgment value of 0.001 mV / sec, and the amount of CO gas consumed was determined to have reached saturation when the error of the detection amount of the last three pulses was within 2.0%, and was determined based on the pulse measurement results until saturation was reached. The start and end of the pulse peak are automatically detected by the "BELCAT-B" software. The injection was terminated when the error of the detection amount of the last three pulses was within 2.0%, which was determined to be when adsorption had reached saturation, and the amount of CO adsorbed was calculated from the difference between the peak area at saturation and the peak area at unsaturation. Furthermore, the surface area, average particle size, and dispersion of the catalyst components in the catalyst were calculated using the "BELCAT-B" software based on the obtained CO adsorption amount. These results are shown in Table 1. The stoichiometric ratios used when calculating the surface area, average particle size, and dispersion of the catalyst components using the "BELCAT-B" software are as described in Table 1.

[0054] (Preparation of BAC) The following hydrogenation reaction was carried out using a 300 mL SUS316 autoclave batch reactor. First, 1.5 g of catalyst was contacted with hydrogen gas at 260 °C and a gas flow rate of 100 mL / min for 7 hours to reduce the catalyst. Next, in the presence of the reduced catalyst, 150 g of a mixture consisting of metaxylylenediamine (20% by mass) as the raw material and water (80% by mass) as the solvent was supplied to the reactor with a catalyst amount of 1.5 g, a reaction temperature of 100 °C, and a hydrogen pressure of 7.0 MPa (gauge pressure, with the pressure reduced as needed during the reaction).

[0055] (Reaction Results) Five hours after the start of the reaction, the reaction product was collected by pressure filtration and analyzed by gas chromatography. The results are shown in Table 1. The gas chromatography analysis conditions were as follows, and quantification was performed using the internal standard method (internal standard substance: diphenylmethane). GC instrument: Shimadzu GC2030 Column: HP-1MS (30 m length × 0.25 mm inner diameter × 0.25 μm film thickness column) Sample introduction temperature: 300°C Split ratio: 10 Temperature program: Hold at 150°C for 5 minutes, then raise to 300°C (10 min), then hold at 300°C for 10 minutes Detector and detection temperature: Flame ionization detector (FID), 300°C Carrier gas: He (46.2 mL / min) Injection volume: 0.2 μL

[0056] [Example 2] In the production of the catalyst of Example 1, alumina (NeoBead (registered trademark) GB-13, specific surface area: 180 m²) ２ Instead of ( / g, manufactured by Mizusawa Chemical Industry Co., Ltd.), alumina (KHO-24, specific surface area: 140 m²) is used. ２ The catalyst for Example 2 was obtained in the same manner as in Example 1, except that a chlorine (manufactured by Sumika Alchem ​​Co., Ltd.) was used. The Cl content in the catalyst was measured in the same manner as in Example 1, and the Cl content was found to be 0.014% by mass.

[0057] [Example 3] In the production of the catalyst of Example 1, alumina (NeoBead (registered trademark) GB-13, specific surface area: 180 m²) ２ Instead of ( / g, manufactured by Mizusawa Chemical Industry Co., Ltd.), alumina (F-200, specific surface area: 350 m²) ２The catalyst for Example 3 was obtained in the same manner as in Example 1, except that a 2 / g (manufactured by BASF) was used.

[0058] [Example 4] In the production of the catalyst of Example 1, alumina (NeoBead (registered trademark) GB-13, specific surface area: 180 m²) ２ Instead of ( / g, manufactured by Mizusawa Chemical Industry Co., Ltd.), alumina (N612N, specific surface area: 191 m²) is used. ２ The catalyst for Example 4 was obtained in the same manner as in Example 1, except that a g of (manufactured by JGC Catalysts & Chemicals Co., Ltd.) was used.

[0059] [Example 5] In the production of the catalyst of Example 1, alumina (NeoBead (registered trademark) GB-13, specific surface area: 180 m²) ２ Instead of ( / g, manufactured by Mizusawa Chemical Industry Co., Ltd.), alumina (N611N3, specific surface area: 180 m²) is used. ２ The catalyst for Example 5 was obtained in the same manner as in Example 1, except that a ( / g, manufactured by JGC Catalysts & Chemicals Co., Ltd.) was used.

