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

Abstract

The present invention relates to a catalyst for producing bis (aminomethyl) cyclohexane, said catalyst having hydrogenation ability and having a desorption peak amount of 0.020 mmol / g-cat or less as measured by the following ammonia temperature-programmed desorption method for the catalyst. (an ammonia temperature programmed desorption method), enabling He gas to be in contact with 150mg of the catalyst for 30 minutes at the temperature of 500 DEG C and the gas flow of 20sccm. Next, a mixed gas containing 5 vol% of NH3 and the balance of He is brought into contact with the catalyst at 50 DEG C at a gas flow rate of 20 sccm for 10 minutes. Then, He gas is brought into contact with the catalyst at a gas flow rate of 20 sccm, the temperature is raised at 10 DEG C / min during this period, and a desorption peak is detected using a thermal conductivity detector.

Description

Technical Field

[0001] This invention relates to catalysts, methods for manufacturing catalysts, and methods for manufacturing bis(aminomethyl)cyclohexane. Background Technology

[0002] bis(aminomethyl)cyclohexane (hereinafter also referred to as "BAC") is an important compound in industry as a raw material for polyamides, bis(isocyanate methyl)cyclohexane, etc. BAC can be obtained, for example, by the contact hydrogenation of phenylenediamine. Regarding this contact hydrogenation, for example, Patent Document 1 proposes a catalyst prepared by adding an alkali metal modifier as an auxiliary agent to ruthenium / alumina as a catalyst component for contact hydrogenation.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Description of Chinese Patent Application Publication No. 112473663 Summary of the Invention

[0006] The problem the invention aims to solve

[0007] The catalyst described in Patent Document 1 has improved selectivity, but there is a recent tendency to expect even higher catalytic performance, so there is room for further improvement.

[0008] The present invention was made in view of the above-mentioned problems, and its object is to provide catalysts, etc., that exhibit excellent BAC selectivity.

[0009] Solution for solving the problem

[0010] The inventors conducted in-depth research and found that the above-mentioned problems could be solved by using a catalyst with specified physical properties, thus completing the present invention.

[0011] That is, the present invention includes the following methods. [1]

[0013] A catalyst, which is capable of hydrogenation, for the preparation of bis(aminomethyl)cyclohexane.

[0014] The desorption peak amount of the aforementioned catalyst, determined by the following ammonia-programmed temperature desorption method, was below 0.020 mmol / g-cat.

[0015] (Ammonia temperature-programmed desorption method)

[0016] He gas was contacted with 150 mg of the aforementioned catalyst at 500 °C and a flow rate of 20 sccm for 30 minutes. Next, a mixture of 5% by volume NH3 and the remainder He was contacted with the aforementioned catalyst at 50 °C and a flow rate of 20 sccm for 10 minutes. Then, He gas was contacted with the aforementioned catalyst at a flow rate of 20 sccm, with the temperature increased at 10 °C / min during this period, and the desorption peak was detected using a thermal conductivity detector. [2]

[0018] According to the catalyst described in [1], the aforementioned catalyst comprises a catalyst component and a support carrying the catalyst component.

[0019] The aforementioned catalyst component includes Ru. [3]

[0021] According to the catalyst described in [1] or [2], wherein the Ru content in the aforementioned catalyst is 0.1 to 10.0% by mass relative to 100% by mass of the catalyst.

[0022] The Na content in the aforementioned catalyst is 0.1 to 10.0% by mass relative to 100% by mass of the catalyst. [4]

[0024] According to the catalyst described in [2] or [3], wherein the support comprises alumina. [5]

[0026] A method for manufacturing a catalyst according to any one of [1] to [4], comprising:

[0027] The process (a) of reacting the catalyst components with the support to obtain the first reactant; and

[0028] Step (b) involves adding an alkali metal to the aforementioned first reactant to obtain the second reactant. [6]

[0030] The method for manufacturing the catalyst according to [5] further includes a step (c) of reducing the aforementioned second reactant to obtain the third reactant.

[0031] The desorption peak amount of the aforementioned third reactant, determined by the aforementioned ammonia-programmed temperature desorption method, was below 0.020 mmol / g-cat. [7]

[0033] According to the method for manufacturing the catalyst described in [6], the aforementioned step (c) is carried out at a temperature of 160 to 360°C. [8]

[0035] The method for manufacturing a catalyst according to any one of [5] to [7], wherein the aforementioned step (a) includes the following steps: after adsorbing the Ru raw material solution onto the support, drying it and contacting it with an alkaline aqueous solution. [9]

[0037] The method for manufacturing a catalyst according to any one of [5] to [7], wherein the aforementioned alkali metal comprises at least one selected from the group consisting of Na, K and Li.

[10]

[0039] A method for producing bis(aminomethyl)cyclohexane, comprising:

[0040] The hydrogenation process involves continuously contacting phenylenediamine with hydrogen in the presence of a catalyst with hydrogenation capabilities to obtain bis(aminomethyl)cyclohexane.

[0041] The desorption peak amount of the aforementioned catalyst, determined by the ammonia-programmed temperature desorption method described below, was below 0.020 mmol / g-cat.

[0042] (Ammonia temperature-programmed desorption method)

[0043] He gas was contacted with 150 mg of the aforementioned catalyst at 500 °C and a flow rate of 20 sccm for 30 minutes. Next, a mixture of 5% by volume NH3 and the remainder He was contacted with the aforementioned catalyst at 50 °C and a flow rate of 20 sccm for 10 minutes. Then, He gas was contacted with the aforementioned catalyst at a flow rate of 20 sccm, with the temperature increased at 10 °C / min during this period, and the desorption peak was detected using a thermal conductivity detector.

