JP7653265B2 - Method for producing hexamethylenediamine - Google Patents

Description

The present invention relates to a method for producing hexamethylenediamine.

Hexamethylenediamine is a very useful monomer as a raw material for nylon, and one of the main methods for producing it is the amination reaction of 1,6-hexanediol. In order to produce hexamethylenediamine efficiently, various catalyst systems have been developed to promote this amination reaction.

Patent documents 1 to 5 disclose technologies for converting 1,6-hexanediol to hexamethylenediamine using a solid catalyst. Patent documents 1 and 2 use a Raney nickel catalyst, Patent document 3 uses a cobalt rod catalyst, Patent document 4 uses a metal-supported catalyst with ruthenium as the active species, and Patent document 5 uses an alloy-supported catalyst with rhenium as the catalytically active species.

U.S. Pat. No. 3,215,742 U.S. Pat. No. 3,268,588 U.S. Pat. No. 3,270,059 U.S. Pat. No. 2,754,330 Chinese Patent No. 106,810,454A

In the amination reaction system of 1,6-hexanediol, for example, hexamethyleneimine and polymers (hereinafter referred to as "amination by-products") are produced as by-products. If these amination by-products could be converted to hexamethylenediamine, the hexamethylenediamine yield of the entire reaction system could be improved, and therefore a technology for converting the amination by-products to hexamethylenediamine is required. Furthermore, the key to realizing efficient hexamethylenediamine production is to simultaneously promote the above-mentioned amination by-product conversion reaction and the conversion reaction from 1,6-hexanediol to hexamethylenediamine, in other words, to develop a technology for obtaining hexamethylenediamine from a mixed raw material of 1,6-hexanediol and amination by-products.

In Patent Documents 1, 2, and 3, the reaction is carried out under high pressure of 13 MPa or more in order to allow the low activity unsupported base metal catalyst to function.

On the other hand, Patent Documents 4 and 5 discuss technologies using supported catalysts, but do not discuss the use of amination by-products as raw materials in the reaction to obtain hexamethylenediamine using these catalysts.

The present invention aims to provide a production method that uses a solid catalyst to produce hexamethylenediamine with high selectivity under mild conditions.

As a result of intensive research conducted by the inventors to achieve the object of the present invention, they discovered that by using a specific solid catalyst and a raw material containing at least (i) hexamethyleneimine or (ii) a specific condensation product, hexamethylenediamine can be obtained with high selectivity under mild conditions using an easy-to-handle and stable catalyst.

That is, the present invention is as follows.
[1]
A method for producing hexamethylenediamine, comprising reacting ammonia with a raw material containing one or more elements selected from the following (i) and (ii) in the presence of a solid catalyst comprising a support and an active component containing one or more metal elements selected from the group consisting of elements of Groups 8, 9, 10, and 11 of the periodic table:
(i) hexamethyleneimine (ii) a condensation product of one or more compounds selected from the group consisting of hexamethyleneimine, 6-aminohexanol, hexamethylenediamine, and 1,6-hexanediol [2]
The method for producing hexamethylenediamine according to [1], wherein the raw material further contains one or more compounds selected from the group consisting of 1,6-hexanediol, 6-aminohexanol, and hexamethylenediamine.
[3]
The method for producing hexamethylenediamine according to [1] or [2], comprising: supplying the raw material.
[4]
The method for producing hexamethylenediamine according to any one of [1] to [3], wherein the raw material includes a recovered liquid obtained by purifying the reaction liquid obtained by the reaction.
[5]
The method for producing hexamethylenediamine according to any one of [1] to [4], wherein the active component of the solid catalyst contains two or more kinds of metal elements selected from among elements of Groups 8, 9, 10, and 11.
[6]
The method for producing hexamethylenediamine according to any one of [1] to [5], wherein the active component of the solid catalyst contains one or more metals selected from the platinum group elements and the iron group elements.

According to the present invention, hexamethylenediamine can be selectively produced with high selectivity under mild conditions using a solid catalyst.

The present invention will be described in detail below. Note that the present invention is not limited to the following embodiment (present embodiment), and can be modified in various ways within the scope of the gist of the invention.

[Method for producing hexamethylenediamine]
The method for producing hexamethylenediamine of the present embodiment includes reacting ammonia with a raw material containing one or more elements selected from the following (i) and (ii) in the presence of a catalyst (hereinafter also simply referred to as a "solid catalyst") composed of a support and an active component containing one or more metal elements selected from among elements of Groups 8, 9, 10, and 11 of the periodic table (hereinafter also referred to as a "reaction step"):
(i) hexamethyleneimine (ii) a condensate of one or more compounds selected from the group consisting of hexamethyleneimine, 6-aminohexanol, hexamethylenediamine, and 1,6-hexanediol

In this embodiment, by using a raw material containing at least (i) hexamethyleneimine or (ii) a specific condensate, hexamethylenediamine is obtained with high selectivity under mild conditions using a specific solid catalyst. The reason for the high selectivity is thought to be that, in the presence of a specific solid catalyst, the concentration of the amination by-product in the system is increased, thereby improving the reaction rate of the conversion reaction from the amination by-product to hexamethylenediamine and suppressing the conversion reaction of hexamethylenediamine to the amination by-product, but the reason is not limited to this.

[1] Reaction step The reaction step is a step of reacting a raw material containing (i) hexamethyleneimine or (ii) a specific condensate with ammonia in the presence of a solid catalyst. The reaction step of this embodiment can be carried out by a conventional method such as a batch method, a semi-batch method, or a continuous method. The method for producing hexamethylenediamine of this embodiment may include supplying the raw material described above (hereinafter also referred to as a "supply step"). In addition, the method for producing hexamethylenediamine of this embodiment may include purifying hexamethylenediamine (hereinafter also referred to as a "separation step"). As the method in the separation step, for example, a separation method such as concentration, distillation, extraction, crystallization, recrystallization, or a combination of these separation methods is used.

