JPH02234A - Production of n-substituted amine - Google Patents

Abstract

PURPOSE:To obtain the title compound in high catalytic activity in high selectivity and in high yield by reacting an alcohol or aldehyde with ammonia or an amine in the presence of a catalyst comprising four components including copper. CONSTITUTION:An alcohol or aldehyde is reacted with ammonia or a primary or secondary amine in the presence of a catalyst containing (A) copper, (B) one or more selected from Cr, Mn, Fe, Co, Ni and Zn of transition metal elements of period 4, (C) a platinum metal element (Pt, Pd, Ru or Rh) and (D) one or more selected from Al, W and Mo in the molar ratio of A:B=(10:90)-(99:1), especially (50:50)-(99:1), (A+B):C=(1:0.001)-(1:0.1) and B:D=(1:0.01)-(1:1) under atmospheric pressure-100 atmospheric pressure (gauge pressure) at 150-250 deg.C to give a N-substituted amine.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for producing a corresponding N-substituted amine by reacting an alcohol or an aldehyde with ammonia or a primary amine or a secondary amine. It is.

The amine produced by the present invention is an industrially important substance as an intermediate for rust preventives, surfactants, bactericidal agents, textile dyeing aids, softeners, and the like.

[Conventional technology]

Conventionally, there are known methods for producing corresponding amines by reacting alcohols or aldehydes with ammonia or primary amines or secondary amines. It has been difficult to selectively obtain specific amines.

Regarding the method of producing the corresponding amine from alcohol and amine, see JP-A-52-19604 (copper chromite catalyst, cobalt catalyst) and JP-A-5359602 (copper-chromite catalyst).
molybdenum, copper-tungsten catalyst), U.S. Patent No. 3.
223.734 (Raney nickel catalyst, copper chromite catalyst), German Patent Application No. 1.493.781 (
There are reports such as cobalt catalyst with carrier) and Japanese Patent Publication No. 57-55704 (copper-nickel catalyst). However, these catalysts do not have sufficient activity or selectivity, and because the amount of catalyst is large, the yield of the target amine is also low. As a method developed to solve these problems,
5, JP-A-62-149646, JP-A-62-149
647, and the method described in JP-A-62-149648. These methods use a copper-nickel-group VIII platinum group element catalyst to obtain the desired amine in high yield.

That is, by adding a small amount of Group VIII platinum group element to a copper-nickel catalyst, which conventionally had insufficient activity and selectivity, the activity and selectivity were improved, and the target amine was obtained in high yield. be.

[Problem that the invention seeks to solve]

However, the method using this catalyst is not necessarily satisfactory in terms of the durability of the catalyst. In other words, compared to other general methods, both activity and selectivity are good, and even if this catalyst is recovered and used several thousand times, there is almost no decrease in activity, but a deterioration in selectivity is observed. Therefore, when considering industrialization, it is desired to further improve the durability of the catalyst from the viewpoint of yield and quality of the N-substituted amine produced.

[Means for solving problems]

Therefore, the present inventors developed a copper-4th period transition metal element-8th period transition metal element, which has better activity and selectivity than other general methods.
As a result of intensive research into increasing the durability of catalytic reactions by adding a small amount of a fourth component metal element to a metal platinum group element catalyst, we found that:
Aluminum, tungsten as the fourth component metal element,
It has been found that when a small amount of molybdenum is added to a copper-4th period transition metal element-8th group platinum group element catalyst, the activity and selectivity are maintained almost the same and the durability is improved. At this time,
As the 4th period transition metal elements, chromium, manganese, iron, cobalt, nickel and zinc are effective, and the 8th period transition metal elements are effective.
As the platinum group elements, platinum, palladium, ruthenium and rhodium were effective.

As a result, by adding aluminum, tungsten, and molybdenum as fourth component metal elements to the copper-fourth period transition metal element-group eight platinum group element catalyst, copper-fourth period transition metal element-group eight platinum group element was added. A high-performance amination catalyst has been found that has activity selectivity equivalent to that of a group element catalyst and exhibits higher durability than a copper-4th period transition metal element-8th group platinum group element catalyst.

