JPH02233A - 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 alkaline (earth) metals selected from Li, Na, K, Rb, Ce, Mg, Ca, Sr and Ba 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, methods for producing corresponding amines by reacting alcohols or aldehydes with ammonia or primary amines or secondary amines are well known. However, it has been difficult to selectively obtain a specific amine by reacting an alcohol or the like with an amine.

Regarding the method of producing the corresponding amine from alcohol and amine, see JP-A-52-19604 (copper chromite catalyst, cobalt catalyst), JP-A-53-59602 (copper-molybdenum, copper-tungsten catalyst), and U.S. Pat. Third
．． No. 223.734 (Raney nickel catalyst, copper chromite catalyst), German Patent Application No. 1.493.781 (supported cobalt catalyst), Japanese Patent Publication No. 57-55704 (
There are reports of copper-nickel catalysts. 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,
65, JP-A-62-149646, JP-A-62-14
9647, 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 reaction using this catalyst is not always a satisfactory method. In other words, it has good activity and selectivity compared to other general methods, but when considering industrialization, there is a need for further improvement in selectivity in terms of yield and quality of the N-substituted amine produced. be done. Furthermore, when the obtained N-substituted amine is converted into a quaternary ammonium salt (tetraalkylammonium salt, trialkylbenzylammonium salt, etc.), there are problems such as deterioration of hue.

[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 studies on increasing the selectivity of catalytic reactions by adding a small amount of a fourth component metal element to a metal platinum group element catalyst, we found that:
As the fourth component metal element, among alkali metals and alkaline earth metals, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, and barium are used as a catalyst for copper - 4th period transition metal element - 8th group platinum group element It has been found that when a small amount is added to , the activity is maintained almost the same and the selectivity is significantly improved. At the same time, we have found that the hue of a quaternary ammonium salt derived from an N-substituted amine produced using this catalyst as a raw material is significantly improved compared to conventional ones. At this time, the fourth period transition metal elements include chromium, manganese,
Iron, cobalt, nickel and zinc were effective, and platinum, palladium, ruthenium and rhodium were effective as group VIII platinum group elements.

As a result, by adding a small amount of alkali metal or alkaline earth metal as the fourth component metal element to the copper-fourth period transition metal element-group eight platinum group element catalyst, copper-fourth period transition metal element- It has an activity equivalent to that of a Group 8 platinum group element catalyst, exhibits much higher selectivity than a copper-4th period transition metal element-Group 8 platinum group element catalyst, and is derived from the obtained N-substituted amine. A high-performance amination catalyst has been found that provides a very good color hue of the quaternary ammonium salt.

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 is significantly superior to the known copper-nickel-Platinum group VIII catalyst. It has excellent performance.

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 the activity of the catalyst hardly decreases even after being collected and reused several to thousands of times. It has the characteristic that there is no

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 set arbitrarily, but the molar ratio of the metal atoms of copper and the fourth period transition metal element is 10. :90 to 99:1 is preferred, more preferably 50:50 to 99:l.

Further, 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 0.001 to 0.0.
It is 5. Further, the molar ratio of the fourth period transition metal element to the fourth component is preferably 1:0, O1 to L:1, and more preferably 0.01 to 0.5.

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 lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, and barium.

The catalyst metal composition requires 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 homogeneous like the complexes described above, 4) Those in the form of a dispersion in the reaction medium as in 1) 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, diatomaceous earth, 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. , are added at the same time so that the pH of the slurry is constant (for example, pH = 7 constant), the metal salt is precipitated on the carrier, dried, and calcined to first form copper - a fourth period transition metal element -
A method in which a platinum group element catalyst is prepared, the resulting three-component catalyst is thoroughly impregnated in an aqueous solution of an alkali metal salt or an alkaline earth metal salt, and then dried and calcined (the above is a coprecipitation method). Any conventionally known method may be used, such as a combination of impregnation methods) or a method of ion exchange with hydrogen or metal contained in zeolite (ion exchange method). In the case of the coprecipitation method, after the metal is deposited, it is thoroughly washed with water, dried at around 100°C, and then calcined at 300°C to 700°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 form is such that 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 that is the raw material used in the present invention is a linear 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 stearyl alcohol, behenyl alcohol, oleyl alcohol, mixed alcohols thereof, Ziegler alcohol obtained by the Ziegler method, oxo alcohol and gel pair alcohol obtained by the oxo method, and aldehydes include: Examples include lauryl aldehyde, oxo aldehyde, and other aldehydes corresponding to the above-mentioned alcohols.

Various polyhydric alcohols can also be used.

For example, 1.3-butanediol, 1゜4-butanediol, 1.5-bentanediol, 1.6-hexanediol, 1.9-nonanediol, etc., and polyhydric alcohols such as diethylene glycol and triethylene glycol. Can be mentioned.