[2] Raw Material The raw material for hexamethylenediamine in this embodiment includes a raw material containing one or more types selected from the following (i) and (ii).
(i) hexamethyleneimine (ii) a condensate of one or more compounds selected from the group consisting of hexamethyleneimine, 6-aminohexanol, hexamethylenediamine, and 1,6-hexanediol

The above-mentioned (i) hexamethyleneimine and (ii) specific condensation products may be contained in the amination by-products obtained by the amination reaction of 1,6-hexanediol. Condensation products (ii) include polymers produced by elimination of ammonia or water from the above-mentioned compounds.

Examples of additional raw materials used in this embodiment include 1,6-hexanediol, 6-aminohexanol, and hexamethylenediamine. In addition, although not particularly limited, from the viewpoint of excellent yield, it is preferable that the raw material includes a recovered liquid obtained by purifying a reaction liquid obtained from a reaction process using a solid catalyst.

From the viewpoint of excellent reaction rate and safety, the amount of ammonia added is, for example, preferably 2 to 500 equivalents relative to the raw material, more preferably 2 to 150 equivalents, and even more preferably 2 to 100 equivalents.

[3] Solid catalyst In the method for producing hexamethylenediamine of this embodiment, a solid catalyst is used. The solid catalyst includes an active component containing one or more metal elements selected from the elements of Groups 8, 9, 10, and 11 of the periodic table, and a support. These solid catalysts give hexamethylenediamine under mild conditions and with high selectivity.

An active component refers to an element that is newly loaded onto the carrier in the catalyst preparation process. Even if the element originally contained in the carrier and the active component are the same type of element, the part loaded in the catalyst preparation process is considered to be the active component.

The metal element contained as the active component is one or more metal elements selected from the group 8, group 9, group 10, and group 11 elements. The active component is fixed to the catalyst support in the form of a metal cation, a metal complex, nanoparticles, etc., and among these, nanoparticles are preferred from the viewpoint of excellent catalytic activity.

From the viewpoint of excellent selectivity to the target product, hexamethylenediamine, the active ingredient preferably contains two or more metal elements selected from the elements of groups 8, 9, 10, and 11. Among these, from the viewpoint of excellent selectivity, it is more preferable that the active ingredient contains one or more metal elements each of the platinum group elements (ruthenium, rhodium, iridium, palladium, and platinum) and the iron group elements (iron, nickel, and cobalt).

The content of the active component is preferably 0.5 to 50 wt % based on the weight of the carrier, and from the viewpoint of excellent catalytic activity, more preferably 1 to 40 wt %.
The content of metal elements is expressed as the wt% of each metal when the weight of the support is taken as 100 wt%. For example, a catalyst expressed as 10 wt% _M1 * 5 wt% _M2 /support has a weight ratio of _M1 : _M2 :support = 10:5:100.
The content of metal elements and the like in the solid catalyst is measured by a calibration curve method using an X-ray fluorescence analyzer, such as Rigaku's "ZSX Primus II."

As the carrier, for example, any one of metal oxides and carbonaceous carriers can be used. Examples of such carriers include titanium oxide, cerium oxide, lanthanum oxide, zirconium oxide, magnesium oxide, molybdenum oxide, niobium oxide, cobalt oxide, nickel oxide, zinc oxide, calcium oxide, barium oxide, titanium nitride, alumina, silica, zeolite, silica alumina, yttria-stabilized zirconia, ceria-zirconia solid solution, lanthanum oxide-zirconia solid solution, hydroxyapatite, hydrotalcite, organic polymers, and activated carbon. Among these, from the viewpoint of excellent catalytic activity, titanium oxide, lanthanum oxide, cerium oxide, niobium oxide, zirconium oxide, magnesium oxide, alumina, yttria-stabilized zirconia, ceria-zirconia solid solution, and lanthanum oxide-zirconia solid solution are preferred, and titanium oxide, zirconium oxide, alumina, yttria-stabilized zirconia, ceria-zirconia solid solution, and lanthanum oxide-zirconia solid solution are more preferred.

The solid catalyst may be prepared by a known method. The method for supporting the metal on the catalyst carrier is not particularly limited, but examples of the method that can be used include the deposition precipitation method, the impregnation method, and the ion exchange method.

[4] Reduction Treatment Step The method for producing hexamethylenediamine of this embodiment preferably includes a reduction treatment of the solid catalyst before the reaction step (hereinafter also referred to as a "reduction treatment step"). Since the solid catalyst is stable in the air, it can be used in the reaction without pretreatment such as reduction. However, from the viewpoint of excellent catalyst stability, it is preferable to perform a reduction treatment before the reaction and use the solid catalyst in the reaction step without exposing it to oxygen after the reduction treatment. The "reduction treatment" refers to treating the solid catalyst with a reducing agent after catalyst preparation. Examples of the reducing agent in the reduction treatment step include hydrogen, metal hydride, ammonia, urea, and carbon monoxide, but it is preferable to use hydrogen from the viewpoint of excellent catalytic activity.

[5] Reaction Product In the method for producing hexamethylenediamine of the present embodiment, a reaction mixture containing hexamethylenediamine can be obtained by the reaction step.

[6] Reaction Conditions From the viewpoint of excellent separability of the solid catalyst after the reaction, the amount of the solid catalyst used is, for example, preferably 5 to 1,000 parts by mass, more preferably 10 to 750 parts by mass, and even more preferably 20 to 500 parts by mass, per 100 parts by mass of 1,6-hexanediol.

The reaction temperature is, for example, preferably 0 to 300°C, more preferably 50 to 270°C, and even more preferably 120 to 250°C.

From the viewpoint of excellent reaction rate and safety, the total reaction pressure is preferably 10 MPaG or less (e.g., 0.1 to 10.0 MPaG), more preferably 0.5 to 7.5 MPaG, and particularly preferably 0.5 to 5.0 MPaG.

[7] Hydrogen Pressure In the method for producing hexamethylenediamine of the present embodiment, it is preferable to carry out the method in the absence of hydrogen, for example, from the viewpoint of excellent atom efficiency. However, the method can also be carried out in the presence of hydrogen, and the hydrogen pressure is, for example, preferably 0 to 10.0 MPa, more preferably 0 to 5.0 MPa, and even more preferably 0 to 1.0 MPa, in terms of absolute pressure, from the viewpoint of excellent reaction rate and safety.