[11]

[0045] According to the method for manufacturing bis(aminomethyl)cyclohexane described in

[10] , the aforementioned catalyst comprises a catalyst component and a support for supporting the catalyst component.

[0046] The aforementioned catalyst component includes Ru.

[12]

[0048] According to the method for producing bis(aminomethyl)cyclohexane described in

[11] , wherein the aforementioned catalyst is obtained by method A,

[0049] The aforementioned manufacturing method (A) includes:

[0050] The process (a) of reacting the aforementioned catalyst component with the aforementioned support to obtain the first reactant; and

[0051] Step (b) involves adding an alkali metal to the aforementioned first reactant to obtain the second reactant.

[13]

[0053] According to the method for manufacturing bis(aminomethyl)cyclohexane described in

[12] , the aforementioned method (A) further includes a step (c) of reducing the aforementioned second reactant to obtain a third reactant.

[0054] The desorption peak amount of the aforementioned third reactant, determined by the aforementioned ammonia-programmed temperature desorption method, was below 0.020 mmol / g-cat.

[14]

[0056] According to the method for manufacturing bis(aminomethyl)cyclohexane described in

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

[15]

[0058] The method for manufacturing bis(aminomethyl)cyclohexane according to any one of

[12] to

[14] , wherein the aforementioned step (a) includes the following steps: after adsorbing the Ru raw material solution onto the carrier, drying it and contacting it with an alkaline aqueous solution.

[16]

[0060] The method for producing bis(aminomethyl)cyclohexane according to any one of

[12] to

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

[17]

[0062] The method for producing bis(aminomethyl)cyclohexane according to any one of

[10] to

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

[0063] The Na content in the aforementioned catalyst is 0.1 to 10.0% by mass relative to 100% by mass of the aforementioned catalyst.

[18]

[0065] The method for manufacturing bis(aminomethyl)cyclohexane according to any one of

[11] to

[17] , wherein the aforementioned support comprises aluminum oxide.

[0066] The effects of the invention

[0067] According to the present invention, catalysts and the like that exhibiting excellent BAC selectivity can be provided. Attached Figure Description

[0068] Figure 1 A graph showing the TPD measurement results of the catalyst obtained in Example 1.

[0069] Figure 2 To express [the opinion / towards] Figure 1 The graph shows the result of multi-point baseline correction.

[0070] Figure 3 A graph showing the TPD determination results of the catalyst obtained in Comparative Example 1.

[0071] Figure 4 To express [the opinion / towards] Figure 3 The graph shows the result of multi-point baseline correction.

[0072] Figure 5 A graph showing the TPD determination results of the catalyst obtained in Comparative Example 2.

[0073] Figure 6 To express [the opinion / towards] Figure 5 The graph shows the result of multi-point baseline correction.

[0074] Figure 7 A graph showing the TPD determination results of the catalyst obtained in Comparative Example 3.

[0075] Figure 8 To express [the opinion / towards] Figure 7 The graph shows the result of multi-point baseline correction. Detailed Implementation

[0076] Hereinafter, a detailed description will be given of a method for carrying out the present invention (hereinafter referred to as "this embodiment"). This embodiment is merely an example for illustrating the present invention and is not intended to limit the invention to its following content. The present invention can be appropriately modified and implemented within its scope.

[0077] <Catalyst>

[0078] The catalyst in this embodiment is a hydrogenation-capable catalyst for preparing bis(aminomethyl)cyclohexane. The desorption peak amount of the aforementioned catalyst, as determined by the following ammonia temperature programmed desorption method (hereinafter also referred to as "TPD determination"), is less than 0.020 mmol / g-cat.

[0079] (Ammonia temperature-programmed desorption method)

[0080] He gas was contacted with 150 mg of the aforementioned catalyst at 500 °C and a flow rate of 20 sccm for 30 minutes. Next, a mixture of 5% by volume NH3 and the remainder He was contacted with the aforementioned catalyst at 50 °C and a flow rate of 20 sccm for 10 minutes. Then, He gas was contacted with the aforementioned catalyst at a flow rate of 20 sccm, with the temperature increased at 10 °C / min during this period, and the desorption peak was detected using a thermal conductivity detector.

[0081] The catalyst in this embodiment is configured as described above, and therefore exhibits excellent BAC selectivity.

[0082] (TPD measurement)

[0083] The catalyst of this embodiment exhibits excellent BAC selectivity because the desorption peak amount measured by the above TPD determination is below 0.020 mmol / g-cat. The reason for this may not be clear, and is not limited here, but is speculated as follows.

[0084] The inventors studied conventional hydrogenation catalysts used in BAC production and found that low-boiling-point impurities are easily generated as byproducts of the hydrogenation reaction, thus limiting the improvement of BAC selectivity. Further research was conducted to investigate this reason, and it was hypothesized that the acid point on the catalyst surface has a significant impact, particularly in the hydrogenation reaction used to produce BAC, and is strongly correlated with the formation of this impurity. Therefore, it was hypothesized that reducing this point could lead to a further improvement in BAC selectivity. Based on this hypothesis, the inventors conducted further research and found that when the desorption peak amount obtained in this determination is used as an indicator, a value below 0.020 mmol / g-cat shows a particular tendency to improve BAC selectivity. The detailed mechanism may not be clear, but the inventors hypothesize as follows. That is, it is believed that the reaction substrate and product contain amino groups in their structure, which react strongly with the active sites on the catalyst surface. Specifically, it is believed that the above-mentioned impurities (byproducts) are generated due to the deamination reaction. Therefore, it is believed that by using the desorption peak value obtained in this determination as an indicator and reducing its value sufficiently, the active sites on the catalyst surface that react strongly with NH3 disappear, thereby inhibiting the deamination reaction and increasing the selectivity.

