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

Abstract

Provided is a catalyst that has hydrogenation ability and is for producing bis (aminomethyl) cyclohexane, wherein the catalyst has a desorption peak amount of 0.020 mmol / g-cat or less as measured by the following ammonia temperature-programmed desorption method.　He gas is brought into contact with 150 mg of the catalyst at 500°C and at a gas flow rate of 20 sccm for 30 minutes. Next, a mixed gas containing 5 vol% NH3 and He as the remainder is brought into contact with the catalyst at 50°C and at a gas flow rate of 20 sccm for 10 minutes. Thereafter, while He gas is brought into contact with the catalyst at a gas flow rate of 20 sccm, the temperature is raised at 10°C / min, and the desorption peak is detected by a thermal conductivity detector.

Description

[Technical Field]

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

[0002] Bis(aminomethyl)cyclohexane (hereinafter also referred to as "BAC") is an industrially important compound used as a raw material for polyamides, bis(isocyanatomethyl)cyclohexane, and the like. BAC can be obtained, for example, by catalytic hydrogenation of xylylenediamine. Regarding such catalytic hydrogenation, for example, Patent Document 1 proposes the use of a catalyst prepared by adding an alkali metal modifier as an auxiliary to ruthenium / alumina as a catalytic component. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Chinese Patent Application Publication No. 112473663 Summary of the Invention [Problem to be solved by the invention]

[0004] Although the catalyst described in Patent Document 1 is said to improve selectivity, there is a recent trend toward even higher catalytic performance, and therefore there is room for further improvement.

[0005] The present invention has been made in view of the above problems, and an object of the present invention is to provide a catalyst and the like that exhibits excellent BAC selectivity. [Means for solving the problem]

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

[0007] That is, the present invention includes the following aspects. [1] A catalyst for producing bis(aminomethyl)cyclohexane, having hydrogenation ability, comprising: The catalyst has a desorption peak amount of 0.020 mmol / g-cat or less when measured by the ammonia temperature programmed desorption method described below. (Ammonia temperature programmed desorption method) He gas is contacted with 150 mg of the catalyst at 500°C and a gas flow rate of 20 sccm for 30 minutes. Next, a mixed gas of 5 volume % NH3 and the remainder He is contacted with the catalyst at 50°C and a gas flow rate of 20 sccm for 10 minutes. Thereafter, while contacting the catalyst with He gas at a gas flow rate of 20 sccm, the temperature is increased at a rate of 10°C / min, and the desorption peak is detected with a thermal conductivity detector. [2] the catalyst includes a catalyst component and a carrier that supports the catalyst component, The catalyst according to [1], wherein the catalyst component contains Ru. [3] the Ru content in the catalyst is 0.1 to 10.0 mass% relative to 100 mass% of the catalyst; The catalyst according to [1] or [2], wherein the content of Na in the catalyst is 0.1 to 10.0 mass % relative to 100 mass % of the catalyst. [4] The catalyst according to [2] or [3], wherein the support comprises alumina. [5] A method for producing the catalyst according to any one of [1] to [4], (a) reacting a catalyst component with a support to obtain a first reactant; (b) adding an alkali metal to the first reactant to obtain a second reactant; A method for producing a catalyst, comprising: [6] further comprising a step (c) of reducing the second reactant to obtain a third reactant; The method for producing a catalyst according to [5], wherein the desorption peak amount of the third reactant measured by the ammonia temperature programmed desorption method is 0.020 mmol / g-cat or less. [7] The method for producing a catalyst according to [6], wherein the step (c) is carried out at a temperature of 160 to 360°C. [8] The method for producing a catalyst according to any one of [5] to [7], wherein the step (a) comprises adsorbing a Ru raw material solution onto a support, drying the support, and contacting the support with a basic aqueous solution. [9] The method for producing a catalyst according to any one of [5] to [7], wherein the alkali metal includes at least one selected from the group consisting of Na, K, and Li.

[10] a hydrogenation step of continuously contacting xylylenediamine with hydrogen in the presence of a catalyst having hydrogenation ability to obtain bis(aminomethyl)cyclohexane; A method for producing bis(aminomethyl)cyclohexane, wherein the catalyst has a desorption peak amount of 0.020 mmol / g-cat or less as measured by the following ammonia temperature programmed desorption method. (Ammonia temperature programmed desorption method) He gas is contacted with 150 mg of the catalyst at 500°C and a gas flow rate of 20 sccm for 30 minutes. Next, a mixed gas of 5 volume % NH3 and the remainder He is contacted with the catalyst at 50°C and a gas flow rate of 20 sccm for 10 minutes. Thereafter, while contacting the catalyst with He gas at a gas flow rate of 20 sccm, the temperature is increased at a rate of 10°C / min, and the desorption peak is detected with a thermal conductivity detector.

[11] the catalyst includes a catalyst component and a carrier that supports the catalyst component, The method for producing bis(aminomethyl)cyclohexane according to

[10] , wherein the catalyst component contains Ru.

