JPS62149647A - Production of n-substituted amine - Google Patents

Abstract

PURPOSE:To obtain the titled substance, by thermally reacting an alcohol or aldehyde with a specific liquid amine in the presence of a highly active and selective catalyst consisting of three metal components containing copper and Ni and further a small amount of a platinum group element of group VIII metal added thereto while adding the liquid amine and removing water formed as a by-product. CONSTITUTION:An alcohol or aldehyde is reacted with a liquid primary or secondary amine (except aliphatic amine) in the presence of a catalyst prepared by adding a platinum group element of group VIII, e.g. platinum, Pd, etc., to copper and nickel (preferably at 1:9-9:1 molar ratio) at about 0.001-0.1 molar ratio based on the total amount of the copper and Ni at 150-250 deg.C under atmospheric pressure - 5atm pressure (gauge pressure) while adding the liquid amine and removing water formed as a by-product by the reaction to afford the aimed N-substituted amine, e.g. laurylmorpholine, etc. USE:An intermediate for rust inhibitors, surfactants, germicides, textile dyeing assistants and flexible bases, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to alcohol or aldehyde and a liquid first
The invention relates to a method for producing a corresponding N-substituted amine by reacting a primary amine or a secondary amine (excluding aliphatic amines).

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

[Conventional technology]

BACKGROUND ART Conventionally, methods for producing corresponding amines by reacting alcohols or aldehydes with ammonia or primary amines or secondary amines are well known. However, reacting alcohol etc. with amine etc.
These methods are mostly methods using gaseous aliphatic amines or methods using gasified liquid amines.

A method for producing a corresponding amine from an alcohol and a gaseous amine is described in JP-A-52-196404 (
copper chromite catalyst, cobalt catalyst), JP-A-53-59
No. 602 (copper-molybdenum, copper-tungsten catalyst),
U.S. Patent No. 3,223,734 (Raney nickel catalyst, copper chromite catalyst), German Patent Application No. 1,49
There are reports such as No. 3,781 (nickel catalyst with support, cobalt catalyst with support). 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. Furthermore, there are very few cases in which the reaction between a liquid amine and an alcohol is carried out under normal pressure or low pressure.

As a method developed to solve these problems, there is a method described in Japanese Patent Publication No. 57-55704. This method uses a copper-nickel binary catalyst to obtain the desired amine in high yield.

[Problem that the invention seeks to solve]

However, when a liquid amine is used in the reaction using this catalyst, if the highly polar amine is present in the system in liquid form from the early stage of the reaction, there is a problem that elution of the reduced catalyst metal, sintering, etc. are likely to occur. Therefore, in order to produce a corresponding amine in high yield by reacting a liquid amine with an alcohol or aldehyde, it is necessary to improve the durability of the metal and the reaction activity as catalyst properties.

[Means for solving problems]

Therefore, the present inventors conducted intensive studies to solve these problems with copper-nickel catalysts, and as a result, developed a new catalyst consisting of a three-component metal consisting of copper and nickel with a small amount of Group 8 platinum group element added. was developed and was able to solve these problems all at once. That is, the present inventors have improved the dehydrogenation and hydrogenation functions required of the catalyst in producing N-substituted amines by reacting alcohols or aldehydes with liquid primary and secondary amines, and have achieved higher dehydrogenation and hydrogenation functions. Aiming to increase activity and selectivity, we searched for new functions and properties through intermetallic composites of copper, nickel, and various third component metal species.

As a result, the present inventors found that by adding a Group 8 platinum group element as a third component metal to copper and nickel as a catalyst metal composition, the combined effect of copper, nickel, and Group 8 platinum group element three component metals was achieved. As a result, we discovered a new function that is extremely stable even in primary and secondary amines that are present in liquid form from the early stage of the reaction, and exhibits high activity and high selectivity even in small amounts, which could not be obtained with the copper-nickel two-component system.

