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

Abstract

Provided is a technique for exhibiting excellent reaction results in the production of BAC. Also provided is a catalyst which is for producing bis(aminomethyl)cyclohexane and which has hydrogenation ability, wherein the catalyst includes a catalyst component and a carrier that supports the catalyst component, and the supported thickness of the catalyst component is greater than 170 μm and equal to or less than 1,321 μm.

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 embodiments: <1> A catalyst for producing bis(aminomethyl)cyclohexane having hydrogenation ability, wherein the catalyst comprises a catalyst component and a carrier supporting the catalyst component, and the thickness of the catalyst component supported is greater than 170 μm and less than or equal to 1321 μm. <2> The catalyst according to <1>, wherein the catalyst component comprises at least one selected from the group consisting of Ru, Rh, Ni, Pd, and Co. <3> The catalyst according to <1> or <2>, wherein the catalyst component contains Ru. <4> The catalyst according to <2> or <3>, wherein the Ru content in the catalyst is 0.1 to 10.0% by mass based on 100% by mass of the catalyst. <5> The catalyst according to any one of <1> to <4>, wherein the carrier contains alumina. <6> A method for producing a catalyst as described in any of <1> to <5>, comprising: a loading step (a) in which a raw material solution containing 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, wherein the Cl concentration of the raw material solution is 0.1 to 12.0 mol / dm 3A method for producing a catalyst. <7> The method for producing a catalyst according to <6>, wherein the supporting step (a) includes reacting a raw material solution containing the chloride of the catalyst component with the carrier. <8> The method for producing a catalyst according to <6> or <7>, wherein in the base treatment step (b), the basic aqueous solution includes an aqueous sodium hydroxide solution. <9> The method for producing a catalyst according to any one of <6> to <8>, wherein the supporting thickness of the catalyst component in the second reactant is greater than 170 μm and less than or equal to 1321 μm. <10> A method for producing bis(aminomethyl)cyclohexane, comprising a hydrogenation step of contacting xylylenediamine with hydrogen in the presence of a catalyst having hydrogenating ability, wherein the catalyst comprises a catalyst component and a carrier supporting the catalyst component, and the supporting thickness of the catalyst component is greater than 170 μm and less than or equal to 1321 μm. <11> The method for producing bis(aminomethyl)cyclohexane according to <10>, wherein the catalyst component comprises at least one selected from the group consisting of Ru, Rh, Ni, Pd, and Co. <12> The method for producing bis(aminomethyl)cyclohexane according to <10> or <11>, wherein the catalyst component comprises Ru. <13> The method for producing bis(aminomethyl)cyclohexane according to <11> or <12>, wherein the Ru content in the catalyst is 0.1 to 10.0% by mass with respect to 100% by mass of the catalyst. <14> The method for producing bis(aminomethyl)cyclohexane according to any one of <10> to <13>, wherein the support comprises alumina. <15> A catalyst manufacturing step for producing the catalyst, the catalyst manufacturing step comprising: a loading step (a) of reacting a raw material solution containing the catalyst component with the 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, wherein the Cl concentration of the raw material solution is 0.1 to 12.0 mol / dm 3 A method for producing bis(aminomethyl)cyclohexane according to any one of <10> to <14>. <16> A method for producing bis(aminomethyl)cyclohexane according to <15>, wherein the supported thickness of the catalyst component of the second reactant is greater than 170 μm and less than or equal to 1321 μm.

[0008] According to the present invention, it is possible to provide a technology that exhibits excellent reaction results in the production of BAC.

[0009] This figure shows a cross-section of the catalyst of Example 1.

[0010] The following describes in detail embodiments for carrying out the present invention (hereinafter referred to as "this embodiment"). This embodiment is illustrative for explaining the present invention and is not intended to limit the present invention to the following content. The present invention can be implemented by modifying it as appropriate within the scope of its gist.

[0011] <Catalyst> The catalyst of this embodiment is a catalyst for producing bis(aminomethyl)cyclohexane, which has hydrogenation ability, and the catalyst comprises a catalyst component and a carrier supporting the catalyst component, wherein the thickness of the supported catalyst component is greater than 170 μm and less than or equal to 1321 μm. Because it is configured as described above, it exhibits excellent reaction performance in the production of BAC.