[12] The catalyst is obtained by production method (A), The production method (A) (a) reacting the catalyst component with the support to obtain a first reactant; (b) adding an alkali metal to the first reactant to obtain a second reactant; The method for producing bis(aminomethyl)cyclohexane according to

[11] , comprising:

[13] The process (A) further comprises a step (c) of reducing the second reactant to obtain a third reactant; The method for producing bis(aminomethyl)cyclohexane according to

[12] , wherein the third reactant has a desorption peak amount of 0.020 mmol / g-cat or less as measured by the ammonia temperature programmed desorption method.

[14] The method for producing bis(aminomethyl)cyclohexane according to

[13] , wherein the step (c) is carried out at a temperature of 160 to 360°C.

[15] The method for producing bis(aminomethyl)cyclohexane according to any one of

[12] to

[14] , wherein the step (a) comprises adsorbing a Ru raw material solution onto a support, drying the adsorbed Ru raw material solution, and contacting the adsorbed Ru raw material solution with a basic aqueous solution.

[16] The method for producing bis(aminomethyl)cyclohexane according to any one of

[12] to

[15] , wherein the alkali metal includes at least one selected from the group consisting of Na, K, and Li.

[17] the Ru content in the catalyst is 0.1 to 10.0 mass% relative to 100 mass% of the catalyst; The method for producing bis(aminomethyl)cyclohexane according to any one of

[10] to

[16] , wherein the content of Na in the catalyst is 0.1 to 10.0 mass % relative to 100 mass % of the catalyst.

[18] The method for producing bis(aminomethyl)cyclohexane according to any one of

[11] to

[17] , wherein the support contains alumina. [Effects of the Invention]

[0008] According to the present invention, a catalyst or the like that exhibits excellent BAC selectivity can be provided. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a graph showing the results of TPD measurement of the catalyst obtained in Example 1. [Figure 2] 2 is a graph showing the results of multipoint baseline correction of the graph in FIG. 1. [Figure 3] 1 is a graph showing the TPD measurement results of the catalyst obtained in Comparative Example 1. [Figure 4] 4 is a graph showing the results of multipoint baseline correction of the graph in FIG. 3. [Figure 5] 1 is a graph showing the TPD measurement results of the catalyst obtained in Comparative Example 2. [Figure 6] 6 is a graph showing the results of multipoint baseline correction of the graph in FIG. 5. [Figure 7] 1 is a graph showing the TPD measurement results of the catalyst obtained in Comparative Example 3. [Figure 8] 8 is a graph showing the results of multipoint baseline correction of the graph in FIG. 7. DETAILED DESCRIPTION OF THE INVENTION

[0010] 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 example for explaining the present invention, and is not intended to limit the present invention to the following content. The present invention can be carried out by appropriately modifying it within the scope of its gist.

[0011] <Catalyst> The catalyst of the present embodiment is a catalyst for producing bis(aminomethyl)cyclohexane, which has hydrogenation ability, and the catalyst has a desorption peak amount of 0.020 mmol / g-cat or less when measured by the following ammonia temperature-programmed desorption method (hereinafter also referred to as "TPD") (hereinafter this measurement is also referred to as "TPD measurement"). (Ammonia temperature programmed desorption method) He gas is contacted with 150 mg of the catalyst at 500°C and a gas flow rate of 20 sccm for 30 minutes. Next, a mixed gas of 5 volume % NH3 and the remainder He is contacted with the catalyst at 50°C and a gas flow rate of 20 sccm for 10 minutes. Thereafter, while contacting the catalyst with He gas at a gas flow rate of 20 sccm, the temperature is increased at a rate of 10°C / min, and the desorption peak is detected with a thermal conductivity detector. The catalyst of this embodiment has the above-described configuration and therefore exhibits excellent BAC selectivity.

[0012] (TPD measurement) The catalyst of this embodiment exhibits excellent BAC selectivity because the desorption peak amount measured by the TPD measurement is 0.020 mmol / g-cat or less. The reason for this is not necessarily clear, and although it is not intended to limit the reason here, it is presumed to be as follows. The present inventors have investigated conventional hydrogenation catalysts for BAC production and found that they are prone to producing low-boiling impurities as by-products during the hydrogenation reaction, limiting the improvement of BAC selectivity. Further investigation into the cause of this finding led them to speculate that the acid sites on the catalyst surface have a significant effect, particularly in the hydrogenation reaction for BAC production, and are strongly related to the generation of these impurities. Therefore, they speculated that reducing these acid sites would lead to further improvements in BAC selectivity. Based on this speculation, the present inventors further investigated the desorption peak amount obtained by this measurement as an indicator and found that BAC selectivity tends to be particularly improved when this value is 0.020 mmol / g-cat or less. Although the detailed mechanism is not entirely clear, the present inventors speculate as follows. In other words, the reaction substrates and products in this study contain amino groups in their structures, which are thought to react strongly with the active sites on the catalyst surface. Specifically, it is thought that a deammoniation reaction occurs, which leads to the production of the above-mentioned impurities (by-products). Therefore, by using the desorption peak amount obtained in this measurement as an indicator and sufficiently reducing this value, the active sites on the catalyst surface that react strongly with NH3 will disappear, and as a result, the deammoniation reaction will be suppressed and the selectivity will be improved. However, the above description merely describes one possible factor that allows the catalyst of this embodiment to exhibit excellent BAC selectivity, and the mechanism of action of this embodiment is not limited to this. In addition to the above viewpoints, from the viewpoint of further improving the BAC yield, the desorption peak amount is preferably 0.015 mmol / g-cat or less. More specifically, the desorption peak amount can be measured based on the method described in the Examples below. The desorption peak amount can be adjusted to fall within the above range, for example, by producing the catalyst according to the production method described below.