[8] Solvent In the method for producing hexamethylenediamine according to the present embodiment, for example, a solvent capable of dissolving ammonia molecules in the reaction step is preferably used. Examples of such a solvent include water, hydrocarbon solvents (e.g., toluene, benzene, xylene, pentane, hexane, decane), ether solvents (e.g., tetrahydrofuran, dioxane, dimethoxyethane), alcohol solvents (ethylene glycol, ethanol, methanol, t-butanol), amide solvents (dimethylacetamide, acetamide, dimethylformamide, N-methylpyrrolidone), halogen solvents (dichloroethane, dichloromethane, chloroform, carbon tetrachloride, trifluorotoluene), and the like.

From the viewpoint of excellent absorption efficiency of gaseous ammonia, the amount of solvent (amount of solvent added) is preferably an amount sufficient to dissolve the ammonia in the reaction system, for example, 50 parts by mass or more, preferably 100 to 10,000 parts by mass, and more preferably 100 to 2,500 parts by mass per 100 parts by mass of the raw material.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the examples described below. In the following table, 1,6-hexanediol is abbreviated as HDL, hexamethylenediamine as HMD, hexamethyleneimine as HMI, and 6-aminohexanol as AHL.

(X-ray fluorescence analysis)
Equipment: Rigaku Corporation, X-ray fluorescence analyzer (ZSX Primus II)
Conditions: Calibration curve method: The acac complex, chloride, or nitrate used in the preparation of each catalyst was used as a standard substance and mixed with the carrier used in the preparation of each catalyst to prepare a standard sample. Using the standard sample, fluorescent X-ray analysis was performed to prepare a calibration curve.
The standard samples for creating the calibration curve were prepared so as to have a concentration range exceeding the upper limit of each catalyst described in the examples and comparative examples.

(GC Analysis)
Equipment: Shimadzu GC-2010plus
Column CP-Volamine
Conditions: Injection temperature: 200°C, Detection temperature: 300°C
Carrier gas: nitrogen (column flow rate 70.8 ml/min, SP ratio 50)
Heating rate: 80°C (15°C/min) to 150°C (31 min hold)
(10℃/min)～210℃(held for 3.3 minutes)～
(15℃/min) ~ 290℃ (held for 2.7 minutes)
Internal standard: Anisole

[Example 1]
Catalyst preparation: Platinum chloride and cobalt nitrate hexahydrate were dissolved in a water solvent, and then supported on a zirconia carrier (RC-100, product of Daiichi Kigenso Kagaku Kogyo Co., Ltd.) by impregnation. The obtained powder was calcined in air at 300°C for 2 hours, and then heated at 300°C for 2 hours under a hydrogen flow. The powder was then collected in air to obtain 10wt%Co*2.5wt%Pt/ _ZrO2 . The amount of metal supported on the catalyst was measured by a calibration curve method using a fluorescent X-ray device.

Preparation of recovered liquid: 1.0 g of 10 wt% Co*2.5 wt% Pt/ _ZrO2 was added to a pressure-resistant reactor, and reduction treatment was performed at 180 ° C. under hydrogen 1 MPaG and water solvent. Then, 2.0 g of 1,6-hexanediol and 64 equivalents of ammonia were added to 1,6-hexanediol, and hydrogen was charged to 1.0 MPa at room temperature, and the reaction was performed at 180 ° C. for 2 hours. At this time, the yield of hexamethylenediamine was 30 mol%, and the selectivity was 39 mol%. The reaction liquid of this reaction was distilled to obtain a recovered liquid from which water, hexamethylenediamine, and hexamethyleneimine were removed. Here, it is preferable not to remove hexamethyleneimine from the recovered liquid, but since hexamethyleneimine has a lower boiling point than hexamethylenediamine, it is removed by distillation.

Reaction evaluation: 1.0 g of 10 wt% Co * 2.5 wt% Pt / ZrO ₂ was added to a pressure-resistant reactor, and a reduction treatment process was performed under hydrogen 1 MPaG and water solvent at 180 ° C. Then, 1,6-hexanediol, hexamethyleneimine, and the recovered liquid obtained above were mixed to obtain a raw material having the composition shown in Table 1, and 64.9 equivalents of ammonia relative to the raw material were added to the pressure-resistant reactor, and hydrogen was charged to 1.0 MPa at room temperature, and then the reaction was performed at 180 ° C. for 2 hours. The yield of the product was measured by the internal standard method using gas chromatography. The composition after the reaction obtained is shown in Table 1. In this example, 54 mol% of the raw material components were consumed, and hexamethylenediamine was obtained with a yield of 40 mol% and a selectivity of 74 mol%.

[Example 2]
Preparation of recovered liquid: The reaction liquid of Example 1 was distilled to obtain a recovered liquid from which water, hexamethylenediamine, and hexamethyleneimine had been removed.

Reaction evaluation: 1.0 g of 10 wt% Co * 2.5 wt% Pt / ZrO ₂ was added to a pressure-resistant reactor, and reduction treatment was performed under hydrogen 1 MPaG and water solvent at 180 ° C. Then, 1,6-hexanediol, hexamethyleneimine, and the recovered liquid obtained above were mixed to obtain a raw material having the composition shown in Table 1, and 67.3 equivalents of ammonia relative to the raw material were added to the pressure-resistant reactor, and hydrogen was charged to 1.0 MPa at room temperature, and then the reaction was performed at 180 ° C. for 2 hours. The composition after the reaction obtained is shown in Table 1. In this example, 51 mol % of the raw material components were consumed, and hexamethylenediamine was obtained with a yield of 41 mol % and a selectivity of 80 mol %.

[Example 3]
Catalyst preparation: Ruthenium chloride and cobalt nitrate hexahydrate were dissolved in water, and then the metal was supported on a zirconia support (RC-100, product of Daiichi Kigenso Kagaku Kogyo Co., Ltd.) by ammonia deposition precipitation method. The resulting powder was collected under air to obtain 10 wt% Co * 2.5 wt% Ru/ _ZrO2 .