[0012] (Thickness of catalyst component support) The catalyst of this embodiment exhibits excellent reaction performance in the production of BAC because the thickness of the catalyst component support is greater than 170 μm and less than or equal to 1321 μm. The reason for this is not entirely clear, and this is not intended to limit the reason, but it is speculated to be as follows. The inventors speculated that there is a relationship between the depth distribution state of the catalyst component supported on the support in the catalyst, i.e., the support thickness, and the reaction performance in the production of BAC, and focused on the above-mentioned thickness of the catalyst component support. In other words, the inventors speculated that if the thickness of the catalyst component support is small, the catalyst component will concentrate on the surface of the support, making it easier for the catalyst components to aggregate, and thus worsening the reaction performance of BAC. On the other hand, from the viewpoint of manufacturing cost, it is preferable to keep the thickness of the catalyst component support below a certain level. Based on these speculations, the inventors continued their investigation and found a tendency that the reaction performance in the production of BAC improves when the thickness of the catalyst component support is set to a specific thickness. In other words, it was found that catalysts with a catalyst component loading thickness of more than 170 μm and 1321 μm or less exhibit superior reaction performance in the production of BAC. However, the above merely describes one possible factor that may explain why the catalyst of this embodiment exhibits superior reaction performance in the production of BAC, and the mechanism of action of this embodiment is not limited thereto. The loading thickness may be 200 μm or more and 1200 μm or less. The loading thickness can be adjusted to the above range, for example, by manufacturing the catalyst based on the manufacturing method described later.

[0013] In this specification, "catalyst component loading thickness" refers to the thickness of the layer on which the catalyst component is loaded inside or on the surface of the support. A specific example will be explained using Figure 1. Figure 1 is an image of a cross-section of the catalyst of Example 1, which will be described later, taken with a microscope. In Figure 1, the black layer is the layer (A) on which the catalyst component is loaded inside or on the surface of the support, and the white part is the support (B) on which the catalyst component is not loaded. When measuring the loading thickness, the boundary between layer (A) and support (B) can be identified by visual inspection of the captured image or by using image editing software. More specifically, it can be measured based on the method described in the Examples, which will be described later.

[0014] (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.

[0015] The content of the catalyst component in this embodiment is not particularly limited, but from the viewpoint of hydrogenation capacity, it is preferably 0.1 to 10.0% by mass relative to 100% by mass of catalyst. When the catalyst in this embodiment contains Ru, from the viewpoint of excellent BAC yield, the Ru content is preferably 0.1 to 10.0% by mass relative to 100% by mass of catalyst. The content of the catalyst component can be measured by X-ray fluorescence analysis (XRF). Alternatively, the content can be specified as the raw material charge ratio during catalyst production.

[0016] (Carrier) The carrier in this embodiment is not particularly limited as long as it can support the catalyst component, and various known carriers can be used. Examples of carriers in this embodiment include alumina, diatomaceous earth, and carbon, and these can be used individually or in combination of two or more. In this embodiment, from the viewpoint of catalyst strength, it is preferable that the carrier contains alumina. The particle size of the carrier is not particularly limited, but may be, for example, 1 mm to 5 mm. The shape of the carrier is not particularly limited, but may be, for example, spherical, needle-shaped, or plate-shaped, or it may be a hollow body or a porous body.

[0017] 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.

[0018] The catalyst of this embodiment may further contain alkaline earth metals. The alkaline earth metals in this embodiment are distinct from the catalyst components described above and are not particularly limited in type; for example, Be, Mg, Ca, Sr, and Ba can be used. These can be used individually or in combination of two or more. The alkaline earth metals in this embodiment preferably contain at least one selected from the group consisting of Be, Mg, and Ca. The alkaline earth metals in this embodiment are more preferably Mg. When the catalyst of this embodiment contains alkaline earth metals, from the viewpoint of further improving the BAC yield, the content of alkaline earth metals is preferably 0.1 to 10.0% by mass per 100% by mass of the catalyst. In particular, when the catalyst of this embodiment contains Mg, from the viewpoint of further improving the BAC yield, the content of Mg is preferably 0.1 to 10.0% by mass per 100% by mass of the catalyst. The content of Mg and other alkaline earth metals can be measured by X-ray fluorescence analysis (XRF). Furthermore, the Mg content and the content of other alkaline earth metals can also be specified as the raw material charge ratio during catalyst production.