[0013] From the viewpoint of catalyst strength, the catalyst of the present embodiment preferably contains a catalyst component and a carrier that supports the catalyst component.

[0014] (catalyst component) The catalyst component in this embodiment is not particularly limited, and various known catalyst components can be used. Examples of the catalyst component in this embodiment include Ru, Rh, and Ni, and these can be used alone or in combination of two or more. In this embodiment, from the viewpoint of hydrogenation ability, the catalyst component preferably contains Ru. The catalyst in this embodiment particularly contains a catalyst component and a support that supports the catalyst component, and it is preferable that the catalyst component contains Ru.

[0015] When the catalyst of the present embodiment contains Ru, the content of Ru is preferably 0.1 to 10.0 mass % relative to 100 mass % of the catalyst, from the viewpoint of hydrogenation ability. The Ru content can be measured by X-ray fluorescence analysis (XRF), and can also be determined as the ratio of raw materials used in producing the catalyst.

[0016] (Carrier) The carrier in this embodiment is not particularly limited as long as it can support the catalyst components, and various known carriers can be used. Examples of the carrier in this embodiment include alumina, diatomaceous earth, and carbon, and these can be used alone or in combination. In this embodiment, from the viewpoint of catalyst strength, it is preferable that the carrier contains alumina.

[0017] (alkali metals) The catalyst of this embodiment preferably contains an alkali metal from the viewpoint of hydrogenation ability. The alkali metal in this embodiment is distinct from the above-described catalyst component, and the type thereof is not particularly limited, and examples thereof include Li, Na, K, Rb, and Cs. These may be used alone or in combination of two or more. From the viewpoint of hydrogenation ability, the alkali metal in this embodiment preferably contains at least one selected from the group consisting of Na, K, and Li. In addition to the above viewpoints, from the viewpoint of further improving the BAC yield, the alkali metal in this embodiment more preferably contains at least one selected from the group consisting of Na and K. When the catalyst of this embodiment contains an alkali metal, from the viewpoint of hydrogenation ability, the content of the alkali metal is preferably 0.1 to 10.0 mass% relative to 100 mass% of the catalyst. In particular, when the catalyst of this embodiment contains Na, from the viewpoint of hydrogenation ability, the content of Na is preferably 0.1 to 10.0 mass% relative to 100 mass% of the catalyst. In particular, the catalyst of this embodiment preferably has a Ru content of 0.1 to 10.0 mass% relative to 100 mass% of the catalyst, and a Na content of 0.1 to 10.0 mass% relative to 100 mass% of the catalyst. The Na content and the other alkali metal content can be measured by the method described in the Examples below. Alternatively, the Na content and the other alkali metal content can be determined as the raw material charging ratio during catalyst production.

[0018] <Catalyst manufacturing method> The method for producing the catalyst of this embodiment is not particularly limited as long as it can produce the catalyst of this embodiment, but it is preferably obtained by the following method. That is, a preferred method for producing the catalyst of this embodiment (hereinafter also referred to as "production method (A)") is a method for producing the catalyst of this embodiment, and includes step (a) of reacting a catalyst component with a support to obtain a first reactant, and step (b) of adding an alkali metal to the first reactant to obtain a second reactant. Because production method (A) is configured as described above, it can efficiently produce a catalyst that exhibits excellent BAC selectivity.

[0019] (Step (a)) In step (a), the catalyst component and the support are reacted to obtain a first reactant. The catalyst component and the support may be selected from those exemplified in the <Catalyst> section. The reaction between the catalyst component and the support may be carried out, for example, by the incipient wetness (IW) method under various known conditions, but is not limited to the following. In this embodiment, from the viewpoint of the hydrogenation ability of the obtained catalyst, step (a) preferably includes adsorbing a Ru raw material solution onto a support, drying the support, and contacting the support with a basic aqueous solution. The Ru raw material solution preferably contains, but is not limited to, ruthenium chloride n-hydrate, for example. The basic aqueous solution preferably contains, but is not limited to, sodium hydroxide, for example.

[0020] (Step (b)) In step (b), an alkali metal is added to the first reactant to obtain a second reactant. The second reactant can be used as the catalyst of this embodiment by itself, or can be used as the catalyst of this embodiment after further adjusting its performance, such as hydrogenation ability, through step (c) described below. The alkali metal can be appropriately selected from those exemplified in the <Catalyst> section. The addition of the alkali metal can be carried out, for example, by the incipient wetness (IW) method under various known conditions, but is not limited to the following. The alkali metal may be added in the form of, for example, a carbonate, hydrogencarbonate, nitrate, hydroxide, or the like, but is not limited to the following. In this embodiment, the alkali metal preferably includes at least one selected from the group consisting of Na, K, and Li, from the viewpoint of the hydrogenation ability of the resulting catalyst.