Preparation of recovered liquid: 1.0 g of 10 wt% Co*2.5 wt% Ru/ _ZrO2 was added to a pressure-resistant reactor, and reduction treatment was performed at 180°C under hydrogen 1 MPaG and water solvent. Then, 2.0 g of 1,6-hexanediol and 32 equivalents of ammonia relative to 1,6-hexanediol were added, and hydrogen was charged to 1.0 MPa at room temperature, and the reaction was performed at 180°C for 2 hours. At this time, the yield of hexamethylenediamine was 25 mol% and the selectivity was 31 mol%. The reaction liquid of this reaction was distilled to obtain a recovered liquid from which water, hexamethylenediamine, and hexamethyleneimine had been removed.

Reaction evaluation: 1.0 g of 10 wt% Co * 2.5 wt% Ru / ZrO ₂ was added to a pressure-resistant reactor, and reduction treatment was performed under hydrogen 1 MPaG and water solvent at 180 ° C. Then, 1,6-hexanediol, hexamethyleneimine, and the recovered liquid obtained above were mixed to obtain a raw material having the composition shown in Table 2, and 32.1 equivalents of ammonia relative to the raw material were added to the pressure-resistant reactor, and hydrogen was filled at room temperature to 1.0 MPa, and the reaction was performed at 180 ° C. for 2 hours. The composition after the reaction obtained is shown in Table 2. In this example, 46 mol% of the raw material components were consumed, and hexamethylenediamine was obtained with a yield of 31 mol% and a selectivity of 67 mol%.

[Example 4]
Preparation of recovered liquid: The reaction liquid of Example 3 was distilled to obtain a recovered liquid from which water, hexamethylenediamine, and hexamethyleneimine had been removed.

Reaction evaluation: 1.0 g of 10 wt% Co * 2.5 wt% Ru / ZrO ₂ was added to a pressure-resistant reactor, and reduction treatment was performed under hydrogen 1 MPaG and water solvent at 180 ° C. Then, 1,6-hexanediol, hexamethyleneimine, and the recovered liquid obtained above were mixed to obtain a raw material having the composition shown in Table 2, and 34.3 equivalents of ammonia relative to the raw material were added to the pressure-resistant reactor, and hydrogen was charged to 1.0 MPa at room temperature, and then the reaction was performed at 180 ° C. for 2 hours. The composition after the reaction obtained is shown in Table 2. In this example, 42 mol % of the raw material components were consumed, and hexamethylenediamine was obtained with a yield of 32 mol % and a selectivity of 76 mol %.

[Example 5]
Preparation of recovered liquid: The reaction liquid of Example 4 was distilled to obtain a recovered liquid from which water, hexamethylenediamine, and hexamethyleneimine had been removed.

Reaction evaluation: 1.0 g of 10 wt% Co*2.5 wt% Ru/ _ZrO2 was added to a pressure-resistant reactor, and reduction treatment was performed at 180 ° C. under hydrogen 1 MPaG and water solvent. Then, 1,6-hexanediol, hexamethyleneimine, and the recovered liquid obtained above were mixed to obtain a raw material having the composition shown in Table 2, and 31.3 equivalents of ammonia relative to the raw material were added to the pressure-resistant reactor, and hydrogen was charged to 1.0 MPa at room temperature, and the reaction was performed at 180 ° C. for 2 hours. The composition of the reaction liquid obtained is shown in Table 2. In this example, 41 mol% of the raw material components were consumed, and hexamethylenediamine was obtained with a yield of 32 mol% and a selectivity of 78 mol%.

[Example 6]
Catalyst preparation: Platinum ammonium nitrate and nickel nitrate hexahydrate were dissolved in a water solvent, and then supported on a 14 wt% Y-stabilized zirconia support (Z-2874, product of Daiichi Kigenso Kagaku Kogyo Co., Ltd.) by impregnation. The resulting powder was calcined in air at 300°C for 2 hours, and then heated in a hydrogen flow at 300°C for 2 hours. The powder was then collected in air to obtain 10 wt% Ni*2.5 wt% Pt/YSZ.

Preparation of recovered liquid: 2.0 g of 10 wt% Ni*2.5 wt% Pt/YSZ was added to a pressure-resistant reactor, and reduction treatment was carried out at 160°C under hydrogen 1 MPaG and water solvent. Then, 4.0 g of 1,6-hexanediol and 8.6 equivalents of ammonia relative to 1,6-hexanediol were added, and hydrogen was charged to 1.0 MPa at room temperature, after which the reaction was carried out at 160°C for 2 hours. At this time, the yield of hexamethylenediamine was 15 mol%, and the selectivity was 21 mol%. The reaction liquid of this reaction was distilled to obtain a recovered liquid from which water, hexamethylenediamine, and hexamethyleneimine had been removed.

Reaction evaluation: 2.0 g of 10 wt% Ni*2.5 wt% Pt/YSZ was added to a pressure reactor, and reduction treatment was performed at 160°C under hydrogen 1 MPaG and water solvent. After that, the raw material of the composition shown in Table 3 obtained by mixing 1,6-hexanediol, hexamethyleneimine, and the recovered liquid obtained above, and 8.6 equivalents of ammonia relative to the raw material were added to the pressure reactor, and after filling with hydrogen to 1.0 MPa at room temperature, the reaction was performed at 160°C for 2 hours. The composition of the reaction liquid obtained is shown in Table 3. In this example, 30 mol% of the raw material components were consumed, and hexamethylenediamine was obtained with a yield of 19 mol% and a selectivity of 63 mol%.

[Example 7]
Preparation of recovered liquid: The reaction liquid of Example 6 was distilled to obtain a recovered liquid from which water, hexamethylenediamine, and hexamethyleneimine had been removed.

