JPH07323226A - Amination catalyst and production of aliphatic amine by using the same - Google Patents

Abstract

PURPOSE:To improve the rate and selectivity of reaction for converting an aliphatic alcohol to an aliphatic amine and improve the mechanical strength of a catalyst by constituting an amination catalyst so as to deposit Al and a Ni based metallic component on a carrier and allowing the aliphatic alcohol to react with ammonia in the presence of the catalyst and hydrogen. CONSTITUTION:The amination catalyst is constituted so that Al and the Ni based metallic component are deposited on the carrier (e.g. silica). The adding quantity of Al is 0.05-40wt.% expressed in terms of Al2O3 per total weight of the catalyst. Also the amination catalyst is constituted so that the Ni based metallic component is constituted of Ni alone or Ni and one or more kind of elements selected among group IV-VI metal element in Period Table (e.g. Y, Cr, Re, Fe, Ru, Co, Rh, Pd, Pt, Cu). Further, the depositing quantity of the Ni based metallic component is defined to 5-70wt.% expressed in terms of metal per total weight of the catalyst. The amination catalyst is improved in the rate and selectivity of the reaction at the time of converting the aliphatic alcohol to the aliphatic amine and is improved in the mechanical strength.

Description

Detailed Description of the Invention

[0001]

This invention relates to amination catalysts.
The present invention also relates to a method for selectively producing an aliphatic amine, which is important as a raw material or an intermediate for various organic industrial products such as agricultural chemicals and chelating agents.

[0002]

2. Description of the Related Art As a method for producing an aliphatic amine by reacting an aliphatic alcohol and ammonia in the presence of hydrogen and a catalyst, for example, nickel alone or nickel and copper in which nickel constitutes at least 50% by weight or Alumina having a surface area of 30-50 m ² / g cobalt,
A method of using a catalyst supported on a microporous refractory oxide such as silica or thoria (Japanese Patent Publication No. 64-9048), and α
-A method of using a nickel-rhenium catalyst supported on a carrier such as alumina, silica, silica-alumina, porous diatomaceous earth, diatomaceous earth and silica-titania (JP-B-6).
No. 0-38380), a method using a nickel-cobalt-copper catalyst supported on a carrier such as alumina or silica (US Pat. No. 4,014,933), and the like are known.

[0003]

However, these methods have problems that the selectivity of the aliphatic amine is not sufficient, that there are many by-products and decomposition by-reaction products, and the catalytic activity is low. From the point of view, it was not satisfactory.

The present invention has been made in view of the above problems, and an object thereof is to provide a catalyst having higher selectivity and higher activity than conventional methods. It is to provide a selective manufacturing method.

[0005]

[Means for Solving the Problems] The present inventors have conducted extensive studies on an amination catalyst and a method for producing an aliphatic amine using the amination catalyst. As a result, a catalyst having aluminum and nickel metal components supported on a carrier has been newly developed. The present invention finds a surprisingly novel fact that the rate and selectivity of the reaction for converting an aliphatic alcohol into an aliphatic amine are significantly increased by using this catalyst, and the mechanical strength of the catalyst is also improved. It came to completion.

That is, the present invention is characterized in that an amination catalyst comprising aluminum and a nickel-based metal component supported on a carrier, and an aliphatic alcohol and ammonia are reacted in the presence of hydrogen and this catalyst. It is a method for producing a group amine.

The present invention will be described in more detail below.

The catalyst of the present invention is a catalyst in which aluminum and nickel metal components are supported on a carrier.

The addition amount of aluminum used in the catalyst of the present invention is not particularly limited, but in order to improve the activity and mechanical strength of the catalyst, it is converted into aluminum oxide (Al ₂ O ₃ ) based on the total weight of the catalyst. Represents 0.05-40% by weight
Is preferable, and a range of 0.3 to 20% by weight is more preferable.

The raw material of aluminum is not particularly limited as long as it is usually available, but a compound capable of forming a homogeneous solution when preparing a catalyst is preferable. For example, aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum alkoxide and the like are used.