In other words, as a result of searching for new functions by combining copper, nickel, and a third component metal, the eighth
It has been found that among the platinum group elements, platinum, palladium, ruthenium, and rhodium in particular exhibit extremely effective functions in the reaction of the present invention. In particular, as a third component metal, only such Group 8 platinum group elements exhibit new functions when combined with copper and nickel, and as other third component metals,
For example, the addition of chromium, iron, zinc, zirconium, manganese, cobalt, etc., had no effect at all, but rather resulted in a decrease in the catalytic function. The inventors have discovered that new catalytic properties that cannot be obtained with other metal compositions are developed for the first time through the interaction between copper, nickel, and the third component metals of group 8 platinum group elements, leading to the present invention.

That is, in the present invention, when an N-substituted amine is produced by reacting an alcohol or aldehyde with a liquid primary amine or secondary amine (excluding aliphatic amines), copper-nickel-Group 8 In the presence of a platinum group, water produced by the reaction is continuously or intermittently removed from the reaction system while adding a liquid amine, at atmospheric pressure or below 5 atm (gauge pressure), at 150 to 250 °C. This method is characterized by producing N-substituted amines in high yields by reacting at high temperatures.

In the method of the present invention, the catalyst is highly active, so the reaction conditions are mild, and the process can be carried out with light equipment, and the amount of catalyst used is very small, so the reaction can be completed in a short time. I can do it. In addition, the previously presented special public
It exhibits several times higher activity than the copper-nisochel catalyst described in No. 55704, and the desired N-substituted amine can be obtained in high yield. In addition, the composite of copper-nickel-group 8 platinum group element increases the durability of the catalyst compared to conventional catalysts, and even if it is collected and reused several to dozens of times, the activity of the catalyst will not decrease. has unique characteristics.

Compared to conventional catalysts, the catalyst of the present invention is stable in polar alcohols and polar amines, and exhibits extremely high activity and selectivity. Therefore, the reaction can be carried out at normal pressure, and the amount of catalyst required can be reduced.
Due to the improved reaction selectivity, the corresponding amine can be obtained in high yield from a branched aliphatic alcohol or aldehyde and a liquid amine, which could not be obtained in high yield using conventional techniques. Furthermore, it has become possible to produce high quality N-substituted amines. In addition, the corresponding N-substituted amines can be produced in extremely high yields even from polyhydric alcohols, which are generally difficult to produce in terms of amine yield and quality due to their tendency to cause side reactions.

The catalyst used in the present invention essentially contains copper, nickel, and Group 8 platinum group elements (hereinafter abbreviated as platinum group elements), and the proportions of copper, nickel, and platinum group elements in the catalyst metal composition used. can be taken arbitrarily.

That is, the molar ratio of the metal atoms of copper and nickel is preferably in the range of 1:9 to 9:1, and the amount of platinum group elements added to the total amount of copper and nickel is in the range of 0.001 to 0.1 (
molar ratio) is preferred.

Platinum group elements particularly suitable for this reaction are platinum, palladium, ruthenium, and rhodium.

Although the three components of copper, nickel, and platinum group elements are essential as the catalyst metal composition, the catalyst suitable for the present invention can be selected from various forms.

That is, in the present invention, when the three components of copper, nickel, and platinum group elements are present in the reaction system as a catalyst composition, the effect due to the interaction between these three components is exhibited for the first time. The composition has an essential catalytic function, and when an alcohol and an amine are reacted, catalytic activity is first expressed by reducing 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, and in the method described in the present invention, copper and nickel are Any form is acceptable as long as the interaction between the metal and the platinum group element 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, nickel, and platinum group elements each supported on a suitable support, or a mixture of copper, nickel, and platinum group elements supported uniformly on the same support;
Those in a form that are dispersed in the reaction medium 3) Alternatively, they become metal colloids in the reaction medium, such as aliphatic carboxylates of these metals or complexes stabilized with appropriate ligands, and are homogeneously dispersed in the reaction medium. 4) A mixture of 1) to 2) which are dispersed in the reaction medium and 3) which are homogeneous in the reaction medium. Alternatively, it may be in a dispersed form before hydrogen reduction and become uniform after hydrogen reduction, and the three component metals that are the essence of the present invention can be reduced by a reduction operation in a hydrogen atmosphere. It is sufficient if the interaction between the three components is expressed.