Reaction evaluation: 2.0 g of 10 wt% Ni*2.5 wt% Pt/YSZ was added to a pressure reactor, and reduction treatment was performed at 160°C under hydrogen 1 MPaG and water solvent. After that, the raw material of the composition shown in Table 3 obtained by mixing 1,6-hexanediol, hexamethyleneimine, and the recovered liquid obtained above, and 8.4 equivalents of ammonia relative to the raw material were added to the pressure reactor, and after filling with hydrogen to 1.0 MPa at room temperature, the reaction was performed at 160°C for 2 hours. The composition of the reaction liquid obtained is shown in Table 3. In this example, 32 mol% of the raw material components were consumed, and hexamethylenediamine was obtained with a yield of 20 mol% and a selectivity of 63 mol%.

[Example 8]
Preparation of recovered liquid: The reaction liquid of Example 7 was distilled to obtain a recovered liquid from which water, hexamethylenediamine, and hexamethyleneimine had been removed.

Reaction evaluation: 2.0 g of 10 wt% Ni*2.5 wt% Pt/YSZ was added to a pressure reactor, and reduction treatment was performed at 160°C under hydrogen 1 MPaG and water solvent. After that, the raw material of the composition shown in Table 3 obtained by mixing 1,6-hexanediol, hexamethyleneimine, and the recovered liquid obtained above, and 8.6 equivalents of ammonia relative to the raw material were added to the pressure reactor, and after filling with hydrogen to 1.0 MPa at room temperature, the reaction was performed at 160°C for 2 hours. The composition of the reaction liquid obtained is shown in Table 3. In this example, 22 mol% of the raw material components were consumed, and hexamethylenediamine was obtained with a yield of 19 mol% and a selectivity of 86 mol%.

[Example 9]
Catalyst preparation: Iridium chloride and nickel nitrate hexahydrate were dissolved in an aqueous solvent, and then supported on a 14 wt% Y-stabilized zirconia support (Z-2874, product of Daiichi Kigenso Kagaku Kogyo Co., Ltd.) by impregnation. The resulting powder was calcined in air at 300°C for 2 hours, and then heated in a hydrogen flow at 300°C for 2 hours. The powder was then collected in air to obtain 10 wt% Ni*2.5 wt% Ir/YSZ.

Preparation of recovered liquid: 2.0 g of 10 wt% Ni*2.5 wt% Ir/YSZ was added to a pressure-resistant reactor, and reduction treatment was carried out at 180°C under hydrogen 1 MPaG and water solvent. Then, 4.0 g of 1,6-hexanediol and 33.2 equivalents of ammonia relative to 1,6-hexanediol were added, and hydrogen was charged to 1.0 MPa at room temperature, after which the reaction was carried out at 180°C for 2 hours. At this time, the yield of hexamethylenediamine was 20 mol%, and the selectivity was 26 mol%. The reaction liquid of this reaction was distilled to obtain a recovered liquid from which water, hexamethylenediamine, and hexamethyleneimine had been removed.

Reaction evaluation: 2.0 g of 10 wt% Ni*2.5 wt% Ir/YSZ was added to a pressure reactor, and reduction treatment was performed at 180°C under hydrogen 1 MPaG and water solvent. After that, the raw material of the composition shown in Table 4 obtained by mixing 1,6-hexanediol, hexamethyleneimine, and the recovered liquid obtained above, and 33.2 equivalents of ammonia relative to the raw material were added to the pressure reactor, and after filling with hydrogen to 1.0 MPa at room temperature, the reaction was performed at 180°C for 2 hours. The composition of the reaction liquid obtained is shown in Table 4. In this example, 47 mol% of the raw material components were consumed, and hexamethylenediamine was obtained with a yield of 33 mol% and a selectivity of 70 mol%.

[Example 10]
Preparation of recovered liquid: The reaction liquid of Example 9 was distilled to obtain a recovered liquid from which water, hexamethylenediamine, and hexamethyleneimine had been removed.

Reaction evaluation: 2.0 g of 10 wt% Ni*2.5 wt% Ir/YSZ was added to a pressure reactor, and a reduction treatment process was carried out at 180°C under hydrogen at 1 MPaG and water solvent. After that, the raw material of the composition shown in Table 4 obtained by mixing 1,6-hexanediol, hexamethyleneimine, and the recovered liquid obtained above, and 33.6 equivalents of ammonia relative to the raw material were added to the pressure reactor, and after filling with hydrogen at room temperature to 1.0 MPa, the reaction was carried out at 180°C for 2 hours. The composition of the reaction liquid obtained is shown in Table 4. In this example, 46 mol% of the raw material components were consumed, and hexamethylenediamine was obtained with a yield of 36 mol% and a selectivity of 78 mol%.

[Example 11]
Catalyst preparation: Ruthenium chloride and chloroplatinic acid were dissolved in a water solvent, and then supported on a zirconia carrier (RC-100, product of Daiichi Kigenso Kagaku Kogyo Co., Ltd.) by impregnation. The obtained powder was calcined in air at 300°C for 2 hours, and then heated in a hydrogen flow at 300°C for 2 hours. The powder was then collected in air to obtain 5wt%Ru*5wt%Pt/ _ZrO2 .

Preparation of recovered liquid: 2.0 g of 5 wt% Ru*5 wt% Pt/ _ZrO2 was added to a pressure-resistant reactor, and reduction treatment was performed at 180°C under hydrogen 1 MPaG and water solvent. Then, 4.0 g of 1,6-hexanediol and 33.5 equivalents of ammonia relative to 1,6-hexanediol were added, and hydrogen was charged to 1.0 MPa at room temperature, and the reaction was performed at 180°C for 2 hours. At this time, the yield of hexamethylenediamine was 22 mol%, and the selectivity was 28 mol%. The reaction liquid of this reaction was distilled to obtain a recovered liquid from which water, hexamethylenediamine, and hexamethyleneimine had been removed.