The nickel-based metal component used in the catalyst of the present invention is a metal component containing nickel and is not particularly limited. However, in order to improve the catalytic activity, nickel alone or nickel and fourth and fifth components are used. A metal component composed of one or more elements selected from the 6-period metal elements is preferable. In this case, it is possible to use a metal component used in a catalyst generally known as a reductive amination catalyst, and in a two-component system, Ni-Pd, Ni-Co, Ni-Rh and Ni-I are used.
r, Ni-Fe, Ni-Ru, Ni-Re, Ni-C
r, Ni-Mo, Ni-Nb, Ni-Zr, Ni-Y,
Ni-Cu, Ni-Zn, etc. can be illustrated. Further, in the three-component system, Ni-Co-Pd, Ni-Co-Rh, Ni
-Co-Fe, Ni-Co-Cu, Ni-Fe-Ru,
Ni-Fe-Cu, Ni-Cr-Cu, Ni-Re-M
O, Ni-Y-Re, Ni-Cu-Zn, etc. can be illustrated. Furthermore, in the four-component system, Ni-Co-Cu-R
u, Ni-Cr-Cu-Ru, Ni-Co-Fe-Re
Etc. can be illustrated. Of these metals used in combination with nickel, Y, Cr, Re, Fe, Ru, Co, R
h, Pd, Pt, and Cu are preferable because they have high catalytic activity. In particular, a catalyst composed of three components of Ni, Co and Cu is preferable because it gives a high aliphatic amine yield.

The amount of the nickel-based metal component supported is not particularly limited, but in order to improve the catalytic activity, it is preferably in the range of 5 to 70% by weight in terms of metal based on the total weight of the catalyst.
The range of 10 to 60% by weight is more preferable.

The content of the nickel metal is not particularly limited, but in order to improve the catalytic activity and the selectivity, the nickel metal content is preferably in the range of 15% by weight or more, and 30% by weight based on the total weight of the metal components. % Or more is more preferable.

Although the composition ratio of the nickel-based metal component is not particularly limited, for example, the nickel-based metal component is Ni,
When composed of three components of Co and Cu, the composition is represented by weight% with respect to the total weight of the catalyst, and each of Ni, Co and Cu is 5 to 35 weight%, 2 to 20 weight%, and 1-1.
A range of 5% by weight is preferred.

The raw material of nickel or the metal element of the 4th, 5th and 6th periods is not particularly limited as long as it is usually available, but nitrates, sulfates, hydrochlorides, formates, acetates, carbonates. Etc. can be used. Further, they may be used in the form of oxides, hydroxides, alkoxides, and various complexes. For example, in the case of nickel, nickel nitrate, nickel sulfate, nickel chloride, nickel formate, nickel acetate, nickel carbonate, nickel oxalate, nickel oxide,
Examples thereof include nickel hydroxide and ethoxide of nickel.

The carrier used in the catalyst of the present invention is not particularly limited, but examples thereof include silica, alumina, zirconia, titania, diatomaceous earth, porous diatomaceous earth, silica-alumina, silica-titania and silica-. One or more substances selected from calcia may be mentioned, of which the silica carrier is particularly preferable. As the carrier, a generally available carrier may be used, or a commercially available carrier may be used by changing its surface area, average pore diameter and the like by modification such as heat treatment or steam treatment in advance.

[0017] When silica is used as the carrier, although the surface area is not particularly limited, the activity of the catalyst, for improved selectivity and mechanical strength, preferably 15~200m ² / g, 41~170m ² / g is more preferred.

The method for preparing the catalyst is not particularly limited, and examples thereof include an impregnation method, a kneading method, a coprecipitation method, and a deposition method. Of these, the impregnation method is preferable.

In the present invention, air calcination of the catalyst precursor does not necessarily have to be carried out at the time of preparing the catalyst.

In the present invention, the reducing conditions of the catalyst are not particularly limited, but in the presence of hydrogen, in order to improve the catalytic activity, 150 to 650 ° C., preferably 170 to 600 ° C.
It is desirable to carry out in the temperature range of 30 minutes to several days.