In the method of the present invention, more preferable forms of the catalyst include stabilization of the catalyst metal, that is, immobilization of the active surface;
In addition, from the viewpoint of durability against catalyst poisoning substances, it is preferable to have these three component metals uniformly supported on a suitable carrier.

When the three component metals of copper, nickel, and platinum group elements of the present invention are supported on a carrier, suitable carriers include those commonly used as catalyst carriers, such as alumina, silica alumina, diatomaceous earth, silica, and activated carbon. , natural and artificial zeolites, etc. can be used. Although the amount of catalyst metal supported on the support can be arbitrarily determined, it is usually in the range of 5 to 70%.

Various methods can be selected for supporting these three component metals on the carrier surface. In this case, the catalyst raw metal may be oxides or hydroxides of copper, nickel, and platinum group elements, or various metal salts thereof. For example, chlorides, sulfates, nitrates, acetates, aliphatic carboxylates of copper, nickel, and platinum group elements, or complexes of these metals, such as acetylacetone complexes and dimethylglyoxime complexes of copper, nickel, and platinum group elements. ,Also,
Furthermore, regarding platinum group elements, carbonyl complexes, amine complexes, phosphine complexes, etc. can also be used. When producing a catalyst using these metal raw materials by supporting them on a carrier, for example, the carrier is thoroughly impregnated with a solution of appropriate salts of copper, nickel, and platinum group elements, and then dried and calcined. Method (impregnation method): Add the carrier to an aqueous solution of copper, nickel, and a suitable salt of a platinum group element, such as copper nitrate, di-nochel nitrate, and an aqueous solution of a platinum group element chloride, mix well, and then add sodium carbonate. A method in which metal salts are precipitated on a carrier by adding an alkaline aqueous solution such as sodium hydroxide or aqueous ammonia (co-precipitation method), and a method in which copper, nickel, and platinum group elements are ion-exchanged with sodium, potassium, etc. on zeolite. (ion exchange method), and furthermore, a method in which copper, nickel, platinum group elements, and aluminum metal are heated and melted, cooled and solidified to form an alloy, and aluminum in the alloy is eluted with caustic soda (alloy method). Either method is fine. In the case of the impregnation method and coprecipitation method, after the metal is deposited, the metal is thoroughly washed with water, dried at around 100℃,
A catalyst is obtained by firing at 300°C to 700°C.

In addition, by such a method, only copper or only copper and nickel are supported on a carrier, and before the reaction, nickel or platinum group element supports, aliphatic carboxylates, or complexes are added. In the reaction medium under hydrogen atmosphere,
A method of combining copper with nickel and platinum group elements is also effective.

More preferably, the catalyst form is such that the three components are uniformly supported on the same carrier.

These three components, copper, nickel, and platinum group elements, are essentially essential to the present invention, and the addition of metals other than these three components in small amounts will not have any effect on changing the properties of these three component metals. For addition of large amounts, please refer to these 3.
This is not preferable because it adversely affects the interaction of component metals.

Furthermore, it has been found that the absence of any of the three components of the catalyst composition of the present invention has an adverse effect on the reaction of the present invention.