That is, in the present invention, alcohol or aldehyde is reacted with ammonia, primary amine, or secondary amine, and N
- When producing a substituted amine, a copper-fourth period transition metal element-a group eight platinum group element-a fourth component metal element catalyst is used, and in the presence of this catalyst, the water produced by the reaction is continuously or Atmospheric pressure or 1
150℃ to 250℃ below 00atm (gauge pressure)
This is a method for producing N-substituted amines in high yield, characterized by carrying out the reaction at a temperature of .

In the method of the present invention, since the catalyst is highly active, the reaction conditions are mild, and the process can be carried out with light equipment.
The amount of catalyst used is very small and the reaction can be completed in a short time.

The catalyst of the present invention exhibits several times higher activity than the copper-nickel catalyst described in Japanese Patent Publication No. 57-55704, has extremely excellent reaction selectivity, and has performance superior to that of the known copper-nickel-Platinum Group VIII catalyst. It is.

Furthermore, the copper-4th period transition metal element-8th group platinum group element-4th component metal element catalyst of the present invention has excellent durability and maintains catalytic activity and selectivity even after being collected and reused several to thousands of times. It has the characteristic that there is almost no decrease in

Since the catalyst of the present invention exhibits extremely high activity and selectivity compared to conventional catalysts, it is possible to carry out reactions at low temperatures and under normal pressure, reducing the amount of catalyst required and improving reaction selectivity. By doing so, it becomes possible to produce the corresponding N-substituted amine in high yield even from branched aliphatic alcohols or aldehydes, which could not be obtained in high yield using conventional techniques. Furthermore, it is possible to produce corresponding N-substituted amines in extremely high yields even from polyhydric alcohols which are difficult to produce in terms of high yield and quality because they tend to cause side reactions during boat fishing.

The catalyst used in the present invention includes copper, a fourth period transition metal element, a group VIII platinum group element (hereinafter abbreviated as platinum group element), and a fourth period transition metal element.
A component metal element (hereinafter abbreviated as the fourth component) is essential,
In the catalyst metal composition used, the ratio of copper, the fourth period transition metal element, the platinum group element, and the fourth component can be arbitrarily set, but the molar ratio of the metal atoms of copper and the fourth period transition metal element is 10. :90 to 99:1 is preferable, and 50:50 to 99:1 is more preferable. The amount of the platinum group element added to the total amount of copper and the fourth period transition metal element is preferably in the range of 0.001 to 0.1 (molar ratio), more preferably in the range of 0.001 to 0.05. Furthermore, the molar ratio of the fourth period transition metal element to the fourth component is preferably 1:0.01 to 1:1, more preferably 1:0.05 to 1:1.

The fourth period transition metal elements particularly suitable for this reaction are chromium,
These are manganese, iron, cobalt, nickel, and zinc, the platinum group elements are platinum, palladium, ruthenium, and rhodium, and the fourth component is aluminum, tungsten, and molybdenum.

The catalyst metal composition must include four components: copper, a fourth period transition metal element, a platinum group element, and a fourth component, but the catalyst suitable for the present invention can be selected from various forms.

That is, in the present invention, when the four components of copper, the fourth period transition metal element, the platinum group element, and the fourth component are present in the reaction system as a catalyst composition, the effect due to the interaction between these four components is exhibited for the first time. This four-component composition has an essential catalytic function, and in the reaction, catalytic activity is first expressed by the reduction operation of each metal component in a hydrogen atmosphere.

Therefore, the difference in the form of the metal before the reduction operation and the state in the system after the reduction operation is not particularly limited in the present invention. Any form may be used as long as the interaction between the fourth period transition metal element, the platinum group element, and the fourth component is exhibited.