There is no limitation on the shape of the catalyst of the present invention, and the catalyst may be used in the form of powder as it is or after being molded depending on the reaction mode.
For example, the suspension bed is used in the form of powder or granules, and the fixed bed is used in the form of tablets or beads.

The catalysts of the invention are particularly suitable as catalysts for the hydroamination of aliphatic alcohols.

The raw materials used in the method of the present invention are aliphatic alcohols and ammonia.

The aliphatic alcohol used in the method of the present invention is a linear or branched, saturated or unsaturated aliphatic alcohol having 1 or more carbon atoms and is not particularly limited. For example, methanol, ethanol, 1-propanol, n-butanol, 2-methylpropanol,
Primary alcohols such as octyl alcohol, stearyl alcohol, oleyl alcohol, 2-propanol, 2
-Secondary alcohols such as butanol and 2-methylbutanol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol and the like, polyhydric alcohols such as diethylene glycol and triethylene glycol, and polyoxyether alcohols. , Benzyl alcohol, amino alcohol, and other alcohols having a functional group other than a hydroxyl group in the molecule.

When applied to amino alcohols, the catalyst of the present invention suppresses the formation of by-products, decomposition reaction products and by-reaction products, so that particularly excellent results are obtained. Examples of such amino alcohols include monoethanolamine, diethanolamine, monopropanolamine and the like. For example, when it is used in the production of ethylenediamine using monoethanolamine, it suppresses the formation of by-products such as dimer, cyclized product and their adducts, as well as decomposition reaction products and side reaction products. The yield of ethylenediamine can be increased.

The amount of the catalyst used in the method of the present invention is not particularly limited as long as it is an amount necessary for the reaction to proceed at an industrially significant rate. In order to improve the speed, LHSV (liquid hourly space velocity; total volume of aliphatic alcohol and ammonia per unit catalyst volume) is preferably in the range of 0.2 to 50 hr ^-1 .

Although the molar ratio of the raw materials supplied in the method of the present invention is not particularly limited, the molar ratio of ammonia / aliphatic alcohol is 1 in order to reduce by-products, reaction pressure and the amount of ammonia to be recovered. The range of -60 is preferable, and the range of 2-50 is more preferable.

The supply amount of hydrogen used in the method of the present invention is not particularly limited, but a hydrogen / aliphatic alcohol molar ratio of 0.
The range of 02 to 20 is preferable, and the range of 0.05 to 15 is more preferable.

In the method of the present invention, the reaction temperature is not particularly limited, but is preferably 120 to 270 ° C., more preferably 150 to 250 ° C. in order to improve the reaction rate and suppress the decomposition reaction of the raw materials and products. .

In the method of the present invention, the reaction pressure is not particularly limited, but is usually 50 to 300 kg / cm ^2.
G. When monoethanolamine is used as the aliphatic alcohol, 100-250 kg / cm ² G
Is preferred.

In the method of the present invention, a reaction solvent may be used for the purpose of increasing the reaction yield or lowering the reaction pressure. The reaction solvent can be used if it dissolves the aliphatic alcohol and / or ammonia and becomes homogeneous and is inert to the intended reaction, and water can be mentioned as a preferred example. When water is used for this purpose, it is 30% by weight with respect to the aliphatic alcohol.
Can be used up to.

In the method of the present invention, the reaction method is not particularly limited, but for example, a fixed bed flow system, or a batch, semi-batch or continuous system using a suspension bed is carried out. In the case of a suspension bed, the catalyst is separated from the reaction solution, recovered and reused.

In the method of the present invention, the reaction solution is separated and recovered by distillation. The separated and recovered raw materials are recycled to the reaction zone again if necessary. material,
The product is usually separated by distillation, but the distillation may be carried out continuously or batchwise.

[0034]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, in order to simplify the description, the raw materials and the obtained products are outlined by the following symbols.