[0085] However, the above is merely an explanation of one of the main reasons why the catalyst of this embodiment exhibits excellent BAC selectivity, and the mechanism of action of this embodiment is not limited thereto.

[0086] In addition to the above viewpoints, from the perspective of further improving BAC yield, the desorption peak amount is preferably below 0.015 mmol / g-cat.

[0087] More specifically, the above-mentioned desorption peak amount can be determined based on the method described in the embodiments described later.

[0088] The aforementioned desorption peak values ​​can be adjusted to the above range, for example, by manufacturing catalysts based on the methods described later.

[0089] From the viewpoint of catalyst strength, the catalyst of this embodiment preferably comprises a catalyst component and a support carrying the catalyst component.

[0090] (Catalyst components)

[0091] The catalyst composition in this embodiment is not particularly limited, and various known substances can be used as the catalyst composition. Examples of catalyst compositions in this embodiment include Ru, Rh, and Ni; one or more of these can be used alone or in combination. In this embodiment, from the viewpoint of hydrogenation capacity, the catalyst composition preferably includes Ru. The catalyst of this embodiment particularly preferably includes a catalyst composition and a support for carrying the catalyst composition, wherein the catalyst composition includes Ru. In the case where the catalyst of this embodiment includes Ru, from the viewpoint of hydrogenation capacity, the Ru content relative to 100% by mass of the catalyst is preferably 0.1 to 10.0% by mass.

[0092] The Ru content mentioned above can be determined by X-ray fluorescence (XRF) analysis. Alternatively, the content can also be determined by the feed ratio during catalyst manufacturing.

[0093] (Carrier)

[0094] In this embodiment, the support is not particularly limited as long as it can support the catalyst components, and various known supports can be used. Examples of supports in this embodiment include alumina, diatomaceous earth, and carbon; one or more of these can be used individually or in combination. In this embodiment, from the viewpoint of catalyst strength, the support preferably contains alumina.

[0095] (Alkali metals)

[0096] From the viewpoint of hydrogenation capacity, the catalyst in this embodiment preferably contains an alkali metal. The alkali metal in this embodiment differs from the catalyst components described above, and its type is not particularly limited; examples include Li, Na, K, Rb, and Cs. One or more of these can be used individually or in combination. From the viewpoint of hydrogenation capacity, the alkali metal in this embodiment preferably contains at least one selected from the group consisting of Na, K, and Li. Furthermore, 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.

[0097] In this embodiment, when the catalyst contains an alkali metal, from the viewpoint of hydrogenation capacity, the alkali metal content is preferably 0.1 to 10.0% by mass relative to 100% by mass of the catalyst. Particularly when the catalyst in this embodiment contains Na, from the viewpoint of hydrogenation capacity, the Na content is preferably 0.1 to 10.0% by mass relative to 100% by mass of the catalyst. In this embodiment, the catalyst particularly preferably has a Ru content of 0.1 to 10.0% by mass relative to 100% by mass, and a Na content of 0.1 to 10.0% by mass relative to 100% by mass of the catalyst.

[0098] The Na content and the content of other alkali metals mentioned above can be determined based on the methods described in the examples below. Alternatively, the Na content and the content of other alkali metals can also be determined based on the feed ratio during catalyst manufacturing.

[0099] <Methods for manufacturing catalysts>

[0100] The method for manufacturing the catalyst in this embodiment is not particularly limited as long as the catalyst of this embodiment can be obtained, but it is preferably obtained by the following method. That is, the preferred method for manufacturing the catalyst of this embodiment (hereinafter also referred to as "method (A)") is the method for manufacturing the catalyst of this embodiment, which includes: a step (a) of reacting the catalyst component with a support to obtain a first reactant; and a step (b) of adding an alkali metal to the aforementioned first reactant to obtain a second reactant. As configured as described above, method (A) can efficiently manufacture a catalyst exhibiting excellent BAC selectivity.

[0101] (Process(a))

[0102] In step (a), the catalyst component is reacted with the support to obtain the first reactant. The catalyst component and support can be any substances exemplified in <Catalyst>. The reaction between the catalyst component and the support is not limited to the following; for example, it can be carried out using the Incipient Wetness Method (IW) under various known conditions.

[0103] In this embodiment, from the viewpoint of the hydrogenation capacity of the obtained catalyst, step (a) preferably includes the following steps: after adsorbing the Ru feedstock solution onto the support, drying it, and contacting it with an alkaline aqueous solution. The Ru feedstock solution is not limited to the following substances, but preferably contains, for example, ruthenium chloride n hydrate. The alkaline aqueous solution is not limited to the following substances, but preferably contains, for example, sodium hydroxide.