Therefore, the forms of metals that are compatible with the method of the present invention include: 1) Forms that can be dispersed in the reaction medium, such as these metals, their oxides or hydroxides, and mixtures thereof; or 2) a mixture of copper, a fourth period transition metal element, a platinum group element, and a fourth component supported on a suitable carrier, or a mixture of copper, a fourth period transition metal element, a platinum group element, and a fourth component; 3) in which the four components are uniformly supported on the same carrier and dispersed in the reaction medium; 3) or stabilized by an aliphatic carboxylate of these metals or a suitable ligand; 4) Those in the form of a metal colloid in the reaction medium and become a homogeneous system like a string, 4) Those in the form of a dispersion in the reaction medium such as l) to 2), and 3) or in a dispersed form before hydrogen reduction.
Any case may be used, such as one that becomes uniform after hydrogen reduction, and the interaction between the four components is expressed by the reduction operation of the four component metals that are the essence of the present invention. Bye.

In the method of the present invention, a more preferable form of catalyst is to prepare these four component metals on a suitable carrier from the viewpoints of stabilization of the catalyst metal, that is, immobilization of the active surface, and durability against catalyst poisoning substances. It is better to have it supported uniformly.

Copper of the present invention, fourth period transition metal element, platinum group element, fourth period transition metal element,
When supporting the four component metals on a carrier, compatible carriers include those commonly used as catalyst carriers,
For example, alumina, silica alumina, diatom, silica,
Activated carbon, natural and artificial zeolites, etc. can be used. Although the amount of catalyst metal supported on the carrier can be arbitrarily determined, it is usually preferably in the range of 5 to 70%.

Various methods can be selected for supporting these four component metals on the carrier surface. In this case, the forms of the catalyst raw metal include copper, fourth period transition metal elements, platinum group elements, and fourth period transition metal elements.
Oxides and hydroxides of the components or their various metal salts can be used.

For example, copper, a fourth period transition metal element, a platinum group element, a chloride, a sulfate, a nitrate, an acetate, an aliphatic carboxylate, or a metal complex thereof, such as copper, a platinum group element, and a fourth component.
Periodic transition metal elements, acetylacetone complexes and dimethylglyoxime complexes of platinum group elements, and carbonyl complexes, amine complexes, phosphine complexes, etc. of platinum group elements can also be used. When producing a catalyst using these metal raw material species by a method of supporting them on a carrier, for example,
The carrier is thoroughly impregnated with a solution of copper, a fourth period transition metal element, a platinum group element, and a suitable salt of the fourth component, and then dried.
A firing method (impregnation method) is used, or after thoroughly mixing the carrier and an aqueous solution of an appropriate salt of copper, a fourth period transition metal element, or a platinum group element, an alkaline aqueous solution such as sodium carbonate, sodium hydroxide, or aqueous ammonia is added. Alternatively, an aqueous solution of an appropriate salt of copper, a fourth period transition metal element, or a platinum group element and an alkaline aqueous solution such as sodium carbonate, sodium hydroxide, or aqueous ammonia are added to the aqueous slurry of the carrier. , the pH of the slurry is constant (e.g. p) I=7
the metal salt is precipitated on the carrier, dried and calcined to prepare a copper-fourth period transition metal element-platinum group element catalyst, and then the resulting three-component catalyst After putting it into an aqueous solution of the fourth component metal salt and thoroughly impregnating it,
There are two methods: drying and firing (a combination of coprecipitation method and impregnation method), ion exchange method with hydrogen or metal contained in zeolite (ion exchange method), and method of ion exchange with hydrogen or metal contained in zeolite.
A method in which a carrier containing only a periodic transition metal element, a platinum group element, and a fourth component, or an oxide, etc., is prepared in advance, and then they are thoroughly mixed, dried, and fired (kneading method)
Any conventionally known method may be used.

In the case of the coprecipitation method, after the metal is deposited, wash thoroughly with water and
After drying at around 0.degree. C., it is calcined at 300.degree. C. to 700.degree. C. to obtain a catalyst.