[0019] <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 raw material solution containing catalyst components is reacted with a carrier 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, wherein the Cl concentration of the raw material solution is 0.1 to 12.0 mol / dm³. 3 Therefore, since manufacturing method (A) is configured as described above, it is possible to efficiently produce a catalyst that exhibits excellent reaction performance in the production of BAC.

[0020] (Supporting step (a)) In supporting step (a), the catalyst component and the support are reacted to obtain a first reaction product. In supporting step (a), it is preferable to obtain the first reaction product by reacting a raw material solution containing 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 is the chloride of the catalyst component described above, but is not limited to chloride. 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 capacity of the obtained catalyst, step (a) preferably includes adsorbing the raw material solution onto the support and then drying it. The raw material solution may include, but is not limited to, catalyst components such as ruthenium-n chloride hydrate, rhodium chloride trihydrate, nickel chloride hexahydrate, sodium palladium chloride trihydrate, and cobalt chloride hexahydrate, as well as sodium metal oxides such as sodium ruthenate. Among these, it is preferable to include 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. While not limited to the examples above, the thickness of the catalyst component support can be controlled within a predetermined range by adjusting the type and concentration of these raw material solutions.

[0021] The Cl concentration of the raw material solution is 0.1 to 12.0 mol / dm³. 3 The concentration is preferably 0.5 to 7.0 mol / dm 3 More preferably 0.8 to 5.0 mol / dm 3 And more preferably 1.0 to 3.0 mol / dm 3By keeping the Cl concentration in the raw material solution within the above range, the loading thickness of the catalyst component can be controlled within a predetermined range, that is, the loading thickness of the catalyst component can be set to more than 170 μm and 1321 μm or less, resulting in better reaction performance in the production of BAC. Furthermore, within the above range of Cl concentration, lowering the Cl concentration tends to decrease the loading thickness of the catalyst component, while increasing the Cl concentration tends to increase the loading thickness of the catalyst component. The Cl concentration in the raw material solution can be adjusted, for example, by changing the type and amount of chloride in the catalyst component, or by adding hydrochloric acid separately.

[0022] In the loading step (a), the loading time for adsorbing the raw material solution onto the carrier is not particularly limited, but from the viewpoint of improving the hydrogenation ability of the resulting catalyst, it is preferably 0.5 to 12 hours, more preferably 0.5 to 8.5 hours, and even more preferably 0.5 to 5 hours.

[0023] (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 can be obtained by going through base treatment step (b), thereby reducing the Cl concentration derived from the raw material solution.

[0024] 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 loading thickness of the catalyst component on the second reactant is preferably more than 170 μm and 1321 μm or less, and more preferably 200 μm or more and 1200 μm or less.

[0025] 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.

[0026] 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.

[0027] (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.

[0028] 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.

[0029] (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.

[0030] <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 to obtain bis(aminomethyl)cyclohexane by contacting xylylenediamine with hydrogen in the presence of a catalyst having hydrogenation ability, wherein the catalyst comprises a catalyst component and a support that carries the catalyst component, and the thickness of the catalyst component supported is greater than 170 μm and less than or equal to 1321 μm. Because the method of this embodiment is configured as described above, BAC can be produced with high reaction performance.

[0031] (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.

[0032] 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").

[0033] 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.

[0034] 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.

[0035] In the production method of the present embodiment, the mixing 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.

[0036] The above alkylamines and alkylenediamines may be used alone, may be used as a mixture of the amines and alkylenediamines, or may be used as a mixture with other organic solvents. Organic solvents that can be mixed include, but are not limited to, for example, alcohols such as methanol, ethanol, isopropyl alcohol, and n-propyl alcohol.

[0037] In the hydrogenation step of the present embodiment, the supply conditions of hydrogen are not particularly limited, but the hydrogen pressure is preferably 5 MPa or more and 15 MPa or less. In a reaction mode in which xylylenediamine and hydrogen are continuously contacted, the hydrogen supply amount per 1 mL of catalyst is preferably 5 NmL / min or more and 50 NmL / min or less. The hydrogen pressure can be specified as a gauge pressure.