[0021] (Process (c)) Preferably, Production Method (A) further comprises step (c) of reducing the second reactant to obtain a third reactant. When the third reactant is used as the catalyst of this embodiment, the hydrogenation ability tends to be higher. From the same viewpoint as above, Production Method (A) preferably provides a desorption peak amount of the third reactant measured by the ammonia temperature programmed desorption method of 0.020 mmol / g-cat or less, more preferably 0.015 mmol / g-cat or less. The temperature conditions for step (c) are not particularly limited, but step (c) is preferably carried out at a temperature of 160 to 360°C from the viewpoint of the hydrogenation ability of the resulting catalyst.

[0022] <Method of producing bis(aminomethyl)cyclohexane> The method for producing bis(aminomethyl)cyclohexane of this embodiment (hereinafter also referred to as the "production method of this embodiment") includes a hydrogenation step in which xylylenediamine is continuously contacted with hydrogen in the presence of a catalyst having hydrogenation ability to obtain bis(aminomethyl)cyclohexane, and the desorption peak amount measured by the ammonia temperature programmed desorption method described below for the catalyst is 0.020 mmol / g-cat or less. (Ammonia temperature programmed desorption method) He gas is contacted with 150 mg of the catalyst at 500°C and a gas flow rate of 20 sccm for 30 minutes. Next, a mixed gas of 5 volume % NH3 and the remainder He is contacted with the catalyst at 50°C and a gas flow rate of 20 sccm for 10 minutes. Thereafter, while contacting the catalyst with He gas at a gas flow rate of 20 sccm, the temperature is increased at a rate of 10°C / min, and the desorption peak is detected with a thermal conductivity detector. The production method of this embodiment is configured as described above, and therefore can produce BAC with high BAC selectivity.

[0023] (Hydrogenation process) In the hydrogenation step of this embodiment, bis(aminomethyl)cyclohexane is obtained by continuously contacting xylylenediamine with hydrogen in the presence of a catalyst having hydrogenation ability. That is, continuous hydrogenation of xylylenediamine is carried out. The bis(aminomethyl)cyclohexane obtained by the production method of this embodiment may be 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, or a mixture thereof.

[0024] In the production method of this embodiment, xylylenediamine, which is one of the raw materials, exists as three isomers: ortho-, meta-, and para-. These isomers can be used alone or as a mixture. In the production method of this embodiment, meta- and para-isomers can be preferably used. That is, the xylylenediamine preferably includes meta-xylylenediamine (hereinafter also referred to as "MXDA") and / or para-xylylenediamine (hereinafter also referred to as "PXDA").

[0025] In the production method of this embodiment, the solvent that can be used is not particularly limited, and various known solvents can be used. Examples of solvents in this embodiment include, but are not limited to, alkylamines and alkylenediamines. These can be used alone, or two or more can be used in combination. When alkylamines and alkylenediamines are contained as solvents, they are separated by distillation from the reaction product and recycled for reuse in an industrial continuous production method. Therefore, it is preferable to select a solvent having 1 to 18 carbon atoms that is liquid at room temperature for easy recycling. In this case, the production of by-products is further suppressed, and the yield of the target product tends to be further increased. Examples of alkylamines in the present embodiment include, but are not limited to, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, isopropylamine, diisopropylamine, butylamine, dibutylamine, tributylamine, hexylamine, cyclohexylamine, 2-ethylhexylamine, etc. These may be used alone or in combination of two or more. Examples of alkylenediamines in the present embodiment include, but are not limited to, ethylenediamine, propylenediamine, 1,4-butylenediamine, hexamethylenediamine, bis(aminomethyl)cyclohexane, etc. These may be used alone or in combination of two or more. In this embodiment, since the bis(aminomethyl)cyclohexane obtained by catalytic reduction can be recycled and reused, the solvent in this embodiment preferably contains 1,3-bis(aminomethyl)cyclohexane and / or 1,4-bis(aminomethyl)cyclohexane.

[0026] In the production method of this 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.

[0027] The alkylamines and alkylenediamines may be used alone, as a mixture of the amines and alkylenediamines, or as a mixture with other organic solvents, including, but not limited to, alcohols such as methanol, ethanol, isopropyl alcohol, and n-propyl alcohol.

[0028] In the hydrogenation step of this embodiment, the hydrogen supply conditions are not particularly limited, but the hydrogen pressure is preferably 5 MPa to 15 MPa, and the hydrogen supply rate per mL of catalyst is preferably 0.5 NmL / min to 2.5 NmL / min. The hydrogen pressure can be specified as a gauge pressure.

[0029] From the viewpoint of hydrogenation ability, the catalyst used in the production method of this embodiment has a desorption peak amount measured by the ammonia temperature programmed desorption method of 0.020 mmol / g-cat or less, and preferably 0.015 mmol / g-cat or less. As the catalyst, any of those described in the <Catalyst> section can be used as appropriate.

[0030] The catalyst in the production method of this embodiment can include a catalyst component and a carrier that supports the catalyst component. As the catalyst component and carrier, those exemplified in <Catalyst> can be appropriately used. From the viewpoint of hydrogenation ability, the catalyst in the production method of the present embodiment preferably contains a catalyst component and a carrier that supports the catalyst component, and the catalyst component preferably contains Ru. In the catalyst used in the production method of this embodiment, the carrier preferably contains alumina.