Reaction evaluation: 2.0 g of 5 wt% Ru*5 wt% Pt/ _ZrO2 was added to a pressure-resistant reactor, and reduction treatment was performed at 180°C under hydrogen 1 MPaG and water solvent. Then, 1,6-hexanediol, hexamethyleneimine, and the recovered liquid obtained above were mixed to obtain a raw material having the composition shown in Table 5, and 33.1 equivalents of ammonia relative to the raw material were added to the pressure-resistant reactor, and hydrogen was charged to 1.0 MPa at room temperature, and the reaction was performed at 180°C for 4 hours. The composition of the reaction liquid obtained is shown in Table 5. In this example, 40 mol% of the raw material components were consumed, and hexamethylenediamine was obtained with a yield of 25 mol% and a selectivity of 63 mol%.

[Example 12]
Catalyst preparation: Ruthenium chloride and chloroauric acid were dissolved in an aqueous solvent, and then supported on a zirconia carrier (RC-100, manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd.) by impregnation. The resulting powder was calcined in air at 300°C for 2 hours, and then heated in a hydrogen stream at 300°C for 2 hours. The powder was then collected in air to obtain 5wt%Au*5wt%Ru/ _ZrO2 .

Preparation of recovered liquid: 2.0 g of 5 wt% Au*5 wt% Ru/ _ZrO2 was added to a pressure-resistant reactor, and reduction treatment was performed at 180°C under hydrogen 1 MPaG and water solvent. Then, 4.0 g of 1,6-hexanediol and 33.9 equivalents of ammonia relative to 1,6-hexanediol were added, and hydrogen was charged to 1.0 MPa at room temperature, and the reaction was performed at 180°C for 2 hours. At this time, the yield of hexamethylenediamine was 21 mol%, and the selectivity was 28 mol%. The reaction liquid of this reaction was distilled to obtain a recovered liquid from which water, hexamethylenediamine, and hexamethyleneimine had been removed.

Reaction evaluation: 2.0 g of 5 wt% Au*5 wt% Ru/ _ZrO2 was added to a pressure-resistant reactor, and reduction treatment was performed at 180°C under hydrogen 1 MPaG and water solvent. Then, 1,6-hexanediol, hexamethyleneimine, and the recovered liquid obtained above were mixed to obtain a raw material having the composition shown in Table 5, and 34.3 equivalents of ammonia relative to the raw material were added to the pressure-resistant reactor, and hydrogen was charged to 1.0 MPa at room temperature, and the reaction was performed at 180°C for 4 hours. The composition of the reaction liquid obtained is shown in Table 5. In this example, 40 mol% of the raw material components were consumed, and hexamethylenediamine was obtained with a yield of 24 mol% and a selectivity of 60 mol%.

[Example 13]
Catalyst preparation: Ruthenium chloride was dissolved in a water solvent and then supported on a zirconia carrier (RC-100, product of Daiichi Kigenso Kagaku Kogyo Co., Ltd.) by impregnation. The resulting powder was calcined in air at 300°C for 2 hours, and then heated in a hydrogen stream at 300°C for 2 hours. The powder was then collected in air to obtain 5 wt% Ru/ _ZrO2 .

Preparation of recovered liquid: 2.0 g of 5 wt% Ru/ _ZrO2 , 4.0 g of 1,6-hexanediol, and 65.9 equivalents of ammonia relative to 1,6-hexanediol were added to a pressure-resistant reactor, and the reactor was filled with hydrogen to 1.0 MPa at room temperature, after which the reaction was carried out at 180°C for 2 hours. At this time, the yield of hexamethylenediamine was 26 mol%, and the selectivity was 36 mol%. The reaction liquid of this reaction was distilled to obtain a recovered liquid from which water, hexamethylenediamine, and hexamethyleneimine had been removed.

Reaction evaluation: 2.0 g of 5 wt% Ru/ _ZrO2 , 1,6-hexanediol, hexamethyleneimine, and the recovered liquid obtained above were mixed in a pressure-resistant reactor to obtain a raw material having the composition shown in Table 6, and 64.9 equivalents of ammonia relative to the raw material were added to the pressure-resistant reactor, and the reactor was filled with hydrogen to 1.0 MPa at room temperature, after which the reaction was carried out at 180°C for 2 hours. The composition of the reaction liquid obtained is shown in Table 6. In this example, 54 mol% of the raw material components were consumed, and hexamethylenediamine was obtained with a yield of 33 mol% and a selectivity of 61 mol%.

[Example 14]
Catalyst preparation: Nickel nitrate hexahydrate was dissolved in a water solvent, and then supported on a zirconia carrier (Daiichi Kigenso Kagaku Kogyo Co., Ltd. product RC-100) by impregnation. The obtained powder was calcined in air at 300°C for 2 hours, and then heated in a hydrogen flow at 300°C for 2 hours. The powder was then collected in air to obtain 10 wt% Ni/ _ZrO2 .

Preparation of recovered liquid: 2.0 g of 10 wt% Ni/ZrO2 was added to a pressure-resistant reactor, and reduction treatment was carried out at 180°C under hydrogen at 1 MPaG and water as a solvent. Then, 4.0 g of 1,6-hexanediol and 63.1 equivalents of ammonia relative to 1,6-hexanediol were added, and hydrogen was charged to 1.0 MPa at room temperature, after which the reaction was carried out at 180°C for 8 hours. At this time, the yield of hexamethylenediamine was 23 mol%, and the selectivity was 25 mol%. The reaction liquid of this reaction was distilled to obtain a recovered liquid from which water, hexamethylenediamine, and hexamethyleneimine had been removed.

Reaction evaluation: 2.0 g of 10 wt% Ni/ _ZrO2 was added to a pressure-resistant reactor, and reduction treatment was performed at 180°C under hydrogen 1 MPaG and water solvent. Then, 1,6-hexanediol, hexamethyleneimine, and the recovered liquid obtained above were mixed to obtain a raw material having the composition shown in Table 6, and 66.3 equivalents of ammonia relative to the raw material were added to the pressure-resistant reactor, and hydrogen was charged to 1.0 MPa at room temperature, and the reaction was performed at 180°C for 8 hours. The composition of the reaction liquid obtained is shown in Table 6. In this example, 44 mol% of the raw material components were consumed, and hexamethylenediamine was obtained with a yield of 33 mol% and a selectivity of 75 mol%.