In addition, in such a method, only copper or only copper and a fourth period transition metal element are supported on a carrier, and before being subjected to the reaction, a carrier of a platinum group element or a fourth component, or an aliphatic carboxylic acid is supported. It is also effective to add a salt or a complex to form a composite of copper, the fourth period transition metal element, the platinum group element, and the fourth component in a hydrogen atmosphere in a reaction medium.

More preferably, the catalyst is in a form in which the four components are uniformly supported on the same carrier.

The four components, copper, the fourth period transition metal element, the platinum group element, and the fourth component, are essentially essential to the present invention.

The alcohol or aldehyde which is the raw material used in the present invention is a straight or branched saturated or unsaturated aliphatic alcohol or aldehyde having 8 to 36 carbon atoms, such as octyl alcohol, lauryl alcohol, myristyl alcohol, Alcohols with branched chains such as stearylalconobehenylalconopeoleyl alcohol, mixed alcohols thereof, Ziegler alcohol obtained by the Ziegler method, oxo alcohol and gelpair alcohol obtained by the oxo method, and are used as aldehydes. Examples include lauryl aldehyde, oxo aldehyde, and other aldehydes corresponding to the above-mentioned alcohols.

Also, various polyhydric alcohols can be used.

For example, 1.3-butanediol, 1゜4-butanediol, 1.5-bentanediol, 1.6-hexanediol, 1.9-nonanediol, etc., and polyhydric compounds such as diethylene glycol and triethylene glycol. Alcohol is an example.

Other alcohols include aromatic alcohols such as benzyl alcohol and phenethyl alcohol, polyoxyether alcohols such as ethylene oxide or propylene oxide adducts of aliphatic alcohols, and amino alcohols such as ethanolamine and jetanolamine.

The alcohol or aldehyde is particularly an aliphatic alcohol or aldehyde selected from saturated or unsaturated straight or branched aliphatic alcohols or aldehydes having 8 to 36 carbon atoms, and aliphatic glycols having 2 to 12 carbon atoms. is preferred. The amine to be reacted with these alcohols or aldehydes may be either gaseous or liquid at room temperature;
or secondary amines, such as monomethylamine, ethylamine, dodecylamine, stearylamine,
Examples include oleylamine, behenylamine, dimethylamine, diethylamine, didodecylamine, distearylamine, dioleylamine, diethylamine, and the like.

In the present invention, it is an essential condition that the water produced by the reaction between alcohol or aldehyde and amine be taken out of the reaction system, and the catalytic performance of the present invention can be fully exhibited if the produced water is not taken out of the system. Can not. That is, the catalyst activity and selectivity are reduced, and N-substituted amines cannot be easily obtained in high yield. For example, if dimethylamine is used as the amine and the reaction is carried out without removing the water produced,
Distillation alone produces many by-products that are difficult to separate, such as monoalkylmethylamines, and also produces large amounts of high-boiling substances such as aldehyde condensates, resulting in a decrease in the yield of the desired N-substituted amine. It ends up.

Removal of water may be carried out intermittently or continuously during the reaction, as long as the produced water does not exist in the reaction system for a long time and is removed appropriately. It is desirable to remove it. Specifically, a common method is to introduce an appropriate amount of hydrogen gas into the reaction system, and distill out the produced water and excess amine (if gaseous amine is used) together with the hydrogen gas. Hydrogen gas can also be recycled by condensing and separating water. It is also possible to add a suitable solvent to the reaction system and remove the produced water by azeotroping with the solvent.

In the method of the present invention, a catalyst previously reduced with hydrogen gas may be used, but the catalyst before reduction is placed in a reactor together with the alcohol or aldehyde as a reaction raw material,
Reduction is carried out by raising the temperature to the reaction temperature while introducing hydrogen gas. That is, the copper-fourth period transition metal element-platinum group element-fourth component catalyst of the present invention has a remarkable feature in that it has a low reduction temperature and can be reduced during the heating process up to the reaction temperature.

Next, preferred embodiments of the method of the present invention will be briefly described.