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, and may be ammonia or saturated or unsaturated straight or branched primary amines having 1 to 24 carbon atoms.
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 a suitable 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 and used 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 metal element 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 increase is started while 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 oily substances, and is passed 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 contained by-products (e.g., hydrocarbons, disproportionate amounts of raw amines). It has been proven that the catalyst of the present invention has high selectivity, and by using a circulator, these gaseous substances can be recycled without a special purification process. I found out that it can be used. 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 is
It can be obtained in extremely pure form by distillation. Further, the obtained N-substituted amine can be converted into a quaternary ammonium salt having a good hue by reacting with methyl chloride, benzyl chloride, or the like.

〔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 1.2 and Comparative Examples 1 to 4 A four-way catalyst of copper-fourth period transition metal element-platinum group element-fourth component supported on synthetic zeolite was prepared as follows.

A 1β flask was charged with synthetic zeolite, and then copper nitrate, nickel nitrate, and palladium chloride were mixed at a molar ratio of each metal atom: Cu:Ni:Pd=4:1:0.0
5 dissolved in water was added, and the temperature was raised while stirring. A 10% Na2CD aqueous solution was gradually added dropwise at 90°C. After aging for 1 hour, the precipitate was filtered and washed with water.
After drying at 80°C for 10 hours, it was fired at 400°C for 3 hours.

The obtained three-way catalyst was mixed with a lithium carbonate aqueous solution (molar ratio: Ni
:Li=l :0.05) and heated to 80℃ again.
After drying for 10 hours, it was fired at 300°C for 1 hour. The amount of the obtained metal oxide supported on the support was 50%.

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

II with condenser and separator for separating produced water
! A flask was charged with 600 g of lauryl alcohol and 1.5 g of the above catalyst (0.25 wt% based on the raw material alcohol), and while stirring, the system was purged with nitrogen and the temperature was started to rise.

When the temperature reaches 100℃, add hydrogen gas to 10J using a flow meter.
It was blown into the system at a flow rate of 7/hr and the temperature was raised to 200°C. At this temperature, the mixed gas of dimethylamine and hydrogen is
It was blown into the reaction system at a flow rate of 1/hr, and the reaction was monitored using the amine value and gas chromatography.

The results are shown in Table-1.

As a result, compared to the conventional Cu/Ni 2 catalyst system (Comparative Example 1), the Cu/fourth period transition metal element (N
l)/Platinum group element (Pd)/Fourth component (Li) The four-component catalyst system is Cu/N i/Platinum group element (Pd) 3
It was found that, like the component catalyst system, it showed high activity and the selectivity was greatly improved.

Next, lauryl dimethylamine produced using these catalysts was purified by distillation, and then reacted with benzyl chloride or methyl chloride under normal reaction conditions to synthesize a quaternary ammonium salt. Then, the hue of the obtained quaternary ammonium salt was measured using Lovibond Red (using a 1-inch cell).

The results are shown in Table-2.

In the reaction between alcohol and monomethylamine, the quaternary
The periodic transition metal element is Cr, the platinum group element is Ru, and the fourth
The reaction activity was investigated by changing the components to Li, Na5K, Rh, and Cs. These quaternary catalysts were prepared in the same manner as in Example 1. In addition, as a comparative example, Cu/Cr/R
A similar reaction was carried out using a u catalyst. Also, the obtained 3
After purifying the grade amine by distillation, it is reacted with methyl chloride, and the color of the resulting quaternary ammonium salt (Lovibond Re
d) was observed.

The results are shown in Table-3.

As a result, when producing distearyl monomethyl tertiary amine through the reaction of stearyl alcohol and monomethyl amine, Li, Na,
K, Cu/Cr/Ru/fourth using Rb5Cs
It was found that the component catalyst showed an activity equal to or higher than that of the Cu/Cr/Ru catalyst (Comparative Example 5), the selectivity was improved, and the hue of the quaternary ammonium salt was improved.

Table main catalyst composition Cu/Ni/Pd/Li=4/110.0
510.05 Cu/Ni = 4/I Cu/Ni/Pd = 4/110.05 As a result, Cu/Ni two-component catalyst system (Comparative Example 3),
Compared to the Cu/Ni/Pd three-component catalyst system (Comparative Example 4),
It has been revealed that the four-component catalyst system of the present invention (Cu/Ni/platinum group element (Pd)/fourth component) has a very good hue of the quaternary ammonium salt.

Examples 3 to 7 and Comparative Example 5 Regarding catalysts consisting of copper, a fourth period transition metal element, a platinum group element, and a fourth component, stearyl Rua Examples 8 to 11 and Comparative Example 6 copper and a fourth period transition metal element Regarding a catalyst consisting of a platinum group element and a fourth component, by the reaction of dodecyl alcohol and ammonia, the fourth period transition metal element in the catalyst is Zn, the platinum group element is pt, and the fourth component is Mg, Ca5S.
The reaction activity was investigated using different types of rSBa. These 4
The base catalyst was prepared in the same manner as in Example 1. Further, as a comparative example, a similar reaction was conducted using a Cu/Zn/Pt catalyst.

The results are shown in Table 4.

As a result, when tridodecylamine is produced by the reaction of dodecyl alcohol and ammonia, Mg and Ca5Sr are used as the fourth component as a catalyst.