[0104] (Process (b))

[0105] In step (b), an alkali metal is added to the first reactant to obtain a second reactant. The second reactant can be used as a catalyst in this embodiment on its own, or it can be used as a catalyst in this embodiment after further adjustments to properties such as hydrogenation capacity in step (c) described later. Regarding the alkali metal, those exemplified in <Catalyst> can be appropriately used. The addition of the alkali metal is not limited to the following; for example, it can be carried out using the initial wet impregnation (IW) method under various known conditions. The alkali metal is not limited to the following substances; for example, it can be added in the form of carbonates, bicarbonates, nitrates, and hydroxides. From the viewpoint of the hydrogenation capacity of the obtained catalyst, the alkali metal in this embodiment preferably includes at least one selected from the group consisting of Na, K, and Li.

[0106] (Process (c))

[0107] Preparation method (A) preferably further includes a step (c) of reducing the second reactant to obtain the third reactant. When the third reactant is used as the catalyst in this embodiment, there is a tendency for the hydrogenation capacity to become higher. From the same viewpoint as above, in preparation method (A), the desorption peak amount of the aforementioned third reactant measured by the aforementioned ammonia temperature-programmed desorption method is preferably 0.020 mmol / g-cat or less, more preferably 0.015 mmol / g-cat or less.

[0108] There are no particular limitations on the temperature conditions for step (c), but from the viewpoint of the hydrogenation capacity of the obtained catalyst, step (c) is preferably carried out at a temperature of 160 to 360°C.

[0109] <Method for the manufacture of bis(aminomethyl)cyclohexane>

[0110] The method for producing bis(aminomethyl)cyclohexane according to this embodiment (hereinafter also referred to as "the method of this embodiment") includes a hydrogenation step in which phenylenediamine is continuously contacted with hydrogen in the presence of a catalyst with hydrogenation capability to obtain bis(aminomethyl)cyclohexane, wherein the desorption peak amount of the catalyst measured by the ammonia temperature-programmed desorption method described below is 0.020 mmol / g-cat or less.

[0111] (Ammonia temperature-programmed desorption method)

[0112] He gas was contacted with 150 mg of the aforementioned catalyst at 500 °C and a flow rate of 20 sccm for 30 minutes. Next, a mixture of 5% by volume NH3 and the remainder He was contacted with the aforementioned catalyst at 50 °C and a flow rate of 20 sccm for 10 minutes. Then, He gas was contacted with the aforementioned catalyst at a flow rate of 20 sccm, with the temperature increased at 10 °C / min during this period, and the desorption peak was detected using a thermal conductivity detector.

[0113] The manufacturing method of this embodiment is configured as described above, thus enabling the production of BAC with a high BAC selectivity.

[0114] (Hydrogenation process)

[0115] In the hydrogenation process of this embodiment, phenylenediamine is continuously contacted with hydrogen in the presence of a catalyst capable of hydrogenation, thereby obtaining bis(aminomethyl)cyclohexane. That is, continuous hydrogenation of phenylenediamine is performed. The bis(aminomethyl)cyclohexane obtained by the method of this embodiment can be 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, or a mixture thereof.

[0116] In the preparation method of this embodiment, phenylenediamine, one of the raw materials, exists in three isomers: ortho, meta, and para. These isomers, either individually or in mixtures, can be used as raw materials. In the preparation method of this embodiment, the meta and para isomers are preferably used. That is, phenylenediamine preferably includes m-phenylenediamine (hereinafter also referred to as "MXDA") and / or p-phenylenediamine (hereinafter also referred to as "PXDA").

[0117] In the preparation method of this embodiment, there is no particular limitation on the solvent that can be used, and various known solvents can be employed. Examples of solvents in this embodiment include, but are not limited to, alkylamines and alkylene diamines. They can be used alone or in combination of two or more. When alkylamines and alkylene diamines are included as solvents, since the reaction products are separated by distillation and recycled, it is preferable to select substances with 1 to 18 carbon atoms as liquids at room temperature for easy recycling in industrial continuous manufacturing methods. In this case, there is a tendency for the formation of byproducts to be further suppressed and the yield of the target product to be further increased.

[0118] Examples of alkylamines used in this embodiment include, but are not limited to, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, isopropylamine, diisopropylamine, butylamine, dibutylamine, tributylamine, hexylamine, cyclohexylamine, and 2-ethylhexylamine. They can be used individually or in combination of two or more.

[0119] Examples of alkylene diamines used in this embodiment include, but are not limited to, ethylenediamine, propylenediamine, 1,4-butanediamine, hexamethylenediamine, and bis(aminomethyl)cyclohexane. They can be used individually or in combination of two or more.

[0120] In this embodiment, bis(aminomethyl)cyclohexane can be recycled from the form obtained by catalytic reduction, therefore the solvent in this embodiment preferably comprises 1,3-bis(aminomethyl)cyclohexane and / or 1,4-bis(aminomethyl)cyclohexane.

[0121] In the preparation method of this embodiment, the mixing weight ratio of alkylamines and alkylene diamines relative to the raw material phenylenediamine (amount of phenylenediamine: total amount of alkylamines and alkylene diamines) is not particularly limited, but is preferably set to 1:30 to 1:1.

[0122] The aforementioned alkylamines and alkylene diamines can be used alone, or in the form of mixtures of amines and alkylene diamines, or in the form of mixtures with other organic solvents. Examples of miscible organic solvents include, but are not limited to, alcohols such as methanol, ethanol, isopropanol, and n-propanol.

[0123] In the hydrogenation process of this embodiment, there are no particular limitations on the hydrogen supply conditions, but it is preferable to set the hydrogen pressure to 5 MPa or more and 15 MPa or less, and the hydrogen supply rate relative to 1 mL of catalyst to 0.5 N mL / min or more and 2.5 N mL / min or less. The above hydrogen pressure can be determined as gauge pressure.