A reaction equipped with a tube for introducing hydrogen and amine, and a condenser and separator for condensing and separating the water produced in the reaction, excess amine (if gaseous amine is used), and distilled oil. A container is charged with alcohol or aldehyde as raw materials and a catalyst. The catalyst can be charged in any amount, but since the catalyst of the present invention has high activity, it is usually 0.1 to 2% by weight based on the alcohol or aldehyde charged.
is within the range of After replacing the inside of the system with nitrogen gas, temperature rise is started without introducing hydrogen.

The reaction temperature is usually 150 to 250°C, but the temperature can be outside this range depending on the type of reaction. During this temperature rise, the catalyst is reduced and becomes an active catalyst. After reaching a predetermined temperature, ammonia or amine is introduced to start the reaction. The amine may be either gaseous or liquid, and its introduction into the system may be continuous, intermittent, or batchwise (in the case of liquid amine). During the reaction, the water produced is discharged from the reaction system together with gaseous substances (hydrogen and excess gaseous amine when using gaseous amine) and a small amount of oily substance, and passes through a condenser and a separator. Separated from oil. The separated oil is returned to the reactor. In addition, as a result of analyzing gaseous substances (hydrogen and excess gaseous amine when using gaseous amine), it was found that most of these gaseous substances contain by-products (e.g., hydrocarbons, due to disproportionation of the raw amine). It has been proven that the catalyst of the present invention has high selectivity, and by using a circulator, these gaseous substances can be reused without a special purification process. I understand. After the reaction is completed, the reactants and the catalyst are separated by distilling the reactants directly or by filtering them. The N-substituted amine obtained by the filtration operation can be obtained in extremely pure form by distillation.

〔Example〕

The present invention will be explained in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited to these Examples.

Example 1 and Comparative Example 1 A four-way catalyst of copper-fourth period transition metal element-platinum group element-fourth component supported on synthetic zeolite was prepared as follows.

Synthetic zeolite was charged into a 1j2 flask, and then copper nitrate, nickel nitrate, palladium chloride, and aluminum nitrate were mixed in the molar ratio of each metal atom: Cu:Ni:Pd:A
A solution dissolved in water was added so that l = 4:1:0.05:0.05, and the temperature was raised while stirring.

A 10% Na, CD, and aqueous solution was gradually added dropwise at 90°C.

After aging for 1 hour, the precipitate was filtered, washed with water, and incubated at 80°C for 1 hour.
After drying for 0 hours, it was fired at 400°C for 3 hours. The amount of the obtained metal oxide supported on the support was 50%.

Next, using this catalyst, alcohol and dimethylamine were reacted. Furthermore, as a comparative example, a reaction was carried out using a copper-nickel-palladium catalyst prepared in the same manner.

11 equipped with a condenser and separator to separate produced water
600 g of lauryl alcohol and 1.5 g of the above catalyst (0.25 wt% based on raw material alcohol) were placed in a flask.
While stirring, the inside of the system was replaced with nitrogen, and temperature elevation was started. 1
When the temperature reaches 00°C, add hydrogen gas to 10j7 using a flow meter.
The mixture was blown into the system at a flow rate of /hr and the temperature was raised to 200°C.

40j of mixed gas of dimethylamine and hydrogen at this temperature!
The reaction system was blown into the reaction system at a flow rate of /hr, and the reaction was monitored using the amine value and gas chromatography.

The reaction results are shown in Table 1, including the results of the reaction using the 10th and 20th recovered catalysts.

As a result, the Cu/fourth period transition metal element (Ni
) / platinum group element (Pd) / fourth component (AI) The four-component catalyst system has high activity and high selectivity, similar to the Cu / Ni / platinum group element (Pd) three-component catalyst system (Comparative Example 1). It was also found that the durability was greatly improved.

Table 1 Examples 2 to 4 and Comparative Example 2 Regarding catalysts consisting of copper, a fourth period transition metal element, a platinum group element, and a fourth component, the fourth period transition in the catalyst was caused by the reaction of stearyl alcohol and monomethylamine. The metal element is Cr, the platinum group element is Ru, and the fourth component is Al5WS.
The reaction activity was examined by replacing it with Mo. These quaternary catalysts were prepared using an impregnation method. In addition, as a comparative example, Cu/Cr
A similar reaction was carried out using a /Ru catalyst.