[0060] [Example 6] In the production of BAC in Example 1, the catalyst of Example 2 was used instead of the catalyst of Example 1, and 150 g of a mixture of para-xylylenediamine (20% by mass) and water (80% by mass) as a solvent was used instead of 150 g of a mixture of metaxylylenediamine (20% by mass) and water (80% by mass) as a solvent. The production of BAC was carried out in the same manner as in Example 1, and the reaction performance was evaluated. The results are shown in Table 1.

[0061] [Example 7] 20 g of alumina (KHO-24, specific surface area: 140 m²) under a temperature of 25°C. ２Using 1 g of ruthenium-n chloride hydrate and 9 g of water, the catalyst components were supported on alumina by the inspirient wetness (IW) method, and then dried at 120°C for 2 hours to obtain support 2. Support 2 was subjected to a base treatment with 60 g of 1 M sodium hydroxide and 300 g of water (temperature conditions: 25°C, treatment time: 48 hours) (i.e., support 2 was in contact with sodium hydroxide and water for 48 hours), and then dried at 110°C for 2 hours to obtain support 3. Next, using 20 g of support 3, 4 g of magnesium nitrate hexahydrate and 4 g of water, magnesium was supported on support 3 by the inspirient wetness (IW) method, and then dried at 110°C for 2 hours to obtain the catalyst of Example 7. The Cl content in the catalyst was measured in the same manner as in Example 1, and the Cl content was found to be 0.009% by mass.

[0062] (Amount of alkaline earth metals in the catalyst) The amount of alkaline earth metals (Mg) contained in the catalyst was determined to be 1.7% by mass, based on 100% by mass of the catalyst, as determined by X-ray fluorescence (XRF) analysis.

[0063] [Example 8] Under a temperature of 25°C, 1 g of ruthenium-n hydrate was dissolved in 600 g of water to obtain an aqueous ruthenium chloride solution. 20 g of alumina (NeoBead® GB-13, specific surface area: 180 m²) was added to the obtained aqueous ruthenium chloride solution. ２ A ruthenium chloride aqueous solution (manufactured by Mizusawa Chemical Industry Co., Ltd.) was added, and the mixture of ruthenium chloride aqueous solution and alumina was stirred for 15 minutes (200 rpm) to support the catalyst component on the alumina (equilibrium adsorption method). The mixture was then recovered by filtration and dried at 120°C for 2 hours to obtain support 4. Support 4 was subjected to a base treatment using 60 g of 1 M sodium hydroxide and 300 g of water (temperature conditions: 25°C, treatment time: 48 hours) (i.e., support 4 was in contact with sodium hydroxide and water for 48 hours), and dried at 110°C for 2 hours to obtain the catalyst of Example 8. The Cl content in the catalyst was measured in the same manner as in Example 1, and the Cl content was found to be 0.024% by mass.

[0064] [Comparative Example 1] Under a temperature of 25°C, 1 g of ruthenium-n hydrate was dissolved in 39 g of water to obtain an aqueous ruthenium chloride solution. 20 g of alumina (NeoBead® GB-13, specific surface area: 180 m²) was added to the obtained aqueous ruthenium chloride solution. ２ ( / g, manufactured by Mizusawa Chemical Industries, Ltd.) was added, and a container containing a mixture of ruthenium chloride aqueous solution and alumina was immersed in a 60°C water bath under reduced pressure until the water in the mixture was gone, thereby supporting the catalyst component on the alumina (evaporation to dryness method). After that, it was dried at 120°C for 2 hours to obtain supported material a. Supported material a was calcined at 400°C in an air atmosphere to obtain the catalyst of Comparative Example 1.

[0065] [Comparative Example 2] In the production of the catalyst of Example 1, the supported material 1 obtained without base treatment was calcined at 400°C in an air atmosphere to obtain the catalyst of Comparative Example 2. The Cl content in the catalyst was measured in the same manner as in Example 1, and the Cl content was found to be 0.971% by mass.

[0066] [Comparative Example 3] The catalyst for Comparative Example 3 was obtained in the same manner as for Comparative Example 1, except that in the preparation of the catalyst for Comparative Example 1, 5 g of sodium ruthenate (Na2(RuO4)) and 35 g of water were used instead of 1 g of ruthenium-n chloride hydrate and 39 g of water.

[0067] [Comparative Example 4] Under a temperature of 25°C, 20 g of alumina (NeoBead® GB-13, specific surface area: 180 m²) ２ Using 5 g of sodium ruthenate (Na2(RuO4)) and 5 g of water (manufactured by Mizusawa Chemical Industries, Ltd.), the catalyst components were supported on alumina by the inspirient wetness (IW) method, and then dried at 120°C for 2 hours to obtain support b. Support b was calcined at 400°C under air to obtain the catalyst of Comparative Example 4.