[0124] From the viewpoint of hydrogenation capacity, the catalyst in the preparation method of this embodiment has a desorption peak amount of 0.020 mmol / g-cat or less, preferably 0.015 mmol / g-cat or less, as determined by the above-described ammonia temperature-programmed desorption method. The catalyst described in <Catalyst> can be appropriately used as this catalyst.

[0125] The catalyst in the preparation method of this embodiment may include a catalyst component and a support for carrying the catalyst component. The catalyst component and the support may be appropriately represented by the substances exemplified in <Catalyst>.

[0126] From the viewpoint of hydrogenation capability, the catalyst in the preparation method of this embodiment preferably includes a catalyst component and a support for carrying the catalyst component, and the aforementioned catalyst component includes Ru.

[0127] In this embodiment, the catalyst carrier preferably comprises alumina.

[0128] In the preparation method of this embodiment, the catalyst preferably contains an alkali metal in addition to the catalyst components and the support. Regarding the alkali metal, those exemplified in the <Catalyst> section can be used appropriately, and from the viewpoint of hydrogenation capacity, it is preferable to include at least one selected from the group consisting of Na, K, and Li.

[0129] In the preparation method of this embodiment, the catalyst preferably has a Ru content of 0.1 to 10.0% by mass relative to 100% by mass of the catalyst, and the alkali metal content of the catalyst is 0.1 to 10.0% by mass relative to 100% by mass of the catalyst.

[0130] In the preparation method of this embodiment, the catalyst preferably has a Ru content of 0.1 to 10.0% by mass relative to 100% by mass and a Na content of 0.1 to 10.0% by mass relative to 100% by mass.

[0131] The catalyst in the preparation method of this embodiment is preferably obtained by preparation method (A), which includes: a step (a) of reacting the aforementioned catalyst component with the aforementioned support to obtain a first reactant; and a step (b) of adding an alkali metal to the aforementioned first reactant to obtain a second reactant. The second reactant can be used as the catalyst in the preparation method of this embodiment, or it can be used as the catalyst in the preparation method of this embodiment after further adjusting its properties such as hydrogenation capacity through the following step (c).

[0132] Here, the preparation method (A) may appropriately adopt the preparation method described in <Methods for Manufacturing Catalysts>.

[0133] That is, from the viewpoint of the hydrogenation capacity of the obtained catalyst, the preparation method (A) preferably further includes the step (c) of reducing the aforementioned second reactant to obtain the third reactant, and the desorption peak amount of the aforementioned third reactant measured by the aforementioned ammonia temperature-programmed desorption method is 0.020 mmol / g-cat or less, more preferably 0.015 mmol / g-cat or less.

[0134] From the viewpoint of the hydrogenation capacity of the obtained catalyst, step (a) preferably includes the following steps: after adsorbing the Ru feedstock solution onto the support, drying it and contacting it with an alkaline aqueous solution.

[0135] From the viewpoint of the hydrogenation capacity of the obtained catalyst, the alkali metal in step (b) preferably includes at least one selected from the group consisting of Na, K and Li.

[0136] From the viewpoint of the hydrogenation capacity of the obtained catalyst, step (c) is preferably carried out at a temperature of 160–360 °C.

[0137] The amount of catalyst in the preparation method of this embodiment is not particularly limited. The WHSV, which is the amount supplied relative to the raw material phenylenediamine, can be set to 0.1 to 5.0, preferably 0.1 to 2.0. The above amount is preferably used when using a catalyst in which about 2% by mass of ruthenium is supported, but this condition can also be used for other catalysts in this embodiment.

[0138] In the hydrogenation process of this embodiment, the reaction temperature is not particularly limited, but is 50 to 150°C, preferably 80 to 130°C.

[0139] The reactor used for implementing the hydrogenation process in this embodiment is not particularly limited; for example, a fixed-bed reactor can be used. When the reactor in this embodiment operates continuously using a solvent, it can be configured such that after separating the dissolved gas from the reaction product using a gas-liquid separator, the BAC obtained through contact hydrogenation can be separated and recycled; alternatively, it can be configured such that the reaction product after gas-liquid separation can be distilled and recycled using a solvent recovery device to separate the solvent. In this embodiment, BAC obtained through contact hydrogenation can also be used as the solvent; in this case, it is preferable to directly recycle the dissolved gas after separating it from the reaction product using a gas-liquid separator.

[0140] (Optional process)

[0141] In addition to the hydrogenation step, the preparation method of this embodiment may include optional steps. The preparation method of this embodiment is not limited to the following; for example, it may further include a purification step. Examples of purification steps include distillation at atmospheric pressure to remove alkylamines, alkylene diamines, and organic solvents, or vacuum distillation, thereby preferably separating the target compound (BAC) from the reaction product.

[0142] Example

[0143] The following examples illustrate this embodiment in more detail, but the scope of this embodiment is not limited to these examples.

[0144] [Example 1]

[0145] (Catalyst manufacturing)

[0146] Using 20 g of alumina, 1 g of ruthenium chloride n hydrate, and 8 g of water, the catalyst components were supported on alumina by initial wet impregnation (IW), and then dried at 120 °C to obtain support 1. Support 1 was then subjected to alkali treatment with 60 g of 1M sodium hydroxide and 300 g of water (i.e., contacting support 1, sodium hydroxide, and water), and dried at 110 °C to obtain support 2. 1.0 g of NaHCO3 and 8 g of water were added to support 2 using the IW method, and the mixture was dried at 110 °C to obtain the catalyst of Example 1.