EDA; ethylenediamine MEA; monoethanolamine PIP; piperazine N-AEP; N- (2-aminoethyl) piperazine HEP; N- (2-hydroxyethyl) piperazine DETA; diethylenetriamine AEEA; N- (2-aminoethyl) ) Ethanolamine TETA; Triethylenetetramine MeEDA; N-Methylethylenediamine MeMEA; N-Methylmonoethanolamine EtEDA; N-Ethylethylenediamine Also, the selectivity of the reaction products in the tables of the following examples (mo).
1%) and the production rate (% by weight) of the decomposition side reaction product are represented by the following equation.

[0036]

[Equation 1]

[0037]

[Equation 2]

In the examples, the term "decomposition side reaction product" means methylamine, ethylamine, methylethylenediamine, methylmonoethanolamine, ethylethylenediamine, pyrazines and the like.

In the examples, the surface area is ACCUSORB.
2100-01 (micromeritics) specific surface area measuring device, average pore size is PORESIZER
It is measured and calculated using a pore distribution measuring device of 9310 (Micromeritics). Also,
The mechanical strength of the catalyst was measured with a Kiya type hardness meter.

Example 1 37.16 g of nickel (II) nitrate hexahydrate and 2
4.69 g of cobalt (II) nitrate hexahydrate and 7.6
66 g of copper (II) nitrate trihydrate and 18.4 g of aluminum nitrate nonahydrate were dissolved in 35 g of water.
g silica molded carrier (trade name CARiACT-50,
Fuji Silysia Chemical, surface area: 77 m ² / g, average pore diameter: 447 A) was immersed for 1 day. This was evaporated to dryness in an evaporation dish on a water bath and then dried at 120 ° C. overnight. 2 l / m
Baking was carried out at 400 ° C. for 1 hour under in dry air circulation. After firing, 37.16 g nickel (II) nitrate hexahydrate, 24.69 g cobalt (II) nitrate hexahydrate and 7.6 g copper (II) nitrate trihydrate and 18. 4 g of aluminum nitrate nonahydrate was dissolved again in 35 g of water. After evaporating this to dryness in an evaporating dish on a hot water bath, 1
Dry overnight at 20 ° C. Then, it was fired at 400 ° C. for 1 hour under a flow of 2 l / min of dry air. 100cc after firing
Reduction was carried out at 450 ° C. for 4 hours under the flow of hydrogen / min and nitrogen gas of 100 cc / min. After reduction, it was cooled to 200 ° C., and 10 cc / min of air and 100 cc / mi were used.
The stabilization treatment was carried out for 2 hours under the flow of n nitrogen gas.
During firing and reduction, the temperature rising rate was 10 ° C./min.
The obtained catalyst is designated as catalyst A. The supported amount of metal is 1 for Ni
5% by weight, 10% by weight of Co, 4% by weight of Cu, and 5% by weight of Al. As a result of measuring the X-ray diffraction of the catalyst, only the diffraction peak of nickel was confirmed, and nickel crystals were obtained from Scherrer's formula. The child diameter was found to be 8.8 nm. The specific surface area of the catalyst A measured by the BET method was 82 m ² / g.

60 parts of catalyst A were added to a tubular reactor having an inner diameter of 21 mm.
It was filled with cc and the reaction pressure was kept at 200 kg / cm ² G while supplying 6 Nl / hr of hydrogen in a continuous flow reactor. Next, MEA: 134 g / hr, Ammonia: 224
While supplying g / hr with a pump, the temperature was raised to 200 ° C. to carry out the reaction. At this time, the NH ₃ / MEA molar ratio is 6,
The H ₂ / MEA ratio was 0.12 and the LHSV was 8.4 hr ⁻¹ . About 3 hours after the start of the reaction, the reaction solution was analyzed by gas chromatography. Further, unreacted ammonia gas and methylamine and ethylamine of the decomposition reaction product were collected in a water trap and analyzed by gas chromatography.
The reaction results are shown in Table 1.

[0042]

[Table 1]

Example 2 Except that 11.04 g of aluminum nitrate nonahydrate and 68 g of silica carrier were used instead of 18.4 g of aluminum nitrate nonahydrate and 66 g of silica carrier of Example 1. A catalyst B was prepared in the same manner as in Example 1. The amount of metal carried is 15% by weight of Ni, 10% by weight of Co, 4% by weight of Cu, and 3% by weight of Al. In the same manner as in Example 1, 60 cc of catalyst B was charged to carry out a continuous reaction. Table 1 shows the reaction results
It is shown together with.