[0031] The catalyst used in the production method of this embodiment preferably contains an alkali metal in addition to the catalyst components and the carrier. As the alkali metal, any of those exemplified in <Catalyst> can be used as appropriate, and from the viewpoint of hydrogenation ability, it is preferable that the catalyst contains at least one selected from the group consisting of Na, K, and Li. In the catalyst used in the production method of the present embodiment, it is preferable that the Ru content in the catalyst is 0.1 to 10.0 mass% relative to 100 mass% of the catalyst, and the alkali metal content in the catalyst is 0.1 to 10.0 mass% relative to 100 mass% of the catalyst. In the catalyst used in the production method of this embodiment, it is preferable that the Ru content in the catalyst is 0.1 to 10.0 mass % relative to 100 mass % of the catalyst, and the Na content in the catalyst is 0.1 to 10.0 mass % relative to 100 mass % of the catalyst.

[0032] The catalyst in the production method of this embodiment is obtained by production method (A), which preferably includes step (a) of reacting the catalyst component with the support to obtain a first reactant, and step (b) of adding an alkali metal to the first reactant to obtain a second reactant. The second reactant can be used as the catalyst in the production method of this embodiment, or it can be used as the catalyst in the production method of this embodiment after further adjusting its performance, such as hydrogenation ability, through step (c) described below. Here, the production method (A) can be suitably adopted from those explained in <Production method of catalyst>. That is, from the viewpoint of the hydrogenation ability of the resulting catalyst, production method (A) further includes step (c) of reducing the second reactant to obtain a third reactant, and the desorption peak amount of the third reactant measured by the ammonia temperature programmed desorption method is preferably 0.020 mmol / g-cat or less, more preferably 0.015 mmol / g-cat or less. From the viewpoint of the hydrogenation ability of the resulting catalyst, step (a) preferably comprises adsorbing a Ru raw material solution onto a carrier, drying the carrier, and contacting the carrier with a basic aqueous solution. The alkali metal in step (b) preferably includes at least one selected from the group consisting of Na, K and Li, from the viewpoint of the hydrogenation ability of the resulting catalyst. Step (c) is preferably carried out at a temperature of 160 to 360°C from the viewpoint of the hydrogenation ability of the resulting catalyst.

[0033] The amount of catalyst in the production method of this embodiment is not particularly limited, but can be 0.1 to 5.0, preferably 0.1 to 2.0, in terms of WHSV relative to the feed amount of the raw material xylylenediamine. The above amount is preferably adopted when using a catalyst of this embodiment that supports about 2 mass % of ruthenium, but the same conditions can also be adopted for other catalysts of this embodiment.

[0034] In the hydrogenation step of this embodiment, the reaction temperature is not particularly limited, but is 50 to 150°C, and preferably 80 to 130°C.

[0035] The reactor for carrying out the hydrogenation step in this embodiment is not particularly limited, and for example, a fixed-bed reactor can be used. When the reactor in this embodiment is carried out continuously using a solvent, it may be configured so that dissolved gases are separated from the reaction product using a gas-liquid separator, and then the BAC obtained by catalytic hydrogenation is separated and recycled, or it may be configured so that the reaction product after gas-liquid separation is subjected to distillation and solvent separation in a solvent recovery facility and then recycled. In this embodiment, the BAC obtained by catalytic hydrogenation can also be used as a solvent, and in this case, it is preferable to separate dissolved gases from the reaction product using a gas-liquid separator and then directly recycle the BAC.

[0036] (Optional process) The production method of this embodiment may include any step other than the hydrogenation step. The production method of this embodiment may further include, for example, a purification step, although this is not limited to the following. Examples of the purification step include distilling off alkylamines, alkylenediamines, and an organic solvent at atmospheric pressure, followed by vacuum distillation, which allows the target compound (BAC) to be preferably separated from the reaction product. [Example]

[0037] The present embodiment will be described in more detail below with reference to examples, but the scope of the present embodiment is not limited to these examples.

[0038] [Example 1] (Catalyst production) Using 20 g of alumina, 1 g of ruthenium chloride n-hydrate, and 8 g of water, the catalyst components were supported on the alumina by the insipient wetness (IW) method, and then dried at 120°C to obtain Support 1. Support 1 was subjected to a base treatment using 60 g of 1 M sodium hydroxide and 300 g of water (i.e., Support 1 was contacted with sodium hydroxide and water), and then dried at 110°C to obtain Support 2. To this, 1.0 g of NaHCO3 and 8 g of water were added by the IW method, and the mixture was dried at 110°C to obtain the catalyst of Example 1.

[0039] (Amount of alkali metal in catalyst) The amount of alkali metal (Na) contained in the catalyst was analyzed by X-ray fluorescence (XRF) analysis and found to be 1.7% by mass, based on 100% by mass of the catalyst, i.e., 0.8 mmol / g-cat.