[0147] (Amount of alkali metals in the catalyst)

[0148] The amount of alkali metal (Na) in the catalyst was analyzed by X-ray fluorescence (XRF), and the result was 1.7% by mass, based on 100% of the catalyst. That is, the amount of alkali metal (Na) is 0.8 mmol / g-cat.

[0149] (TPD measurement)

[0150] He gas was contacted with 150 mg of catalyst at 500 °C and a flow rate of 20 sccm for 30 minutes. Next, a mixture of 5% by volume NH3 and the remainder He was contacted with the catalyst at 50 °C and a flow rate of 20 sccm for 10 minutes. Then, He gas was contacted with the catalyst at a flow rate of 20 sccm, with the temperature increased at 10 °C / min during this period, and the desorption peak was detected using a thermal conductivity detector (Microtrac BEL "BEL-CAT B"). Specifically, for the desorption peak, the peak appearing between 50 and 350 °C was calculated from the area of ​​the vertically segmented high-temperature side peak after multi-point baseline correction. Multi-point baseline correction was performed using known methods for the start and end points of the peak. The desorption peak amount (mmol / g-cat) was determined by measuring the calibration pulse of NH3. That is, the value was calculated using the calibration factor based on the method described in the "BEL-CAT B" manual (assuming the gas type of the desorption peak is NH3). The TPD measurement results of the catalyst of Example 1 are shown below. Figure 1 (before multi-point baseline correction) and Figure 2 (After multi-point baseline correction). It should be noted that the arrows in each figure correspond to the positions corrected by multi-point baseline correction (selecting the start and end points of the peak). Based on the above results, the desorption peak amount in Example 1 is 0.005 (mmol / g-cat).

[0151] (The manufacture of BAC)

[0152] The following hydrogenation reaction was carried out using a fixed-bed, externally heated, flow-through reactor with an inner diameter of 17 mm (Φ) and a flow rate of 320 mm (L). First, hydrogen gas was contacted with 16 mL of catalyst at 260 °C and a flow rate of 100 mL / min for 7 hours to reduce the catalyst. Then, in the presence of the reduced catalyst, a mixture containing 16 mL of catalyst, at 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 relative to 1 mL of catalyst), was supplied to the reactor at a rate of 45 g / h.

[0153] (Reaction Results)

[0154] The reaction products were collected 1 hour after the reaction started, 24 hours later, and analyzed by gas chromatography. The results showed that the BAC selectivity was 94.2% and the MXDA conversion rate was 88.9%. The gas chromatography analysis conditions were as follows, and quantification was performed by the area percentage method.

[0155] GC device: Shimadzu GC2030

[0156] Column: HP-1MS (30m length × 0.25mm inner diameter × 0.25μm film thickness)

[0157] Sample introduction temperature: 300℃

[0158] Flow split ratio: 10

[0159] Temperature program: Hold at 150℃ for 5 minutes, then increase to 300℃ (10 minutes) and hold at 300℃ for 10 minutes.

[0160] Detector and detection temperature: Flame ionization detector (FID), 300℃

[0161] Carrier gas: He (46.2 mL / min)

[0162] Injection volume: 0.2 μL

[0163] (Reduction of the catalyst and TPD determination)

[0164] In addition, 150 mg of the catalyst obtained in the "Catalyst Preparation" (i.e., the catalyst before its use in the "BAC Preparation") was reduced by contacting it with hydrogen gas at 260°C and a flow rate of 50 sccm for 30 minutes. Then, He gas was contacted with the reduced catalyst at 500°C and a flow rate of 20 sccm for 30 minutes. Next, a mixture of 5% by volume NH3 and the remainder He gas was contacted with the catalyst at 50°C and a flow rate of 20 sccm for 10 minutes. Then, He gas was contacted with the catalyst at a flow rate of 20 sccm, with the temperature increased at 10°C / min during this period, and the desorption peak was detected using a thermal conductivity detector (Microtrac BEL "BEL-CAT B"). Multipoint baseline correction and calculation of the desorption peak amount (mmol / g-cat) were performed in the same manner as described above. The result showed that the desorption peak amount of the reduced catalyst was 0.005 (mmol / g-cat), which was very consistent with the value before reduction.

[0165] [Example 2]

[0166] In the preparation of the catalyst in Example 1, 1.0 g of K₂CO₃ was used instead of 1.0 g of NaHCO₃. Otherwise, the catalyst of Example 2 was obtained in the same manner as in Example 1. The alkali metal content of the obtained catalyst was determined in the same manner as in Example 1, and TPD was also measured. The desorption peak amount of Example 2 was 0.002 (mmol / g-cat). Furthermore, using the catalyst of Example 2, BAC was prepared 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%.

[0167] The results are shown in Table 1.

[0168] [Example 3]

[0169] In the preparation of the catalyst in Example 1, 1.0 g of LiOH was used instead of 1.0 g of NaHCO3. Otherwise, the catalyst of Example 3 was obtained in the same manner as in Example 1. The alkali metal content of the obtained catalyst was determined in the same manner as in Example 1, and TPD was also performed. The desorption peak amount of Example 3 was 0.019 (mmol / g-cat). Furthermore, using the catalyst of Example 3, BAC was prepared in the same manner as in Example 1, and the reaction results were evaluated. The BAC selectivity was 94.0%.