Example 3 Except that 55.2 g of aluminum nitrate nonahydrate and 56 g of silica carrier were used instead of 18.4 g of aluminum nitrate nonahydrate and 66 g of silica carrier of Example 1. A catalyst C was prepared in the same manner as in Example 1. The amount of metal carried is N
i is 15% by weight, Co is 10% by weight, Cu is 4% by weight,
Al was 15% by weight. In the same manner as in Example 1, 60 cc of catalyst C was charged to carry out a continuous reaction. Table 1 shows the reaction results
It is shown together with.

Comparative Example 1 A catalyst D was prepared in the same manner as in Example 1 except that the aluminum nitrate nonahydrate of Example 1 was not added and 71 g of a silica carrier was used. The amount of metal supported was 15% by weight of Ni, 10% by weight of Co, and 4% by weight of Cu. In the same manner as in Example 1, 60 cc of catalyst D was charged to carry out a continuous reaction. The reaction results are also shown in Table 1. Example 4 30.97 g of nickel (II) nitrate hexahydrate and 0.
9 g of ammonium perrhenate and 11.5 g of aluminum nitrate nonahydrate were dissolved in 37 g of water, and 45.6 g of the same silica molding carrier as in Example 1 was immersed in this for one day. After evaporating this to dryness in an evaporating dish on a hot water bath, 1 at 120 ° C
Dried overnight. Next, under a dry air flow of 2 l / min, 40
Baking at 0 ° C. for 1 hour. After firing, 30.97 g of nickel (II) nitrate hexahydrate, 0.9 g of ammonium perrhenate and 11.5 g of aluminum nitrate nonahydrate were again immersed in 37 g of water. . This was evaporated to dryness in an evaporation dish on a water bath and then dried at 120 ° C. overnight. Then, it was fired at 400 ° C. for 1 hour under a flow of 2 l / min of dry air. After firing, 100 cc / min hydrogen and 100
The mixture was reduced at 450 ° C. for 4 hours under a nitrogen gas flow of cc / min. After reduction, it is cooled to 200 ° C. and 10 cc / mi
Stabilization was carried out for 2 hours under the flow of n air and 100 cc / min of nitrogen gas. During firing and reduction, the temperature rising rate was 10 ° C./min. The obtained catalyst is designated as catalyst E. The amount of metal supported was 20% by weight of Ni, 2% by weight of Re, and 5% by weight of Al. As a result of measuring the X-ray diffraction of the catalyst, only the diffraction peak of nickel was confirmed.
When the nickel crystallite size is calculated from the rrerr formula, it is 1
It was 0.7 nm. The specific surface area of the catalyst E measured by the BET method was 97 m ² / g. Next, in the same manner as in Example 1, 60 cc of the catalyst E was charged and a continuous reaction was carried out. The reaction results are shown in Table 2.

[0046]

[Table 2]

Comparative Example 2 A catalyst F was prepared in the same manner as in Example 4 except that the aluminum nitrate nonahydrate of Example 4 was not added, using 48.8 g of a silica carrier. The supported amount of metal is Ni = 20
%, Re was 2% by weight, and 60 cc of the catalyst F was charged in the same manner as in Example 4 to carry out a continuous reaction. The reaction results are also shown in Table 2.