[0040] (TPD measurement) He gas was contacted with 150 mg of catalyst at 500°C for 30 minutes at a gas flow rate of 20 sccm. The catalyst was then contacted with a mixed gas of 5% NH3 by volume and the remainder He at 50°C for 10 minutes at a gas flow rate of 20 sccm. The catalyst was then heated at a rate of 10°C / min while contacting with He gas at a gas flow rate of 20 sccm. Desorption peaks were detected using a thermal conductivity detector (Microtrac-Bell "BEL-CAT B"). Specifically, peaks appearing between 50 and 350°C were calculated from the vertically divided high-temperature peak area after multipoint baseline correction. Multipoint baseline correction was performed using the start and end points of the peaks, as known in the art. The desorption peak amount (mmol / g-cat) was determined by calibration pulse measurement using NH3. Specifically, the value was calculated using the calibration factor according to the method described in the "BEL-CAT B" manual (assuming the gas species of the desorption peak was NH3). The TPD measurement results for the catalyst of Example 1 are shown in Figure 1 (before multi-point baseline correction) and Figure 2 (after multi-point baseline correction). The arrows in each figure correspond to the positions corrected by multi-point baseline correction (selected peak start and end points). As a result, the desorption peak amount for Example 1 was 0.005 (mmol / g-cat).

[0041] (BAC manufacturing) The following hydrogenation reaction was carried out using a fixed-bed, externally heated flow reactor with an inner diameter of 17 mm and a flow rate of 320 mm. First, hydrogen gas was contacted with 16 mL of catalyst 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 meta-xylylenediamine (4% by mass) as a raw material and 1,3-bis(aminomethyl)cyclohexane (96% by mass) as a solvent was fed to the reactor at a rate of 45 g / hr under the following conditions: catalyst amount 16 mL, reaction temperature 100°C, hydrogen pressure 8.7 MPa (gauge pressure), and hydrogen feed rate 25 NmL / min (1.6 NmL / min per mL of catalyst).

[0042] (Reaction results) After 24 hours had passed since the start of the reaction, the reaction product was sampled for 1 hour and analyzed by gas chromatography. The BAC selectivity was 94.2%. The MXDA conversion was 88.9%. The gas chromatographic analysis conditions were as follows, and quantification was performed by the area percentage method. GC equipment: Shimadzu GC2030 Column: HP-1MS (length 30 m × inner diameter 0.25 mm × film thickness: 0.25 μm) Sample introduction temperature: 300℃ Split ratio: 10 Temperature program: After holding at 150°C for 5 minutes, the temperature was raised to 300°C (10 minutes), and then held at 300°C for 10 minutes. Detector and detection temperature: Hydrogen flame ionization detector (FID), 300°C Carrier gas: He (46.2 mL / min) Injection volume: 0.2μL

[0043] (Catalyst reduction and TPD measurement) Separately, 150 mg of the catalyst obtained in the "Catalyst Production" section above (i.e., the catalyst before use in the "BAC Production" section above) was contacted with hydrogen gas at 260°C and a gas flow rate of 50 sccm for 30 minutes to reduce the catalyst. The reduced catalyst was then contacted with He gas at 500°C and a gas flow rate of 20 sccm for 30 minutes. The catalyst was then contacted with a mixed gas of 5 vol% NH3 and the remainder He at 50°C and a gas flow rate of 20 sccm for 10 minutes. The catalyst was then heated at a rate of 10°C / min while contacting with He gas at a gas flow rate of 20 sccm. The desorption peak was detected using a thermal conductivity detector (Microtrack-Bell "BEL-CAT B"). Multipoint baseline correction and calculation of the desorption peak amount (mmol / g-cat) were performed as described above. The desorption peak amount of the reduced catalyst was 0.005 (mmol / g-cat), which closely matched the value before reduction.

[0044] [Example 2] A catalyst of Example 2 was obtained in the same manner as in Example 1, except that 1.0 g of K2CO3 was used instead of 1.0 g of NaHCO3 in the production of the catalyst of Example 1. The alkali metal content of the obtained catalyst was measured in the same manner as in Example 1, and TPD measurement was also carried out. As a result, the desorption peak amount of Example 2 was 0.002 (mmol / g-cat). Furthermore, BAC was produced using the catalyst of Example 2 in the same manner as in Example 1, and the reaction results were evaluated. The BAC selectivity was 94.2%. The MXDA conversion was 90.7%. The results are shown in Table 1.

[0045] [Example 3] A catalyst of Example 3 was obtained in the same manner as in Example 1, except that 1.0 g of LiOH was used instead of 1.0 g of NaHCO3 in the production of the catalyst of Example 1. The amount of alkali metal in the obtained catalyst was measured in the same manner as in Example 1, and TPD measurement was also carried out. As a result, the desorption peak amount of Example 3 was 0.019 (mmol / g-cat). Furthermore, BAC was produced using the catalyst of Example 3 in the same manner as in Example 1, and the reaction results were evaluated. The BAC selectivity was 94.0%. The results are shown in Table 1.

[0046] [Example 4] The catalyst of Example 4 was obtained in the same manner as in Example 1, except that 4.0 g of LiNO was used instead of 1.0 g of NaHCO in the production of the catalyst of Example 1. The alkali metal content of the obtained catalyst was measured in the same manner as in Example 1, and TPD measurement was also carried out. As a result, the desorption peak amount of Example 4 was 0.001 (mmol / g-cat). Furthermore, BAC was produced using the catalyst of Example 4 in the same manner as in Example 1, and the reaction results were evaluated. The BAC selectivity was 94.3%. The BAC yield was higher than that of Example 3. The results are shown in Table 1. Furthermore, for the catalyst of Example 4, reduction of the catalyst and TPD measurement were carried out in the same manner as in Example 1. As a result, the desorption peak amount of the catalyst after reduction was 0.001 (mmol / g-cat), which was in good agreement with the value before reduction.