[0170] The results are shown in Table 1.

[0171] [Example 4]

[0172] In the preparation of the catalyst in Example 1, 4.0 g of LiNO3 was used instead of 1.0 g of NaHCO3. Otherwise, the catalyst of Example 4 was obtained in the same manner as in Example 1. The alkali metal content of the obtained catalyst was determined in the same manner as in Example 1, and TPD was also performed. The desorption peak amount of Example 4 was 0.001 (mmol / g-cat). Furthermore, using the catalyst of Example 4, BAC was prepared 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.

[0173] The results are shown in Table 1.

[0174] Furthermore, for the catalyst of Example 4, the reduction and TPD determination of the catalyst were carried out in the same manner as in Example 1. The results showed that the desorption peak of the reduced catalyst was 0.001 (mmol / g-cat), which was very consistent with the value before reduction.

[0175] [Comparative Example 1]

[0176] In the preparation of the catalyst in Example 1, without adding 1.0 g of NaHCO3, the resulting supported material 2 was directly used as the catalyst of Comparative Example 1.

[0177] The alkali metal content of the catalyst in Comparative Example 1 was determined in the same manner as in Example 1, and TPD determination was also performed. The desorption peak amount of Comparative Example 1 was 0.036 (mmol / g-cat). Furthermore, BAC was prepared using the catalyst of Comparative Example 1 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.

[0178] The results are shown in Table 1. Additionally, the TPD determination results of the catalyst in Comparative Example 1 are shown in Table 1. Figure 3 (before multi-point baseline correction) and Figure 4 (After multi-point baseline correction). It should be noted that the arrows in each figure correspond to the positions that have been corrected by multi-point baseline correction (selecting the start and end points of the peak).

[0179] [Comparative Example 2]

[0180] The catalyst was manufactured under the same manufacturing conditions as in Example 10 of Patent Document 1, serving as the catalyst for Comparative Example 2. Specifically, using 10 g of alumina, 1 g of ruthenium chloride n hydrate, and 200 g of water, the catalyst components were supported on alumina by equilibrium adsorption (impregnation for 12 hours), and then dried at 100°C for 12 hours to obtain support a. Support a was calcined in air at 500°C to obtain support b. Support b was contacted with 10% hydrogen / nitrogen gas at 150°C for 10 hours to obtain support c. Na was added to support c by equilibrium adsorption using 0.5 g of Na₂CO₃ and 200 g of water, and then dried to obtain the catalyst of Comparative Example 2.

[0181] For the catalyst of Comparative Example 2, TPD determination was performed in the same manner as in Example 1.

[0182] The TPD determination results of the catalyst of Comparative Example 2 are shown below. Figure 5 (before multi-point baseline correction) and Figure 6 (After multi-point baseline correction). It should be noted that the arrows in each figure correspond to the positions corrected by multi-point baseline correction (selecting the start and end points of the peak). As a result, the desorption peak amount in Comparative Example 2 was 0.054 (mmol / g-cat).

[0183] [Comparative Example 3]

[0184] The catalyst was manufactured under the same manufacturing conditions as Comparative Example 1 of Patent Document 1, and was used as the catalyst of Comparative Example 3.

[0185] For the catalyst of Comparative Example 3, TPD determination was performed in the same manner as in Example 1.

[0186] The TPD determination results of the catalyst of Comparative Example 3 are shown below. Figure 7 (before multi-point baseline correction) and Figure 8 (After multi-point baseline correction). It should be noted that the arrows in each figure correspond to the positions corrected by multi-point baseline correction (selecting the start and end points of the peak). As a result, the desorption peak amount in Comparative Example 3 was 0.023 (mmol / g-cat).

[0187] [Table 1]

[0188] According to the catalyst manufacturing 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 entering the catalyst, resulting in a tendency for the control of the aforementioned desorption peak to become difficult. In contrast, according to the catalyst manufacturing methods of Examples 1 to 4, the alkali metal is added by the IW method after alkali treatment, so compared with Comparative Examples 2 and 3, the amount of alkali metal entering the catalyst can be easily controlled, resulting in a tendency for the control of the aforementioned desorption peak to become easier. As for the BAC selectivity, it was confirmed that Examples 1 to 4 were all higher than Comparative Example 1. In addition, the BAC yield of Examples 1 and 2 was higher than that of Examples 3 and 4, and in the case of Na and K as alkali metals, not only was the selectivity improved, but the yield also tended to be further improved. It should be noted that in this comparison, given the current performance level required for catalysts, a difference of more than 0.1 in the BAC selectivity and / or BAC yield is considered significant.

[0189] [Comparative Example 4]

[0190] In the production of BAC in Comparative Example 1, the m-phenylenediamine (4% by mass) used as a raw material was changed to p-phenylenediamine (4% by mass), and the solvent was changed from 1,3-bis(aminomethyl)cyclohexane to 1,4-bis(aminomethyl)cyclohexane. Otherwise, the production of BAC was carried out in the same manner as in Comparative Example 1, and the reaction results were evaluated (BAC selectivity and PXDA conversion were calculated).

[0191] [Example 5]

[0192] In the production of BAC in Comparative Example 4, the catalyst of Example 1 was used instead of the catalyst of Comparative Example 4. Otherwise, the production of BAC was carried out in the same manner as in Comparative Example 4, and the reaction results were evaluated. The BAC selectivity of Example 5 was 0.5% higher than that of Comparative Example 4. The PXDA conversion of Example 5 was 4.0% higher than that of Comparative Example 4. The yield of Example 5 was 4.2% higher than that of Comparative Example 4.