Example 5 43.36 g of nickel (II) nitrate hexahydrate and 1
0.64 g of copper (II) nitrate trihydrate, 2.69 g of chromium (III) nitrate nonahydrate and 12.88 g of aluminum nitrate nonahydrate were dissolved in 20 g of water. Then, 42.7 g of the same silica molding carrier as used in Example 1 was immersed for 1 day. After evaporating this to dryness in an evaporating dish on a hot water bath, 1 at 120 ° C
Dried overnight. Next, under a dry air flow of 2 l / min, 40
Baking at 0 ° C. for 1 hour. After firing, 43.36 g nickel (II) nitrate hexahydrate and 10.64 g copper nitrate (I
I) trihydrate and 2.69 g of chromium (III) nitrate.
The nonahydrate and 12.88 g of aluminum nitrate nonahydrate were dissolved again in 20 g of water. This was evaporated to dryness in an evaporation dish on a water bath and then dried at 120 ° C. overnight. Then, it was fired at 400 ° C. for 1 hour under a flow of 2 l / min of dry air. After firing, 100 cc / min hydrogen and 100
The mixture was reduced at 450 ° C. for 4 hours under a nitrogen gas flow of cc / min. After reduction, it is cooled to 200 ° C. and 10 cc / mi
Stabilization was carried out for 2 hours under the flow of n air and 100 cc / min of nitrogen gas. During firing and reduction, the temperature rising rate was 10 ° C./min. The obtained catalyst is referred to as catalyst G. The amount of metal supported was 25 wt% for Ni, 8 wt% for Cu, 1 wt% for Cr, and 5 wt% for Al.
As a result of measuring the line diffraction, only the diffraction peak of nickel was confirmed, and the crystallite diameter of nickel was calculated from Scherrer's formula to be 11.1 nm. The specific surface area of the catalyst G measured by the BET method was 95 m.
It was ² / g. Then, as in Example 1, the catalyst G was added to 60
A continuous reaction was carried out with cc filling. The reaction results are also shown in Table 2.

Comparative Example 3 Catalyst H was prepared in the same manner as in Example 6 except that the aluminum nitrate nonahydrate of Example 5 was not added, using 46.2 g of the silica carrier. The amount of metal supported is 25 for Ni
% By weight, 8% by weight of Cu and 1% by weight of Cr, and 60 cc of the catalyst H was charged in the same manner as in Example 5 to carry out a continuous reaction. The reaction results are also shown in Table 2.

Example 6 19.82 g of nickel (II) nitrate hexahydrate and 1
9.75 g of cobalt (II) nitrate hexahydrate and 28.
93 g of iron (III) nitrate nonahydrate, 1.2 g of ruthenium trichloride and 36.79 g of aluminum nitrate nonahydrate were dissolved in 33 g of water, and the same silica molded carrier as in Example 1 was dissolved therein. 82.5 g was immersed for 1 day. This was evaporated to dryness in an evaporation dish on a water bath and then dried at 120 ° C. overnight. Then, it was fired at 400 ° C. for 1 hour under a flow of 2 l / min of dry air. After firing, 100 cc / min hydrogen and 100 c
Reduction was carried out at 450 ° C. for 4 hours under a nitrogen gas flow of c / min. After reduction, cool down to 200 ° C, 10cc / min
The stabilizing treatment was carried out for 2 hours under the flow of air and nitrogen gas of 100 cc / min. During firing and reduction, the temperature rising rate was 10 ° C./min. The obtained catalyst is designated as catalyst I. The supported amount of metal is 4% by weight of Ni, 4% by weight of Co,
Fe 4% by weight, Ru 0.5% by weight, Al 5% by weight
As a result of measuring the X-ray diffraction of the catalyst, only the diffraction peak of nickel was confirmed, and the crystallite diameter of nickel was found to be 11.1 nm from the Scherrer equation.
The specific surface area of this catalyst I was measured by the BET method and found to be 68 m ² / g. Next, Example 1
90 cc of catalyst I as described above, LHSV; 8.4
A continuous reaction was carried out at hr ^-1 . The reaction results are also shown in Table 2.

Comparative Example 4 A catalyst J was prepared in the same manner as in Example 6 except that the aluminum nitrate nonahydrate of Example 6 was not added, using 87.5 g of a silica carrier. The amount of supported metal is 4% by weight for Ni, 4% by weight for Co, 4% by weight for Fe, and 0.5 for Ru.
% By weight, and 90 cc of catalyst J was charged in the same manner as in Example 6 to carry out a continuous reaction. The reaction results are also shown in Table 2.