[0038] From the viewpoint of hydrogenation ability, the catalyst used in the production method of the present embodiment has a supported thickness of the catalyst component of more than 170 µm and 1321 µm or less, and preferably 200 µm or more and 1200 µm or less. As the catalyst, those described in <Catalyst> can be appropriately employed.

[0039] The catalyst in the production method of the present embodiment can include a catalyst component and a carrier that supports the catalyst component, and for the catalyst component and the carrier, those exemplified in <Catalyst> can be appropriately employed.

[0040] From the viewpoint of hydrogenation ability, the catalyst in the production method of the present embodiment includes a catalyst component and a carrier that supports the catalyst component, and the catalyst component preferably contains at least one selected from the group consisting of Ru, Rh, Ni, Pd and Co, and more preferably contains Ru. In the catalyst used in the production method of the present embodiment, the carrier preferably contains alumina.

[0041] 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.

[0042] 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.

[0043] The catalyst in the manufacturing method of this embodiment is obtained by manufacturing method (A), which includes a loading step (a) in which a raw material solution containing the catalyst component is reacted with the 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, wherein the Cl concentration of the raw material solution is 0.1 to 12.0 mol / dm³. 3It is preferable that the second reactant is used as a 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 loading thickness of the catalyst component of the second reactant is preferably more than 170 μm and 1321 μm or less, and more preferably 200 μm or more and 1200 μm or less. From the viewpoint of the hydrogenation capacity of the obtained catalyst, the loading step (a) preferably includes adsorbing the raw material solution onto the support and then drying it. In the base treatment step (b), it is preferable that the basic aqueous solution 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 capacity 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 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.

[0044] 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.

[0045] (Optional Step) The production method of the present embodiment may include optional steps in addition to the hydrogenation step. Although the production method of the present embodiment is not limited to the following, it may further include a purification step, for example. The purification step includes, for example, distilling off alkylamines, alkylenediamines and an organic solvent under normal pressure, followed by vacuum distillation, whereby the target product (BAC) can be preferably separated from the reaction product.

[0046] Hereinafter, the present embodiment will be described in more detail with reference to examples, but the scope of the present embodiment is not limited by these examples.

[0047] [Example 1] (Production of Catalyst) Under a temperature condition of 25°C, a raw material solution obtained by mixing 20 g of alumina (KHO-24, manufactured by Sumitomo Chemical Co., Ltd.), 1.07 g of ruthenium chloride n-hydrate, and 6.48 g of water (Cl concentration: 1.63 mol / dm 3 ) was used to support a catalyst component on alumina by the incipient wetness (IW) method, followed by drying at 120°C for 2 hours to obtain a supported product 1. The supported product 1 was subjected to base treatment using 61 g of 1M sodium hydroxide and 299 g of water (temperature condition: 25°C, treatment time: 48 hours) (that is, the supported product 1, sodium hydroxide and water were brought into contact for 48 hours), and dried at 110°C for 2 hours to obtain the catalyst of Example 1.

[0048] (Support Thickness of Catalyst Component) For the obtained catalyst, the catalyst was cut with a scalpel to obtain a cross-section of the catalyst, the cross-section was observed using a digital microscope (VHX-S550, manufactured by Keyence Corporation), and the support thickness of the catalyst component was measured. First, Image 1 was obtained with a digital microscope (Figure 1). In the obtained Image 1, using image processing software attached to the digital microscope, in the layer (A) where the catalyst component is supported on the inside or surface of the carrier, the distance between two points in the depth direction from the boundary between the visually identified carrier (B) and the layer (A) supporting the catalyst component to the surface of the layer (A) supporting the catalyst component was measured. Two measurement points were selected: the point where the support thickness of the catalyst component was the largest and the point where the thickness was the smallest. The above measurement was performed on 10 catalysts, and the average value of the measured support thicknesses was taken as the support thickness of the catalyst component.

[0049] (Production of BAC) The following hydrogenation reaction was carried out using a fixed-bed, externally heated, flow-through reactor with an inner diameter of 17 mmφ and a length of 320 mmL. First, 16 mL 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, a mixture consisting of 16 mL of catalyst, a reaction temperature of 100°C, a hydrogen pressure of 8.7 MPa (gauge pressure), and a hydrogen supply rate of 25 N mL / min (1.6 N mL / min per 1 mL of catalyst) was supplied to the reactor at a rate of 45 g / hr, consisting of metaxylylenediamine (4 mass%) as the raw material and 1,3-bis(aminomethyl)cyclohexane (96 mass%) as the solvent.