[0193] [Example 6]

[0194] In the production of BAC in Comparative Example 4, the catalyst of Example 2 was used instead of the catalyst of Comparative Example 4. Otherwise, the production of BAC was carried out in the same manner as in Comparative Example 4, and the reaction results were evaluated. The BAC selectivity of Example 6 was 1.1% higher than that of Comparative Example 4. The PXDA conversion of Example 6 was 4.2% higher than that of Comparative Example 4. The yield of Example 6 was 5.0% higher than that of Comparative Example 4.

[0195] As can be seen from the comparison between Examples 5-6 and Comparative Example 4, the catalysts of Examples 1-2 exhibited higher catalytic performance than the catalyst of Comparative Example 1, even when PXDA was used as the raw material for BAC manufacturing.

[0196] This application is based on Japanese Patent Application No. 2023-058039, filed on March 31, 2023, the contents of which are incorporated herein by reference.

Claims

1. A catalyst having hydrogenation capability for the preparation of bis(aminomethyl)cyclohexane, The desorption peak amount of the catalyst, determined by the following ammonia-programmed temperature desorption method, was below 0.020 mmol / g-cat. Ammonia temperature-programmed desorption method: He gas was contacted with 150 mg of the catalyst at 500 °C and a flow rate of 20 sccm for 30 minutes; then, a mixture of 5% by volume NH3 and the remainder He was contacted with the catalyst at 50 °C and a flow rate of 20 sccm for 10 minutes; then, He gas was contacted with the catalyst at a flow rate of 20 sccm, during which the temperature was increased at 10 °C / min, and the desorption peak was detected using a thermal conductivity detector.

2. The catalyst according to claim 1, wherein, The catalyst comprises a catalyst component and a support carrying the catalyst component. The catalyst component contains Ru.

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

4. The catalyst according to claim 3, wherein, The carrier contains aluminum oxide.

5. A method for manufacturing the catalyst according to claim 1, comprising: Step a: reacting the catalyst components with the support to obtain the first reactant; as well as Step b involves adding an alkali metal to the first reactant to obtain the second reactant.

6. The method for manufacturing the catalyst according to claim 5, further comprising: Step c involves reducing the second reactant to obtain the third reactant. The desorption peak amount of the third reactant, determined by the ammonia-programmed temperature desorption method, was below 0.020 mmol / g-cat.

7. The method for manufacturing the catalyst according to claim 6, wherein, The process c is carried out at a temperature of 160–360°C.

8. The method for manufacturing the catalyst according to claim 5, wherein, The process a includes the following steps: after the Ru raw material solution is adsorbed onto the carrier, it is dried and then contacted with an alkaline aqueous solution.

9. The method for manufacturing the catalyst according to claim 5, wherein, The alkali metal comprises at least one selected from the group consisting of Na, K, and Li.

10. A method for producing bis(aminomethyl)cyclohexane, comprising: The hydrogenation process involves continuously contacting phenylenediamine with hydrogen in the presence of a catalyst with hydrogenation capabilities to obtain bis(aminomethyl)cyclohexane. The desorption peak amount of the catalyst, determined by the following ammonia-programmed temperature desorption method, was below 0.020 mmol / g-cat. Ammonia temperature-programmed desorption method: He gas was contacted with 150 mg of the catalyst at 500 °C and a flow rate of 20 sccm for 30 minutes; then, a mixture of 5% by volume NH3 and the remainder He was contacted with the catalyst at 50 °C and a flow rate of 20 sccm for 10 minutes; then, He gas was contacted with the catalyst at a flow rate of 20 sccm, during which the temperature was increased at 10 °C / min, and the desorption peak was detected using a thermal conductivity detector.

11. The method for producing bis(aminomethyl)cyclohexane according to claim 10, wherein, The catalyst comprises a catalyst component and a support carrying the catalyst component. The catalyst component contains Ru.

12. The method for producing bis(aminomethyl)cyclohexane according to claim 11, wherein, The catalyst is obtained by method A. The manufacturing method A includes: Step a: reacting the catalyst component with the support to obtain the first reactant; and Step b involves adding an alkali metal to the first reactant to obtain the second reactant.

13. The method for producing bis(aminomethyl)cyclohexane according to claim 12, wherein, The preparation method A further includes step c: reducing the second reactant to obtain the third reactant. The desorption peak amount of the third reactant, determined by the ammonia-programmed temperature desorption method, was below 0.020 mmol / g-cat.

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

15. The method for producing bis(aminomethyl)cyclohexane according to claim 14, wherein, The process a includes the following steps: after the Ru raw material solution is adsorbed onto the carrier, it is dried and then contacted with an alkaline aqueous solution.

16. The method for producing bis(aminomethyl)cyclohexane according to claim 15, wherein, The alkali metal comprises at least one selected from the group consisting of Na, K, and Li.

17. The method for producing bis(aminomethyl)cyclohexane according to claim 16, wherein, The Ru content in the catalyst is 0.1% to 10.0% by mass relative to 100% of the catalyst. The Na content in the catalyst is 0.1 to 10.0% by mass relative to 100% by mass of the catalyst.

18. The method for producing bis(aminomethyl)cyclohexane according to claim 17, wherein, The carrier contains aluminum oxide.

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