[Example 15]
Catalyst preparation: Cobalt nitrate hexahydrate was dissolved in a water solvent, and then impregnated onto a zirconia carrier (RC-100, manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd.). The resulting powder was calcined in air at 300°C for 2 hours, and then heated in a hydrogen stream at 300°C for 2 hours. The powder was then collected in air to obtain 10 wt% Co/ _ZrO2 .

Preparation of recovered liquid: 2.0 g of 10 wt% Co/ _ZrO2 was added to a pressure-resistant reactor, and reduction treatment was performed at 180°C under hydrogen 1 MPaG and water solvent. Then, 4.0 g of 1,6-hexanediol and 63.1 equivalents of ammonia relative to 1,6-hexanediol were added, and hydrogen was charged to 1.0 MPa at room temperature, and the reaction was performed at 180°C for 8 hours. At this time, the yield of hexamethylenediamine was 25 mol% and the selectivity was 28 mol%. The reaction liquid of this reaction was distilled to obtain a recovered liquid from which water, hexamethylenediamine, and hexamethyleneimine had been removed.

Reaction evaluation: 2.0 g of 10 wt% Co/ _ZrO2 was added to a pressure-resistant reactor, and reduction treatment was performed at 180°C under hydrogen 1 MPaG and water solvent. Then, 1,6-hexanediol, hexamethyleneimine, and the recovered liquid obtained above were mixed to obtain a raw material having the composition shown in Table 6, and 65.3 equivalents of ammonia relative to the raw material were added to the pressure-resistant reactor, and hydrogen was charged to 1.0 MPa at room temperature, and the reaction was performed at 180°C for 8 hours. The composition of the reaction liquid obtained is shown in Table 6. In this example, 40 mol% of the raw material components were consumed, and hexamethylenediamine was obtained with a yield of 32 mol% and a selectivity of 80 mol%.

[Example 16]
Catalyst preparation: 10 wt% Co*2.5 wt% Pt/ _ZrO2 was obtained in the same manner as in Example 1.

Reaction evaluation: 2.0 g of 10 wt% Co * 2.5 wt% Pt / ZrO ₂ was added to a pressure-resistant reactor, and reduction treatment was performed at 180 ° C under hydrogen 1 MPaG and water solvent. Then, 1,6-hexanediol, hexamethyleneimine, 6-aminohexanol, and hexamethylenediamine polymer (bishexamethylenetriamine) were mixed to obtain a raw material of the composition shown in Table 7, and 64.9 equivalents of ammonia relative to the raw material were added to the pressure-resistant reactor, and hydrogen was charged to 1.0 MPa at room temperature, and then the reaction was performed at 180 ° C for 2 hours. The composition of the reaction solution obtained is shown in Table 7. In this example, 49 mol % of the raw material components were consumed, and hexamethylenediamine was obtained with a yield of 36 mol % and a selectivity of 73 mol %.

[Example 17]
Catalyst preparation: 10 wt % Ni*2.5 wt % Pt/YSZ was obtained in the same manner as in Example 6.

Reaction evaluation: 2.0 g of 10 wt% Ni*2.5 wt% Pt/YSZ was added to a pressure-resistant reactor, and reduction treatment was performed at 180°C under hydrogen 1 MPaG and water solvent. After that, the raw material of the composition shown in Table 7 obtained by mixing 1,6-hexanediol, hexamethyleneimine, 6-aminohexanol, and hexamethylenediamine polymer (bishexamethylenetriamine) and 34.0 equivalents of ammonia relative to the raw material were added to the pressure-resistant reactor, and hydrogen was charged to 1.0 MPa at room temperature, and the reaction was performed at 180°C for 2 hours. The composition of the reaction liquid obtained is shown in Table 7. In this example, 47 mol% of the raw material components were consumed, and hexamethylenediamine was obtained with a yield of 39 mol% and a selectivity of 83 mol%.

[Example 18]
Catalyst preparation: 10 wt % Ni*2.5 wt % Ir/YSZ was obtained in the same manner as in Example 9.

Reaction evaluation: 2.0 g of 10 wt% Ni*2.5 wt% Ir/YSZ was added to a pressure-resistant reactor, and reduction treatment was performed at 160°C under hydrogen 1 MPaG and water solvent. After that, the raw material of the composition shown in Table 7 obtained by mixing 1,6-hexanediol, hexamethyleneimine, 6-aminohexanol, and hexamethylenediamine polymer (bishexamethylenetriamine) and 9.1 equivalents of ammonia relative to the raw material were added to the pressure-resistant reactor, and hydrogen was charged to 1.0 MPa at room temperature, and the reaction was performed at 160°C for 2 hours. The composition of the reaction liquid obtained is shown in Table 7. In this example, 31 mol% of the raw material components were consumed, and hexamethylenediamine was obtained with a yield of 21 mol% and a selectivity of 68 mol%.

[Example 19]
Catalyst preparation: 5 wt% Ru*5 wt% Pt/ _ZrO2 was obtained in the same manner as in Example 11.

Reaction evaluation: 2.0 g of 5 wt% Ru*5 wt% Pt/ _ZrO2 was added to a pressure-resistant reactor, and reduction treatment was performed at 180 ° C. under hydrogen 1 MPaG and water solvent. Then, 1,6-hexanediol, hexamethyleneimine, 6-aminohexanol, and hexamethylenediamine polymer (bishexamethylenetriamine) were mixed to obtain a raw material having the composition shown in Table 7, and 32.4 equivalents of ammonia relative to the raw material were added to the pressure-resistant reactor, and hydrogen was charged to 1.0 MPa at room temperature, and the reaction was performed at 180 ° C. for 4 hours. The composition of the reaction solution obtained is shown in Table 7. In this example, 43 mol% of the raw material components were consumed, and hexamethylenediamine was obtained with a yield of 26 mol% and a selectivity of 60 mol%.

[Example 20]
Catalyst preparation: 10 wt% Co*2.5 wt% Ru/ _ZrO2 was obtained in the same manner as in Example 3.