[0047] [Comparative Example 1] In the production of the catalyst of Example 1, 1.0 g of NaHCO3 was not added, and the obtained support 2 was used as the catalyst of Comparative Example 1 as it was. For the catalyst of Comparative Example 1, the amount of alkali metal was measured and TPD measurement was also carried out in the same manner as in Example 1. As a result, the desorption peak amount for Comparative Example 1 was 0.036 (mmol / g-cat). Furthermore, using the catalyst of Comparative Example 1, BAC was produced in the same manner as in Example 1, and the reaction results were evaluated. The BAC selectivity was 91.8%. The BAC yield was lower than that of Example 1. The results are shown in Table 1. The TPD measurement results for the catalyst of Comparative Example 1 are shown in Figure 3 (before multi-point baseline correction) and Figure 4 (after multi-point baseline correction). The arrows in each figure correspond to the positions corrected by multi-point baseline correction (selected peak start and end points).

[0048] Comparative Example 2 A catalyst was produced under the same production conditions as in Example 10 of Patent Document 1, and designated as the catalyst of Comparative Example 2. Specifically, using 10 g of alumina, 1 g of ruthenium chloride n-hydrate, and 200 g of water, the catalytic components were supported on the alumina by equilibrium adsorption (12-hour immersion), and then dried at 100°C for 12 hours to obtain supported material a. Supported material a was calcined in air at 500°C to obtain supported material b. Supported material b was contacted with 10% hydrogen / nitrogen gas at 150°C for 10 hours to obtain supported material c. Na was added to supported material c by equilibrium adsorption using 0.5 g of Na2CO3 and 200 g of water, and the resulting mixture was dried to obtain the catalyst of Comparative Example 2. For the catalyst of Comparative Example 2, TPD measurement was carried out in the same manner as in Example 1. The TPD measurement results for the catalyst of Comparative Example 2 are shown in Figure 5 (before multi-point baseline correction) and Figure 6 (after multi-point baseline correction). The arrows in each figure correspond to the positions corrected by multi-point baseline correction (selected peak start and end points). As a result, the desorption peak amount for Comparative Example 2 was 0.054 (mmol / g-cat).

[0049] Comparative Example 3 A catalyst was produced under the same production conditions as in Comparative Example 1 of Patent Document 1, and designated as the catalyst of Comparative Example 3. For the catalyst of Comparative Example 3, TPD measurement was carried out in the same manner as in Example 1. The TPD measurement results for the catalyst of Comparative Example 3 are shown in Figure 7 (before multi-point baseline correction) and Figure 8 (after multi-point baseline correction). The arrows in each figure correspond to the positions corrected by multi-point baseline correction (selected peak start and end points). As a result, the desorption peak amount for Comparative Example 3 was 0.023 (mmol / g-cat).

[0050] [Table 1]

[0051] According to the catalyst production methods of Comparative Examples 2 and 3, since the alkali metal is added by the equilibrium adsorption method, it is difficult to control the amount of alkali metal taken into the catalyst, and as a result, it is evaluated that it tends to be difficult to control the desorption peak amount. In contrast, according to the catalyst production methods of Examples 1 to 4, since the alkali metal is added by the IW method after the base treatment, it is easier to control the amount of alkali metal taken into the catalyst than in Comparative Examples 2 and 3, and as a result, it is evaluated that it tends to be easier to control the desorption peak amount.

[0052] It was confirmed that the BAC selectivity was higher in all of Examples 1 to 4 than in Comparative Example 1. Furthermore, the BAC yield in Examples 1 and 2 was higher than the BAC yield in Examples 3 and 4, and there was a tendency for the alkali metals Na and K to further improve not only the selectivity but also the yield. In this comparison, in view of the level of performance required of recent catalysts, a difference in BAC selectivity or BAC yield exceeding 0.1 was evaluated as being significant.

[0053] Comparative Example 4 BAC was produced in the same manner as in Comparative Example 1, except that in the production of BAC in Comparative Example 1, the raw material was changed from meta-xylylenediamine (4 mass%) to para-xylylenediamine (4 mass%) and the solvent was changed from 1,3-bis(aminomethyl)cyclohexane to 1,4-bis(aminomethyl)cyclohexane, and the reaction results were evaluated (BAC selectivity and PXDA conversion were calculated).

[0054] [Example 5] BAC was produced in the same manner as in Comparative Example 4, except that the catalyst of Example 1 was used instead of the catalyst of Comparative Example 4, and the reaction results were evaluated. The BAC selectivity of Example 5 was 0.5% higher than the BAC selectivity of Comparative Example 4. The PXDA conversion of Example 5 was 4.0% higher than the PXDA conversion of Comparative Example 4. The yield of Example 5 was 4.2% higher than the yield of Comparative Example 4.