Example 7 37.16 g of nickel (II) nitrate hexahydrate and 1
8.4 g of aluminum nitrate nonahydrate was dissolved in 73 g of water, and 80 g of the same silica molded carrier as in Example 1 was immersed in this for one day. After evaporating this to dryness in an evaporating dish on a hot water bath, 1
Dry overnight at 20 ° C. Then, it was fired at 400 ° C. for 1 hour under a flow of 2 l / min of dry air. After firing 37.16
g of nickel (II) nitrate hexahydrate and 18.4 g of aluminum nitrate nonahydrate were immersed again in a solution of 73 g of water. After evaporating this to dryness in an evaporating dish on a hot water bath, 1
Dry overnight at 20 ° C. Then, it was fired at 400 ° C. for 1 hour under a flow of 2 l / min of dry air. 100cc after firing
Reduction was carried out at 450 ° C. for 4 hours under the flow of hydrogen / min and nitrogen gas of 100 cc / min. After reduction, it was cooled to 200 ° C., and 10 cc / min of air and 100 cc / mi were used.
The stabilization treatment was carried out for 2 hours under the flow of n nitrogen gas.
During firing and reduction, the temperature rising rate was 10 ° C./min.
The obtained catalyst is designated as catalyst K. The supported amount of metal is 1 for Ni
5% by weight and 5% by weight of Al. As a result of measuring the X-ray diffraction of the catalyst, only the diffraction peak of nickel was confirmed, and S
The crystallite diameter of nickel was 11.2 nm when calculated from the Cherrer equation. Also, regarding catalyst K, BE
The specific surface area measured by the T method was 81 m ² / g. Next, in the same manner as in Example 1, 60 cc of the catalyst K was charged and a continuous reaction was carried out. The reaction results are also shown in Table 2.

Comparative Example 5 A catalyst L was prepared in the same manner as in Example 7 except that the aluminum nitrate nonahydrate of Example 7 was not added and 85 g of the silica carrier was used. The amount of metal supported was 15% by weight of Ni, and 60 cc of the catalyst L was charged in the same manner as in Example 7 to carry out a continuous reaction. The reaction results are also shown in Table 2.

Examples 8 to 12 Catalyst M was prepared in the same manner as in Example 1 except that the silica molded carrier used in Example 1 was replaced by the molded carrier shown in Table 3.
Catalyst N, catalyst O, catalyst P, and catalyst Q were prepared. The loading amount of metal is 15 wt% for Ni, 10 wt% for Co, and 4 for Cu.
% By weight and 5% by weight of Al. In the same manner as in Example 1, 60 cc of each catalyst was charged to carry out a continuous reaction. The reaction results are shown in Table 4.

[0055]

[Table 3]

[0056]

[Table 4]

Comparative Examples 6 to 10 Catalyst R, the same as in Comparative Example 1, except that the silica molded carrier used in Comparative Example 1 was replaced by the molded carrier shown in Table 3.
Catalyst S, catalyst T, catalyst U, and catalyst V were prepared. The loading amount of metal is 15 wt% for Ni, 10 wt% for Co, and 4 for Cu.
% By weight. In the same manner as in Comparative Example 1, 60 cc of each catalyst was charged to carry out a continuous reaction. The reaction results are also shown in Table 4.

Examples 13 to 16 Catalyst W, catalyst X, catalyst Y, and catalyst Z were prepared in the same manner as in Example 1, except that the same silica molded carrier as in Example 1 was used and the composition of the metal component and carrier shown in Table 5. did. Next, in the same manner as in Example 1, 60 cc of each catalyst was filled and a continuous reaction was carried out. The reaction results are shown in Table 6.