The alcohol or aldehyde that is the raw material used in the present invention is linear or branched and has 8 to 36 carbon atoms.
saturated or unsaturated aliphatic alcohols or aldehydes, such as octyl alcohol, lauryl alcohol, myristyl alcohol, stearyl alcohol, behenyl alcohol, oleyl alcohol, etc., and mixed alcohols thereof, as well as Ziegler alcohol obtained by the Ziegler process, oxo Alcohols having a branched chain such as oxo alcohol and Guerbet alcohol obtained by synthesis, and examples of the aldehyde include lauryl aldehyde, oxo aldehyde, and other aldehydes corresponding to the above-mentioned alcohols.

Various polyhydric alcohols can also be used.

Examples include 1,3-butanediol, 1,4-butanediol, 1,5-bentanediol, 1.6-hexanediol, and polyhydric alcohols such as diethylene glycol, triethylene glycol, and propylene glycol. Other alcohols include aromatic alcohols such as benzyl 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 linear or branched aliphatic alcohols or aldehydes having 8 to 36 carbon atoms, and aliphatic glycols having 2 to 12 carbon atoms. is preferred. The liquid amines to be reacted with these alcohols or aldehydes include amines that are liquid at room temperature (excluding aliphatic amines);
Alternatively, amines that become liquid when heated or amines dissolved in a suitable inert solvent, such as cyclohexylamine, dicyclohexylamine, benzylamine,
Alicyclic or aromatic primary or secondary amines such as xylylene diamine, heterocyclic amines such as morpholine, piperidine, piperazine, monoethanolamine, jetanolamine, etc. and polyamines having a primary or secondary amino group such as ethylenediamine, diethylenetriamine, and dimethylaminopropylamine.

In the present invention, in the reaction with an alcohol or an aldehyde, it is an essential condition that water produced in the reaction be taken out of the reaction system while adding liquid amines into the reaction system.

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 during the reaction, and distill out the produced water and excess amine together with the hydrogen gas, and then condense and separate the produced water in a condenser. It is also possible to recycle hydrogen gas. It is also possible to add a suitable solvent to the reaction system and remove the produced water by azeotropic distillation with this solvent.

In the method of the present invention, a catalyst that has been reduced in advance with hydrogen gas may be used, but the unreduced catalyst is placed in a reactor together with the reaction raw material alcohol or aldehyde, and while hydrogen gas is introduced, the reaction temperature is increased. It is reduced by raising the temperature to . That is, the copper-nickel-group 8 platinum group element catalyst of the present invention has a remarkable feature in that it has a low reduction temperature and can be reduced during the process of heating up to the reaction temperature.

Embodiments of the method of the present invention will be briefly described.

The raw alcohol or aldehyde and the raw material alcohol or aldehyde are placed in a reaction vessel 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, and distilled oil. Prepare the catalyst. Although any amount of catalyst can be charged, since the catalyst of the present invention has high activity, the amount is usually in the range of 0.1% to 2% by weight based on the charged alcohol or aldehyde. After replacing the inside of the system with nitrogen gas, hydrogen is introduced before heating is started. The reaction temperature is usually about 180 to 230°C, but temperatures outside this range can be used depending on the type of reaction. During this temperature rise, the catalyst is reduced and becomes an active catalyst. After reaching a predetermined temperature, amine is introduced to start the reaction.

During the reaction, the water produced is discharged from the reaction system together with gaseous substances (hydrogen and excess amine) and a small amount of oil, and is separated from the oil through a condenser and a separator.

The separated oil is returned to the reactor. It has been found that by using a circulator these gaseous substances and excess amine can be reused without special purification steps.

After the reaction is complete, the reactant can be directly distilled or filtered to obtain an extremely pure form.

〔Example〕

The present invention will be explained in more detail with reference to the following examples and comparative examples.

Example 1 and Comparative Examples 1 and 2 A three-way catalyst of copper-nickel-platinum group element supported on synthetic zeolite was prepared by a coprecipitation method.

The precipitate was filtered, washed with water, dried, and calcined at 600°C. The amount of the obtained metal oxide supported on the support was 50%.

Next, using this catalyst, alcohol was reacted with morpholine as a liquid heterocyclic amine.