[0050] (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

[0051] [Example 2] In the production of the catalyst in Example 1, 6.14 g of water was used instead of 6.48 g of water, and 0.40 g of 36% hydrochloric acid was added to the raw material solution (Cl concentration 2.15 mol / dm³). 3 Except for the point that ( ) was used, and in the base treatment step, 88 g of 1 M sodium hydroxide and 272 g of water were used instead of 61 g of 1 M sodium hydroxide and 299 g of water, the catalyst of Example 2 was obtained in the same manner as in Example 1.

[0052] [Example 3] In the preparation of the catalyst of Example 1, 5.88 g of water was used instead of 6.48 g of water, and 0.70 g of 36% hydrochloric acid was added to the raw material solution (Cl concentration 2.54 mol / dm³). 3Except for the point that ( ) was used, and in the base treatment step, 92 g of 1 M sodium hydroxide and 268 g of water were used instead of 61 g of 1 M sodium hydroxide and 299 g of water, the catalyst of Example 3 was obtained in the same manner as in Example 1.

[0053] [Example 4] In the production of the catalyst of Example 1, 5.60 g of water was used instead of 6.48 g of water, and 1.04 g of 36% hydrochloric acid was added to the raw material solution (Cl concentration 2.99 mol / dm³). 3 Except for the point that ) was used, and in the base treatment step, 100 g of 1 M sodium hydroxide and 260 g of water were used instead of 61 g of 1 M sodium hydroxide and 299 g of water, the catalyst of Example 4 was obtained in the same manner as in Example 1.

[0054] [Example 5] In the production of the catalyst of Example 1, 7.92 g of 36% hydrochloric acid was used instead of 6.48 g of water to produce a raw material solution (Cl concentration 11.94 mol / dm³). 3 Except for the point that ( ) was used, and in the base treatment step, 217 g of 1 M sodium hydroxide and 143 g of water were used instead of 61 g of 1 M sodium hydroxide and 299 g of water, the catalyst of Example 5 was obtained in the same manner as in Example 1.

[0055] [Comparative Example 1] At a temperature of 25°C, 20 g of alumina (KHO-24, manufactured by Sumitomo Chemical Co., Ltd.) was mixed with 2.053 g of ruthenium chloride trihydrate and 400 g of water to prepare a raw material solution (Cl concentration: 0.06 mol / dm³). 3 The material was immersed in a solution, stirred for 10 minutes, and then immersed for a further 12 hours. Next, it was recovered by filtration, washed with water and ethanol, and then dried at 100°C for 12 hours to obtain support 2. Support 2 was calcined at 400°C for 5 hours in an air atmosphere to obtain support 3. Support 3 was reduced at a reaction temperature of 250°C for 6 hours in a mixed atmosphere of hydrogen gas and nitrogen gas (hydrogen volume percentage 10%) to obtain support 4. Support 4 was dispersed in 380 mL of water, and then 4.755 g of lithium hydroxide was added to the dispersion and stirred for 24 hours. Next, it was recovered by filtration, washed with water and ethanol, and then dried at 100°C for 12 hours to obtain the catalyst of Comparative Example 1.

[0056] [Comparative Example 2] At a temperature of 25°C, 20 g of alumina (KHO-24, manufactured by Sumitomo Chemical Co., Ltd.) was mixed with 0.27 g of ruthenium chloride trihydrate and 10 g of water to form a raw material solution (Cl concentration: 0.30 mol / dm³). 3 The material was immersed in a solution of hydrogen and nitrogen gas (hydrogen by volume 10%), stirred for 5 minutes, and then immersed in an 80°C water bath for 4 hours. Next, it was washed with water, recovered by filtration, and dried at 105°C for 12 hours to obtain support 5. Support 5 was calcined in a muffle furnace at 200°C for 3 hours (heated to 200°C at a rate of 2°C / min, then held for 3 hours) to obtain support 6. Support 6 was reduced in a mixed atmosphere of hydrogen gas and nitrogen gas (hydrogen by volume 10%) at a reaction temperature of 250°C for 4 hours to obtain support 7. Support 7 was added to an aqueous sodium nitrate solution (an aqueous solution prepared by dissolving 0.074 g of sodium nitrate in 10 mL of water), stirred for 5 minutes, and then immersed in an 80°C water bath for 4 hours. Next, it was dried at 105°C for 12 hours to obtain support 8. The supported material 8 was calcined in a muffle furnace at 200°C for 3 hours (heated to 200°C at a rate of 2°C / min, then held for 3 hours) to obtain the catalyst of Comparative Example 2.