[0055] [Example 6] BAC was produced in the same manner as in Comparative Example 4, except that the catalyst of Example 2 was used instead of the catalyst of Comparative Example 4, and the reaction results were evaluated. The BAC selectivity of Example 6 was 1.1% higher than the BAC selectivity of Comparative Example 4. The PXDA conversion of Example 6 was 4.2% higher than the PXDA conversion of Comparative Example 4. The yield of Example 6 was 5.0% higher than the yield of Comparative Example 4.

[0056] Comparing Examples 5 and 6 with Comparative Example 4, it can be seen that the catalysts of Examples 1 and 2 exhibit higher catalytic performance than the catalyst of Comparative Example 1, even when PXDA is used as the raw material for BAC production.

[0057] This application is based on a Japanese patent application (Patent Application No. 2023-058039) filed on March 31, 2023, the contents of which are incorporated herein by reference.

Claims

1. A catalyst for producing bis(aminomethyl)cyclohexane, having hydrogenation ability, comprising: the catalyst has a desorption peak amount of 0.020 mmol / g-cat or less as measured by the ammonia temperature programmed desorption method described below; the catalyst comprises an alkali metal, a catalytic component, and a support that supports the catalytic component; the catalyst component contains at least one selected from the group consisting of Ru, Rh, and Ni, the support comprises at least one selected from the group consisting of alumina, diatomaceous earth, and carbon; The catalyst, wherein the alkali metal comprises at least one selected from the group consisting of Li, Na, K, Rb, and Cs. (Ammonia temperature programmed desorption method) 150 mg of the catalyst was contacted with He gas at 500° C. and a gas flow rate of 20 sccm for 30 minutes. Then, 5% by volume of NH 3 The catalyst is contacted with a mixed gas of 1000 ppm ...

2. The catalyst described in claim 1, wherein the catalytic component comprises Ru.

3. The Ru content in the catalyst is 0.1 to 10.0 mass% relative to 100 mass% of the catalyst, The catalyst according to claim 2, wherein the Na content in the catalyst is 0.1 to 10.0 mass% relative to 100 mass% of the catalyst.

4. The catalyst of claim 3 wherein the support comprises alumina.

5. A method for producing the catalyst according to claim 1, comprising: (a) reacting the catalyst component with the support to obtain a first reactant; (b) adding the alkali metal to the first reactant to obtain a second reactant; A method for producing a catalyst, comprising:

6. further comprising a step (c) of reducing the second reactant to obtain a third reactant; 6. The method for producing a catalyst according to claim 5, wherein the desorption peak amount of the third reactant measured by the ammonia temperature programmed desorption method is 0.020 mmol / g-cat or less.

7. The method for producing a catalyst according to claim 6, wherein the step (c) is carried out at a temperature of 160 to 360°C.

8. 6. The method for producing a catalyst according to claim 5, wherein the step (a) comprises adsorbing the Ru raw material solution onto the support, drying the adsorbed Ru raw material solution, and contacting the adsorbed Ru raw material solution with a basic aqueous solution.

9. a hydrogenation step of continuously contacting xylylenediamine with hydrogen in the presence of a catalyst having hydrogenation ability to obtain bis(aminomethyl)cyclohexane, the catalyst has a desorption peak amount of 0.020 mmol / g-cat or less as measured by the ammonia temperature programmed desorption method described below; the catalyst comprises an alkali metal, a catalytic component, and a support that supports the catalytic component; the catalyst component contains at least one selected from the group consisting of Ru, Rh, and Ni, the support comprises at least one selected from the group consisting of alumina, diatomaceous earth, and carbon; The method for producing bis(aminomethyl)cyclohexane, wherein the alkali metal includes at least one selected from the group consisting of Li, Na, K, Rb, and Cs. (Ammonia temperature programmed desorption method) 150 mg of the catalyst was contacted with He gas at 500° C. and a gas flow rate of 20 sccm for 30 minutes. Then, 5% by volume of NH 3 The catalyst is contacted with a mixed gas of 1000 ppm ...

10. The method for producing bis(aminomethyl)cyclohexane according to claim 9, wherein the catalyst component contains Ru.

11. The catalyst is obtained by the production method (A), The production method (A) (a) reacting the catalyst component with the support to obtain a first reactant; (b) adding the alkali metal to the first reactant to obtain a second reactant; The method for producing bis(aminomethyl)cyclohexane according to claim 10, comprising:

12. The process (A) further comprises a step (c) of reducing the second reactant to obtain a third reactant; 12. The method for producing bis(aminomethyl)cyclohexane according to claim 11, wherein the third reactant has a desorption peak amount of 0.020 mmol / g-cat or less as measured by the ammonia temperature programmed desorption method.

13. The method for producing bis(aminomethyl)cyclohexane according to claim 12, wherein the step (c) is carried out at a temperature of 160 to 360°C.

14. 14. The method for producing bis(aminomethyl)cyclohexane according to claim 13, wherein the step (a) comprises adsorbing a Ru raw material solution onto a carrier, drying the adsorbed Ru raw material solution, and contacting the adsorbed Ru raw material solution with a basic aqueous solution.

15. The Ru content in the catalyst is 0.1 to 10.0 mass% relative to 100 mass% of the catalyst, 15. The method for producing bis(aminomethyl)cyclohexane according to claim 14, wherein the Na content in the catalyst is 0.1 to 10.0 mass% relative to 100 mass% of the catalyst.

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