300 g of lauryl alcohol and 1.5 g of the above catalyst (based on alcohol: 0.5%) were charged into a 1β flask equipped with a condenser and separator to separate water produced by the reaction, and while stirring, the system was flushed with nitrogen. The air was replaced and the temperature started to increase.

When the temperature reaches 100℃, use a flow meter to supply hydrogen gas at 101/h.
The mixture was blown into the system at a flow rate of 200°C and the temperature was raised to 200°C. At this temperature, morpholine was added in liquid form through the inlet tube, with a ratio of 1% to alcohol.
It was introduced into the reaction system at a rate of 5 mole%/Hr, and the reactant was tracked using the amine value and gas chromatography.

Further, as Comparative Examples 1 and 2, similar reactions were carried out using catalysts consisting of two components of copper/nickel and those consisting of two components of copper/ruthenium. Note that the reaction was performed under atmospheric pressure.

The results are shown in Table-1.

Table 1 Catalyst amount: 1.0 wt% based on alcohol Reaction time: 8 hours Results show that the catalyst system of the present invention (Example-1) has extremely high Active/
It has been found that the corresponding amines can be prepared with high selectivity.

In addition, as in Comparative Example 2, it was found that the two components of Cu/Ru were sufficient for this reaction in terms of activity and selectivity, and that the effect was expressed by using the three components of Cu/Ni/platinum group elements. .

Examples-2 to 4. Comparative Examples 3 to 7 Next, the effects of catalysts made of copper, nickel, and a third component metal were investigated in the same reaction as in Example-1, with various kinds of third component metals in the catalyst. A three-component catalyst was produced in the same manner as in Example-1.

The results are shown in Table-2.

Table 2 Reaction temperature: 200°C Morpholine addition time: 8 hours Morpholine addition amount (molar ratio to alcohol): 1.2 Catalyst addition amount: 2: alcohol: 1. Owt%t% composition ratio: Cu
/Ni/third component = 8/210.08 (molar ratio) As a result, when N-laurylmorpholine is produced by the reaction of lauryl alcohol and morpholine, Fe is used as the third component of the catalyst used.

Catalyst systems to which Zn, Zr, Cr, Co, etc. were added had poor reaction activity. On the other hand, as the third component of the present invention,
Platinum group elements (Pt, Pd, Rh, Ru) with Cu/
It has been found that the catalyst system composited with Ni exhibits extremely high activity and selectivity.

Examples 5 to 11 Next, using the catalyst of the present invention, various alcohols and various liquid amines were reacted in the same manner as in Example-1. The results are shown in Table-3.

Table-3 1), -2) Secondary amine% Catalyst: Cu/Ni/Ru=4/110.04
(Mole ratio) 1 mol χ to alcohol Amine addition rate: 5 to 15 mole
It has been found that the corresponding N-substituted amines can be produced with high activity and selectivity by reacting polyhydric alcohols (linear, branched, aromatic), polyhydric alcohols, or aldehydes with various liquid amines.

Claims (1)

[Claims] 1. An alcohol or an aldehyde and a liquid primary amine or secondary amine (excluding aliphatic amines) are mixed into an amine in the presence of a copper-nickel-group VIII platinum group element catalyst. A method for producing an N-substituted amine, which is characterized in that the reaction is carried out at a temperature of 150°C to 250°C under atmospheric pressure or under pressure of 5 atm (gauge pressure) or less while adding and removing water produced by the reaction. . 2. The method for producing an N-substituted amine according to claim 1, wherein the Group 8 platinum group element is one or more selected from platinum, palladium, ruthenium, and rhodium. 3. The molar ratio of copper and nickel metal atoms in the copper-nickel-group 8 platinum group element catalyst is 1:9 to 9 for copper:nickel.
:1, and the mole ratio of the Group 8 platinum group element to the sum of copper and nickel is 0.001 to 0.1. Production method.