[0068] For the catalysts obtained in Examples 2-5, 7-8, and Comparative Examples 1-4, the amount of CO adsorbed was measured by the CO pulse measurement method in the same manner as in Example 1. Furthermore, the surface area, average particle size, and dispersion of the catalyst components in the catalyst were calculated from the above CO adsorbed amounts. In addition, BAC production was carried out using the catalysts obtained in Examples 2-8 and Comparative Examples 1-4 in the same manner as in Example 1, and the reaction performance was evaluated. These results are shown in Table 1.

[0069]

[0070] The catalyst component is supported on a carrier by the IW method or equilibrium adsorption method, and obtained through a base treatment step, with a CO adsorption capacity of 0.20 cm³. ３ The catalysts of Examples 1 to 8, which had a concentration of 1 / g-cat or higher, were found to have higher BAC reaction performance compared to Comparative Examples 1 to 4. Furthermore, in Comparative Examples 1 to 4, which were obtained without a base treatment step, the CO adsorption amount was 0.20 cm³ regardless of the method of supporting the catalyst component. ３ It was shown that it is more difficult to control than / g-cat.

Claims

1. A catalyst having hydrogenation ability for producing bis(aminomethyl)cyclohexane, wherein the amount of CO adsorbed to the catalyst, as measured by the CO pulse measurement method described below, is 0.20 cm³. ３ A catalyst having a concentration of 1 / g-cat or higher. (CO pulse measurement method) (1) Contact 50 mg of the catalyst in a sample tube with He gas at a gas flow rate of 50 sccm for 20 minutes, raising the catalyst temperature to 260°C. (2) Contact the catalyst that has gone through (1) with He gas at a gas flow rate of 50 sccm for 15 minutes, maintaining the catalyst temperature at 260°C during this time. (3) Apply H to the catalyst that has gone through (2). ２ (1) Contact the catalyst with the gas at a gas flow rate of 50 sccm for 30 minutes, during which time the catalyst temperature is maintained at 260°C. (4) Contact the catalyst that has gone through (3) with He gas at a gas flow rate of 50 sccm for 15 minutes, during which time the catalyst temperature is maintained at 260°C. (5) Contact the catalyst that has gone through (4) with He gas at a gas flow rate of 50 sccm, during which time the catalyst temperature is lowered to 50°C. (6) Contact the catalyst that has gone through (5) with He gas at a gas flow rate of 50 sccm for 15 minutes, during which time the catalyst temperature is maintained at 50°C. (7) The catalyst that has gone through (6) above is brought into contact with He gas at a gas flow rate of 30 sccm, during which time the catalyst temperature is maintained at 50°C, and a CO / He mixed gas with a CO concentration of 10 volume% is flowed into the measuring tube at a gas flow rate of 50 sccm for 60 seconds, and then injected into the sample tube after 10 seconds. (8) Based on the results of (7) above, the amount of CO adsorbed is calculated from the amount of CO gas consumed. Here, pulse detection is based on a pulse detection judgment value of 0.001 mV / sec, and the amount of CO gas consumed is determined to have reached saturation when the error of the detection amount of the last 3 pulses becomes within 2.0%, and is determined based on the pulse measurement results until saturation is reached.

2. The catalyst according to claim 1, wherein the catalyst comprises a catalytic component and a carrier supporting the catalytic component, and the catalytic component comprises at least one selected from the group consisting of Ru, Rh, Ni, Pd, and Co.

3. The amount of CO adsorbed by the CO pulse measurement method is 10.00 cm³. ３ The catalyst according to claim 1, wherein the ion content is 1 / g-metal or higher.

4. The catalyst according to claim 2, wherein the average particle size of the catalyst component is 15.00 nm or less.

5. The catalyst according to claim 2, wherein the Ru content in the catalyst is 0.1 to 10.0% by mass based on 100% by mass of the catalyst.

6. The catalyst according to claim 1, wherein the Cl content in the catalyst is 0.001 to 0.1% by mass based on 100% by mass of the catalyst.

7. The catalyst according to claim 2, wherein the carrier comprises alumina.

8. A method for producing a catalyst according to claim 1, comprising: a supporting step (a) of reacting a catalyst component with a support to obtain a first reactant; and a base treatment step (b) of adding a basic aqueous solution to the first reactant to obtain a second reactant.