[0057] The catalyst load thickness was measured for the catalysts obtained in Examples 2-5 and Comparative Examples 1-2 in the same manner as in Example 1. Furthermore, BAC was produced using the catalysts obtained in Examples 2-5 in the same manner as in Example 1, and the reaction performance was evaluated. In addition, for the catalysts of Comparative Examples 1-2, the catalyst reduction treatment performed in Example 1 was omitted when producing BAC. These results are shown in Table 1.

[0058]

[0059] The catalysts of Examples 1 to 5, in which the supported thickness of the catalyst component was greater than 170 μm and less than or equal to 1321 μm, were confirmed to have higher BAC reaction performance compared to the catalysts of Comparative Examples 1 and 2. Furthermore, the catalyst component was found to be present and the Cl concentration was 0.1 to 12.0 mol / dm³. 3 The catalysts of Comparative Examples 1 and 2, which were obtained without going through a loading step (a) in which a raw material solution 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, were shown to be difficult to control the loading thickness of the catalyst component to more than 170 μm and less than or equal to 1321 μm.

Claims

1. A catalyst for producing bis(aminomethyl)cyclohexane having hydrogenation ability, wherein the catalyst comprises a catalytic component and a carrier supporting the catalytic component, and the thickness of the supported catalytic component is greater than 170 μm and less than or equal to 1321 μm.

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

3. The catalyst according to claim 1, wherein the catalyst component includes Ru.

4. 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.

5. The catalyst according to claim 1, wherein the carrier comprises alumina.

6. A method for producing a catalyst according to claim 1, comprising: a loading step (a) of reacting a raw material solution containing 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, wherein the Cl concentration of the raw material solution is 0.1 to 12.0 mol / dm³ 3 A method for manufacturing a catalyst.

7. The method for producing a catalyst according to claim 6, wherein the supporting step (a) includes reacting a raw material solution containing the chloride of the catalyst component with the carrier.

8. The method for producing a catalyst according to claim 6, wherein in the base treatment step (b), the basic aqueous solution contains an aqueous sodium hydroxide solution.

9. The method for producing a catalyst according to claim 6, wherein the supported thickness of the catalyst component in the second reactant is greater than 170 μm and less than or equal to 1321 μm.

10. A method for producing bis(aminomethyl)cyclohexane, comprising a hydrogenation step of contacting xylylenediamine with hydrogen in the presence of a catalyst having hydrogenation ability, wherein the catalyst comprises a catalyst component and a carrier supporting the catalyst component, and the thickness of the supported catalyst component is greater than 170 μm and less than or equal to 1321 μm.

11. The method for producing bis(aminomethyl)cyclohexane according to claim 10, wherein the catalyst component comprises at least one selected from the group consisting of Ru, Rh, Ni, Pd, and Co.

12. The catalyst component contains Ru. The method for producing bis(aminomethyl)cyclohexane according to claim 10.

13. The method for producing bis(aminomethyl)cyclohexane according to claim 11, wherein the Ru content in the catalyst is 0.1 to 10.0% by mass based on 100% by mass of the catalyst.

14. The method for producing bis(aminomethyl)cyclohexane according to claim 10, wherein the carrier contains alumina.

15. A catalyst manufacturing step for producing the catalyst, the catalyst manufacturing step comprising: a loading step (a) of reacting a raw material solution containing the catalyst component with the 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, wherein the Cl concentration of the raw material solution is 0.1 to 12.0 mol / dm 3 The method for producing bis(aminomethyl)cyclohexane according to claim 10.

16. The method for producing bis(aminomethyl)cyclohexane according to claim 15, wherein the supported thickness of the catalyst component in the second reactant is greater than 170 μm and less than or equal to 1321 μm.

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