[0059]

[Table 5]

[0060]

[Table 6]

Examples 17 to 19 Instead of the silica molded carrier used in Example 1, silica carriers manufactured by Fuji Silysia Chemical Ltd. having different surface areas (trade name: CA) are used.
RiACT-15, surface area; 168 m ² / g, average pore size; 160 A, trade name CARiACT-30, surface area; 109 m ² / g, average pore size; 279 A, trade name
Catalyst A2, catalyst B2, and catalyst C2 were prepared in the same manner as in Example 1 except that CARiACT-80, surface area; 44 m ² / g, average pore size; 639A) were used. The amount of metal supported was 15% by weight of Ni, 10% by weight of Co, 4% by weight of Cu, and 5% by weight of Al. In the same manner as in Example 1, 60 cc of each catalyst was charged to carry out a continuous reaction. The reaction results are also shown in Table 6.

Example 20 Example 1 was applied to a basket attached to the upper part of the 1 l autoclave.
100 g of the same silica molded carrier as above was charged, 350 cc of water was added to the bottom of the autoclave, and the temperature was set to 210 ° C. for 24 hours.
A silica molded carrier having a small surface area (surface area: 30 m ² / g, average pore diameter: 965A) was prepared by steaming. Next, a catalyst D2 was prepared in the same manner as in Example 1 except that the above steam-treated silica molded carrier was used in place of the silica molded carrier used in Example 1. The amount of metal carried is N
i is 15% by weight, Co is 10% by weight, Cu is 4% by weight,
Al was 5% by weight. In the same manner as in Example 1, 60 cc of the catalyst D2 was charged to carry out a continuous reaction. Table 6 shows the reaction results
It is shown together with.

[0063]

INDUSTRIAL APPLICABILITY As described in detail above, according to the present invention, the amination catalyst is not only improved in the activity of converting an aliphatic alcohol to an aliphatic amine and the selectivity, but is also important as an industrial catalyst. Since the mechanical strength is improved,
It is extremely useful industrially.

When monoethanolamine is used as the aliphatic alcohol, the reaction rate for converting monoethanolamine into ethylenediamine is improved, and side reaction products and raw materials and decomposition products of the products are formed. Therefore, ethylenediamine can be obtained with high selectivity and high yield.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B01J 23/86 Z 23/89 Z C07C 209/16 211/03 8517-4H 211/10 // C07B 61/00 300

Claims (13)

[Claims] 1. An amination catalyst comprising an aluminum and nickel metal component supported on a carrier. 2. The amount of aluminum added is expressed in terms of aluminum oxide (Al ₂ O ₃ ) based on the total weight of the catalyst, and is 0.05.
The amination catalyst according to claim 1, which is about 40% by weight. 3. The amination catalyst according to claim 1 or 2, wherein the nickel-based metal component comprises nickel alone or nickel and one or more elements selected from metal elements of the fourth, fifth and sixth periods. . 4. The metal element of the fourth, fifth and sixth periods is Y, C
r, Re, Fe, Ru, Co, Rh, Pd, Pt, Cu
An amination catalyst according to claim 3 comprising 5. The amination catalyst according to claim 1, wherein the amount of the nickel-based metal component supported is 5 to 70% by weight in terms of metal based on the total weight of the catalyst. 6. The amination catalyst according to claim 1, wherein the content of nickel metal is 15% by weight or more based on the total weight of the metal component containing nickel. 7. The carrier is one or more substances selected from silica, alumina, zirconia, titania, diatomaceous earth, porous diatomaceous earth, silica-alumina, silica-titania and silica-calcia. The amination catalyst according to any one of items 1 to 4. 8. The amination catalyst according to claim 7, wherein the carrier is silica. 9. The nickel-based metal component is Ni, Co, Cu.
9. The amination catalyst according to claim 8, which comprises the following three components: 10. A method for producing an aliphatic amine, which comprises reacting an aliphatic alcohol with ammonia in the presence of hydrogen and the amination catalyst according to any one of claims 1 to 9. 11. The method for producing an aliphatic amine according to claim 10, wherein the molar ratio of ammonia, hydrogen and aliphatic alcohol is 1 to 60: 0.02 to 20: 1. 12. The method for producing an aliphatic amine according to claim 10, wherein the reaction temperature is 120 to 270 ° C. and the pressure is 50 to 300 kg / cm ² G. 13. The method for producing ethylenediamine according to claim 10, wherein the aliphatic alcohol is monoethanolamine.