9. A method for producing a catalyst according to claim 8, comprising reacting the chloride of the catalyst component with the carrier in the supporting step (a).

10. The method for producing a catalyst according to claim 8, wherein in the base treatment step (b), the basic aqueous solution contains an aqueous sodium hydroxide solution.

11. The method for producing a catalyst according to claim 8, wherein the base treatment step (b) is carried out at a temperature of 10 to 90°C.

12. The amount of CO adsorbed to the second reactant, as measured by the CO pulse measurement method, is 0.20 cm³. ３ A method for producing a catalyst according to claim 8, wherein the amount is 1 / g-cat or more.

13. The process includes a hydrogenation step of obtaining bis(aminomethyl)cyclohexane by contacting xylylenediamine with hydrogen in the presence of a catalyst having hydrogenation ability, wherein the amount of CO adsorbed onto the catalyst, as measured by the CO pulse measurement method described below, is 0.20 cm³. ３ A method for producing bis(aminomethyl)cyclohexane having a concentration of 1 / g-cat or higher. (CO pulse measurement method) (1) Contact 50 mg of the catalyst in a sample tube with He gas at a gas flow rate of 50 sccm for 20 minutes, raising the catalyst temperature to 260°C. (2) Contact the catalyst that has gone through (1) with He gas at a gas flow rate of 50 sccm for 15 minutes, maintaining the catalyst temperature at 260°C during this time. (3) Apply H to the catalyst that has gone through (2). ２ (1) Contact the catalyst with the gas at a gas flow rate of 50 sccm for 30 minutes, during which time the catalyst temperature is maintained at 260°C. (4) Contact the catalyst that has gone through (3) with He gas at a gas flow rate of 50 sccm for 15 minutes, during which time the catalyst temperature is maintained at 260°C. (5) Contact the catalyst that has gone through (4) with He gas at a gas flow rate of 50 sccm, during which time the catalyst temperature is lowered to 50°C. (6) Contact the catalyst that has gone through (5) with He gas at a gas flow rate of 50 sccm for 15 minutes, during which time the catalyst temperature is maintained at 50°C. (7) The catalyst that has gone through (6) above is brought into contact with He gas at a gas flow rate of 30 sccm, during which time the catalyst temperature is maintained at 50°C, and a CO / He mixed gas with a CO concentration of 10 volume% is flowed into the measuring tube at a gas flow rate of 50 sccm for 60 seconds, and then injected into the sample tube after 10 seconds. (8) Based on the results of (7) above, the amount of CO adsorbed is calculated from the amount of CO gas consumed. Here, pulse detection is based on a pulse detection judgment value of 0.001 mV / sec, and the amount of CO gas consumed is determined to have reached saturation when the error of the detection amount of the last 3 pulses becomes within 2.0%, and is determined based on the pulse measurement results until saturation is reached.

14. The method for producing bis(aminomethyl)cyclohexane according to claim 13, wherein the catalyst comprises a catalytic component and a carrier supporting the catalytic component, and the catalytic component comprises at least one selected from the group consisting of Ru, Rh, Ni, Pd, and Co.

15. The amount of CO adsorbed by the CO pulse measurement method of the catalyst is 10.00 cm³. ３ A method for producing bis(aminomethyl)cyclohexane according to claim 13, wherein the amount is 1 / g-metal or more.

16. The method for producing bis(aminomethyl)cyclohexane according to claim 14, wherein the average particle size of the catalyst component is 15.00 nm or less.

17. The method for producing bis(aminomethyl)cyclohexane according to claim 14, wherein the Ru content in the catalyst is 0.1 to 10.0% by mass based on 100% by mass of the catalyst.

18. The method for producing bis(aminomethyl)cyclohexane according to claim 14, wherein the carrier contains alumina.

19. A method for producing bis(aminomethyl)cyclohexane according to claim 13, further comprising a catalyst production step for producing the catalyst, wherein the catalyst production step comprises: a supporting step (a) for reacting the catalyst component with the support to obtain a first reactant; and a base treatment step (b) for adding a basic aqueous solution to the first reactant to obtain a second reactant.

20. The amount of CO adsorbed to the second reactant, as measured by the CO pulse measurement method, is 0.20 cm³. ３ A method for producing bis(aminomethyl)cyclohexane according to claim 19, wherein the amount is 1 / g-cat or more.

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