Table 2 shows the results of the reaction using the 10th recovered catalyst.
Shown below.

As a result, when producing distearyl monomethyl tertiary amine through the reaction of stearyl alcohol and monomethyl amine, Al5W, M
The Cu/Cr/Ru/fourth component catalyst using o
It was found that the catalyst exhibited activity and selectivity equivalent to or higher than those of the Cr/Ru catalyst (Comparative Example 2), and the durability was significantly improved.

Regarding a catalyst consisting of copper, a fourth period transition metal element, a platinum group element, and a fourth component, by reaction with dodecyl alcohol and ammonia, the fourth period transition metal element in the catalyst is changed to Zn, the platinum group element is changed to pt, The fourth component is AI, W SM
The reaction activity was examined by changing the type of These quaternary catalysts were prepared in the same manner as in Example 2. Further, as a comparative example, a similar reaction was conducted using a Cu/2n/Pt catalyst.

Table 3 shows the results of the reaction using the 10th recovered catalyst.
Shown below.

As a result, when tridodecylamine is produced by the reaction of dodecyl alcohol and ammonia, AI and WSM are used as the fourth component as a catalyst.

The Cu/Zn/Pt/fourth component catalyst using Cu/Z
Activity equivalent to or higher than n/Pt catalyst (Comparative Example 3),
It was found that it showed selectivity while improving durability.

Example 8 and Comparative Example 4 Lauryl alcohol and ammonia were reacted using a Cu/Co/Pd/fourth component (AI) catalyst.

In this reaction, the ammonia introduction flow rate was set to 301 /
The reaction was monitored using the amine value and gas chromatography. As a comparative example, Cu/Co
A similar reaction was carried out using a /Pd catalyst system.

Table 4 shows the results of the reaction using the 10th recovered catalyst.
Shown below.

As a result, in this catalyst system, the reaction between lauryl alcohol and ammonia produces Cu/Co/Pd/fourth component (AI).
It was found that by using a catalyst, a secondary amine could be produced with higher durability than the Cu/Co/Pd catalyst system (Comparative Example 4).

The reaction between alcohol and stearylamine was carried out. In this reaction, stearylamine was introduced in liquid form into the reaction system all at once, and the reaction was monitored using the amine value and gas chromatography. As a comparative example, a similar reaction was conducted using a Cu/Mn/Ru catalyst system.

Table 5 shows the results of the reaction using the 10th recovered catalyst.
Shown below.

As a result, with this catalyst system, the reaction between lauryl alcohol and stearylamine can proceed with extremely high activity and high selectivity, similar to the Cu/Mn/Ru catalyst system (Comparative Example 5). Cu/Mn/Ru catalyst system (
It was found that the corresponding amine could be produced with higher durability than Comparative Example 5).

Table Cu/Co/Pd; %Relative supported amount Cu/Co/Pd catalyst system; Molar supported amount 3/110.03 40% 3/110.0310.5 40% Reaction conditions; Alcohol; Lauryl alcohol Ammonia amine introduction rate: 30j! /hr Reaction temperature: 180°C Catalyst addition amount: 0.25% based on alcohol Example 9 and Comparative Example 5 Lauri table Cu/Mn/Ru using Cu/Mn/Ru/fourth component (W) catalyst: mole Specific supported amount Cu/Mn/Ru/W; molar specific supported amount 4/110.1 20% 4/110.110.3 20% Reaction conditions; Alcohol; lauryl alcohol amine; stearyl amine alcohol/amine = 1 Reaction temperature: 180°C Catalyst addition amount: 1.0% based on alcohol Examples 10 to 18 Using the catalyst of the present invention, the effect of the reaction of various alcohols or aldehydes with dimethylamine on the corresponding tertiary amine synthesis was investigated. did. Note that the catalyst was prepared using an impregnation method.