The Cu/Zn/Pt/fourth component catalyst using Ba is Cu
/Zn/pt catalyst (Comparative Example 6) showed an activity equal to or higher than that, and on the other hand, it was found that the selectivity was improved.

Table Cu/Zn/Pt: Molar supported amount Cu/Zn/Pt/4th component; Molar supported amount 5/110.05 50% 5/110.0510.5 50% Reaction conditions; Alcohol: Dodecyl alcohol Ammonia amine introduction rate: 10j! /hr Reaction temperature: 180°C Catalyst addition amount: 1.0% relative to alcohol Example 12 and Comparative Example 7 Reaction between lauryl alcohol and methylamine was performed using a Cu/Co/Pd/fourth component (Ba) catalyst. Ta.

In this reaction, the introduction flow rate of methylamine was changed to 3H/
The reaction was monitored using the amine value and gas chromatography. In addition, the obtained secondary amine was purified by distillation and then reacted with benzyl chloride to produce 4
Color of grade ammonium salt (Lovibond Red)
observed. As a comparative example, a similar reaction was conducted using a Cu/Co/Pd catalyst system.

The results are shown in Table-5.

As a result, in this catalyst system, the reaction between lauryl alcohol and methylamine produces four components (Cu/Co/Pd/i) (B
a) By using a catalyst, dilaurylmethylamine can be produced with higher selectivity than the Cu/Co/Pd catalyst system (Comparative Example 7), and quaternary It was found that the hue of the ammonium salt was better than that of the conventional one.

Table book Cu/Co/Pd: Morjohi 3/110
．． 03 Supported amount 40% Cu/Co/Pd/Ba; molar ratio 3/110.
0310.5 Supported amount: 40% Reaction conditions: Alcohol; Lauryl alcohol amine; Methylamine amine introduction rate: 30β/hr Reaction temperature: 180°C Catalyst addition amount: 0.25% relative to alcohol Example 13 and Comparative Example 8 Cu/ A reaction between lauryl alcohol and stearylamine was carried out using a Mn/Ru/fourth component (Ca) 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/Mn/Ru catalyst system.

The results are shown in Table-6.

As a result, with this catalyst system, the reaction between lauryl alcohol and stearylamine can proceed with extremely high activity, similar to the Cu/Mn/Ru catalyst system (Comparative Example 8). Ru catalyst system (Comparative Example 8)
It was found that the corresponding amines could be produced with high selectivity compared to

Table: Cu/Mn/Ru/Ca; molar loading amount Cu/Mn/Ru; molar ratio loading 1 4/110.110.3 20% 4/110.1 20% Reaction conditions: Alcohol; lauryl alcohol Mine: stearylamine alcohol/amine = 1 Reaction temperature: 180°C Catalyst addition amount: 1.0% relative to alcohol Examples 14 to 17 Using the catalyst of the present invention, various alcohols or aldehydes were reacted with dimethylamine to produce the corresponding reaction. The effect on tertiary amine synthesis was investigated. Note that the catalyst was prepared using an impregnation method.

The results are shown in Table-7.

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, tertiary amines with extremely high activity and high selectivity were It has been found that amines can be produced in high yields.

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 18 and Comparative Example 9 Next, behenyl alcohol and stearylamine were reacted using a Cu/Mn/Rh 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/Mn/Rh catalyst system.

The results are shown in Table-8.

As a result, it was found that with this catalyst system, the corresponding amine can be produced with high selectivity even in the reaction of a long-chain alcohol and a long-chain amine.

Table 8 Cu/Mn/Rh/K; Molar supported amount Cu/Mn/Rh; Molar supported amount 951510, 0510.5 40% 951510, 05 40% Reaction conditions; Alcohol/1min (molar ratio) = 1 Reaction degree: 200°C Catalyst addition amount: 2% vs. alcohol Example 19 and Comparative Example 1O The reaction between lauryl alcohol and stearylamine was performed using a Cu/Fe/Pd/fourth component catalyst. . In this reaction, distearylamine 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 (gauge pressure).

The results are shown in Table-9.

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 10). .

Table-9 Cu/Fe/Pd/K; molar ratio 6/110.
0110.8 Supported amount 20% Cu/Fe/Pd; molar ratio 6/110. Previously supported amount: 20% Reaction conditions: Alcohol: lauryl alcohol amine; stearyl amine alcohol/amine = 1 Reaction temperature: 160°C Catalyst addition amount: 1.0% to alcohol Example 20 Filtration from the reaction product of Example 1 The catalyst was recovered and the amination reaction was repeated under the same conditions.

The results are shown in Table-10.

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 4th period transition metal elements), Group 8 platinum group elements as the third component, and lithium, sodium, potassium, rubidium, and cesium among alkali metals and alkaline earth metals as the fourth component In the presence of a catalyst consisting of four components, one or more selected from magnesium, calcium, strontium, and barium (hereinafter referred to as the fourth component metal element), a large amount of water is removed while removing the water generated in the reaction. A method for producing an N-substituted amine, characterized in that the reaction is carried out at a temperature of 150°C to 250°C under atmospheric pressure or an increased pressure of 100 atmospheres (gauge pressure) or less. 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.