Reaction evaluation: 1.0 g of 10 wt% Co * 2.5 wt% Ru / _ZrO2 was added to a pressure-resistant reactor, and reduction treatment was performed at 180 ° C. under hydrogen 1 MPaG and water solvent. Then, hexamethyleneimine and 64.7 equivalents of ammonia relative to hexamethyleneimine were added to the pressure-resistant reactor, and hydrogen was charged to 1.0 MPa at room temperature, and then the reaction was performed at 180 ° C. for 2 hours. The composition of the reaction solution obtained is shown in Table 8. In this example, 70 mol % of the raw material components were consumed, and hexamethylenediamine was obtained with a yield of 45 mol % and a selectivity of 64 mol %.

[Example 21]
Catalyst preparation: 10 wt% Co*2.5 wt% Ru/ _ZrO2 was obtained in the same manner as in Example 3.

Reaction evaluation: 1.0 g of 10 wt% Co*2.5 wt% Ru/ _ZrO2 was added to a pressure-resistant reactor, and reduction treatment was performed at 180°C under hydrogen 1 MPaG and water solvent. Then, a mixed raw material of hexamethyleneimine and 1,6-hexanediol and 66.2 equivalents of ammonia relative to the raw material were added to the pressure-resistant reactor, and after filling with hydrogen at room temperature to 1.0 MPa, a reaction was performed at 180°C for 2 hours. The composition of the reaction solution obtained is shown in Table 8. In this example, 70 mol% of the raw material components were consumed, and hexamethylenediamine was obtained with a yield of 43 mol% and a selectivity of 61 mol%.

[Example 22]
Catalyst preparation: 10 wt% Co*2.5 wt% Ru/ _ZrO2 was obtained in the same manner as in Example 3.

Reaction evaluation: 1.0 g of 10 wt% Co*2.5 wt% Ru/ _ZrO2 was added to a pressure reactor, and reduction treatment was performed at 180°C under hydrogen 1 MPaG and water solvent. Then, a mixed raw material of hexamethyleneimine and 1,6-hexanediol and 67.4 equivalents of ammonia relative to the raw material were added to the pressure reactor, and hydrogen was charged to 1.0 MPa at room temperature, and then the reaction was performed at 180°C for 2 hours. The composition of the reaction solution obtained is shown in Table 8. In this example, 62 mol% of the raw material components were consumed, and hexamethylenediamine was obtained with a yield of 46 mol% and a selectivity of 74 mol%.

[Example 23]
Catalyst preparation: 10 wt% Co*2.5 wt% Ru/ _ZrO2 was obtained in the same manner as in Example 3.

Reaction evaluation: 1.0 g of 10 wt% Co * 2.5 wt% Ru / _ZrO2 was added to a pressure-resistant reactor, and reduction treatment was performed at 160 ° C. under hydrogen 10 MPaG and water solvent. Then, hexamethylenediamine polymer (bishexamethylenetriamine) and 32.5 equivalents of ammonia relative to the hexamethylenediamine polymer were added to the pressure-resistant reactor, and hydrogen was charged to 1.0 MPa at room temperature, and then the reaction was performed at 160 ° C. for 2 hours. The composition of the reaction solution obtained is shown in Table 9. In this example, 20 mol % of the raw material components were consumed, and hexamethylenediamine was obtained with a yield of 13 mol % and a selectivity of 65 mol %.

[Example 24]
Catalyst preparation: 10 wt% Co*2.5 wt% Pt/ _ZrO2 was obtained in the same manner as in Example 1.

Reaction evaluation: 1.0 g of 10 wt% Co * 2.5 wt% Pt / _ZrO2 was added to a pressure-resistant reactor, and reduction treatment was performed at 180 ° C. under hydrogen 1 MPaG and water solvent. Then, hexamethylenediamine polymer (bishexamethylenetriamine) and 34.3 equivalents of ammonia relative to the hexamethylenediamine polymer were added to the pressure-resistant reactor, and hydrogen was charged to 1.0 MPa at room temperature, and then the reaction was performed at 180 ° C. for 2 hours. The composition of the reaction solution obtained is shown in Table 9. In this example, 26 mol% of the raw material components were consumed, and hexamethylenediamine was obtained with a yield of 16 mol% and a selectivity of 62 mol%.

[Example 25]
Catalyst preparation: 10 wt % Ni*2.5 wt % Pt/YSZ was obtained in the same manner as in Example 6.

Reaction evaluation: 1.0 g of 10 wt% Ni*2.5 wt% Pt/YSZ was added to a pressure reactor, and reduction treatment was performed at 180°C under hydrogen 1 MPaG and water solvent. Then, hexamethylenediamine polymer (bishexamethylenetriamine) and 32.5 equivalents of ammonia relative to the hexamethylenediamine polymer were added to the pressure reactor, and after filling with hydrogen to 1.0 MPa at room temperature, the reaction was performed at 180°C for 2 hours. The composition of the reaction solution obtained is shown in Table 9. In this example, 30 mol% of the raw material components were consumed, and hexamethylenediamine was obtained with a yield of 18 mol% and a selectivity of 60 mol%.

Claims (4)

A method for producing hexamethylenediamine, comprising reacting ammonia with a raw material containing one or more of the following (i) and (ii) in the presence of a solid catalyst containing a support and an active component containing one or more metal elements selected from the group consisting of elements of Groups 8, 9, 10, and 11 of the periodic table :
The method for producing said solid catalyst, wherein the active components of said solid catalyst comprise platinum and cobalt and/or nickel .
(i) hexamethyleneimine (ii) a condensate of one or more compounds selected from the group consisting of hexamethyleneimine, 6-aminohexanol, hexamethylenediamine, and 1,6-hexanediol The method for producing hexamethylenediamine according to claim 1, wherein the raw material further contains one or more compounds selected from the group consisting of 1,6-hexanediol, 6-aminohexanol, and hexamethylenediamine. The method for producing hexamethylenediamine according to claim 1 or 2, which includes supplying the raw material. The method for producing hexamethylenediamine according to any one of claims 1 to 3, wherein the raw material includes a recovered liquid obtained by purifying the reaction liquid obtained by the reaction.