Table 6 shows the results of the reaction using the 10th recovered catalyst.
Shown below.

From the above results, it was found that using the catalyst of the present invention, even in reactions with secondary amines using branched alcohols, polyhydric alcohols (glycols), and aldehydes as starting materials, extremely high activity, high selectivity, and high durability were achieved. It has been found that tertiary amines can be produced in high yield using this method.

Normally, when such branched-chain alcohols, polyhydric alcohols, or aldehydes are used as starting materials, side reactions such as their decomposition and condensation generally increase, but the catalyst composition of the present invention It has been proven that the catalyst consisting of the following is an extremely excellent catalyst that solves these problems.

Example 14 and Comparative Example 6 Lauryl alcohol and stearylamine were reacted using a Cu/Fe/Pd/fourth component (MO) catalyst.

In this reaction, stearylamine was introduced in liquid form into the reaction system all at once, and the reaction was monitored using the amine value and gas chromatography. As a comparative example, a similar reaction was conducted using a cu/Fe/Pd catalyst system. The reaction pressure was 50 atm (
Reaction conditions: Alcohol; lauryl alcohol amine; stearyl amine Alcohol/amine = 1 Reaction temperature: 160°C Catalyst addition amount: 2 vs. alcohol 1.0% Example 15 and Comparative Example 7 Next, Cu /Mn/Rh/Mo catalyst was used to react behenyl alcohol with stearylamine.

In this reaction, stearylamine was introduced in liquid form into the reaction system all at once, and the reaction was monitored using the amine value and gas chromatography. As a comparative example, a similar reaction was conducted using a Cu/Mn/Rh catalyst system.

Table 8 shows the results of the reaction using the 10th recovered catalyst.
Shown below.

As a result, it was found that the catalyst system of the present invention can produce corresponding amines with high activity, high selectivity, and high durability even in the reaction of long-chain alcohols and long-chain amines.

It was.

Table 7 shows the results of the reaction using the 10th recovered catalyst.
Shown below.

As a result, it was found that this catalyst system can produce the corresponding amine through the reaction of lauryl alcohol and stearyl amine with extremely high activity and selectivity compared to the Cu/Fe/Pd catalyst system (Comparative Example 6). .

Table-7 This Cu/Fe/Pd/Mo; Mole supported amount Cu/Fe/Pd; Molar ratio Supported amount 6/110.0110.8 20% 6/110.01 20%

Claims (1)

[Claims] 1 Alcohol or aldehyde and ammonia or primary amine or secondary amine, copper as the first component,
As the second component, one selected from chromium, manganese, iron, cobalt, nickel, and zinc among the fourth period transition metal elements.
(hereinafter abbreviated as fourth period transition metal element), Group 8 platinum group element as the third component, and one or more selected from aluminum, tungsten, and molybdenum as the fourth component (hereinafter referred to as fourth component metal element) In the presence of a catalyst consisting of four components (abbreviated as ), while removing the water produced in the reaction,
Atmospheric pressure or under pressure of 100 atmospheres (gauge pressure) or less, 15
A method for producing an N-substituted amine, characterized by carrying out the reaction at a temperature of 0°C to 250°C. 2. The method for producing an N-substituted amine according to claim 1, wherein the Group VIII platinum group element is one or more selected from platinum, palladium, ruthenium, and rhodium. 3 Copper - 4th period transition metal element - 8th group platinum group element - 4th component metal element The molar ratio of the copper of the catalyst and the metal atom of the 4th period transition metal element is copper:4th period transition metal element: 10: 90
99:1 to 99:1, and the molar ratio of the Group VIII platinum group element to the sum of copper and the fourth period transition metal element is 0.001 to 0.1, and the ratio of the fourth period transition metal element to the fourth period transition metal element is Production of an N-substituted amine according to claim 1 or 2, wherein the molar ratio of the component metal elements is 1:0.01 to 1:1: fourth period transition metal element: fourth component metal element. Method.