JPS62149646A - Production of n-substituted amine - Google Patents

Abstract

PURPOSE:To obtain the titled compound in high yield, by heating an alcohol or aldehyde and ammonia in the presence of a catalyst, consisting of three metal components containing copper, Ni and a small amount of a platinum group element of group VIII metal added thereto and capable of exhibiting high activity and selectivity while removing water formed as a by-product. CONSTITUTION:An alcohol or aldehyde and ammonia are reacted in the presence of a catalyst prepared by adding a platinum group element of group VIII metal, e.g. Pt, Ni, etc., to copper and nickel (preferably at 1:9-9:1 molar ratio), preferably at about 0.001-0.1 molar ratio based on the total amount of the copper and nickel at 150-250 deg.C under atmospheric pressure - 5atm pressure (gauge pressure) while removing water formed by the reaction to give the aimed N- substituted amine, e.g. trilaurylamine, etc. EFFECT:The durability of the catalyst is increased to permit recovery and reuse thereof several times - tens of times. USE:An intermediate for rust inhibitors, surfactants, germicides, textile dyeing assistants and flexible bases, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing corresponding N-substituted amines by reacting alcohols or aldehydes with ammonia.

The N-substituted amines produced according to the present invention are industrially important substances as intermediates for rust preventives, surfactants, fungicides, textile 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.

Regarding the method of producing the corresponding amine from alcohol and amine, see JP-A-52-196404 (copper chromite catalyst, cobalt catalyst) and JP-A-53-59602.
No. (ε same morphine, ↑ same tungsten catalyst),
U.S. Patent No. 3,223,734 (Raney nickel catalyst, copper chromite catalyst), German Patent Application No. L493
, No. 781 (supported nickel catalyst, supported cobalt catalyst), etc.

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, there is a method described in Japanese Patent Publication No. 57-55704. This method uses a copper-nickel binary catalyst.

[Problem that the invention seeks to solve]

However, reactions using this catalyst are also not always satisfactory. That is, although the catalytic activity is better than other general methods, it is highly dependent on the reaction temperature, and the activity may decrease significantly as the reaction temperature decreases. Depending on the type of alcohol targeted, the reaction temperature may be increased,
It is necessary to increase the amount of catalyst added. When such an operation is performed, side reactions which are undesirable in terms of amine quality are likely to be produced, and the yield of the desired amine is low. In order to produce amines in high yields, catalyst properties are required that enable reaction at lower temperatures, exhibit high activity with a small amount of catalyst, and exhibit high selectivity.

[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 aimed to improve the dehydrogenation and hydrogenation functions required of the catalyst and to achieve higher activity and selectivity when producing amines by reacting alcohols or aldehydes with ammonia. We searched for new functions and properties through metal-to-metal composites of nickel and various third component metals.

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 shows high activity and high selectivity in small amounts, which was not possible 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. It was discovered that new catalytic properties that cannot be obtained with other metal compositions are developed for the first time through the interaction between the three component metals of copper, nickel, and Group 8 platinum group elements, leading to the present invention.

That is, the present invention uses a catalyst of a group 8 platinum group element when producing N-substituted amines by reacting alcohol or aldehyde with ammonia,
In the presence of this catalyst, water produced by the reaction is continuously or intermittently removed from the reaction system while
Below atmospheric pressure (gauge pressure), 150°C to 250'C
This method is characterized by producing N-substituted amines in high yield by reacting at a temperature of .

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-nickel catalyst described in No. 55704, and has extremely excellent reaction selectivity. Cave-2.

By combining the three components of KEL - Group 8 platinum group elements, the durability of the catalyst is increased compared to conventional catalysts, and even if the catalyst is collected and reused several to dozens of times, the activity of the catalyst will hardly decrease. It has the characteristics that it does not have.

The catalyst of the present invention exhibits extremely high activity and selectivity compared to conventional catalysts, so it is possible to react at low temperatures and at normal pressure, reducing the amount of catalyst required and improving reaction selectivity. This makes it possible to produce high-yield, high-quality N-substituted amines from branched aliphatic alcohols or aldehydes, from which conventional techniques have not been able to produce the corresponding amines in high yields. It has become possible. In addition, it has become possible to produce N-substituted amines in extremely high yields even from polyhydric alcohols, which are generally prone to side reactions (difficult to produce in terms of amine yield and quality).

Furthermore, according to the catalyst of the present invention, by controlling the flow rate of the introduced ammonia gas, primary,
It is possible to produce secondary and tertiary amines.

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 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). preferable.

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 reacting alcohol and ammonia, catalytic activity is first expressed by the reduction operation of each metal component in a hydrogen atmosphere. Therefore, differences in the form of the metal in the reduction operation section and the state in the system after the reduction operation are 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;
3) Alternatively, aliphatic carboxylates of these metals or complexes stabilized with appropriate ligands may form metal colloids in the reaction medium and form a homogeneous system. 4) A mixture of a form that is dispersed in the reaction medium as in 1) to 2) and a form that is homogeneous in the reaction medium as in 3), 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 It is sufficient if the interaction between the 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, with respect to platinum group elements, carbonyl complexes, amine complexes, phosphates, yne 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): The carrier is mixed thoroughly with an aqueous solution of copper, nickel, and a suitable salt of a platinum group element, such as copper nitrate, nickel nitrate, and platinum group element chloride, and then sodium carbonate or water is added. A method in which metal salts are precipitated on a carrier by adding an alkaline aqueous solution such as sodium oxide or aqueous ammonia (coprecipitation method), or ion exchange of copper, 2.7 Kel, and platinum group elements with sodium, potassium, etc. on zeolite. There are conventional methods such as the ion exchange method, and the method of heating and melting copper, nickel, platinum group elements, and aluminum metal, cooling and solidifying it to form an alloy, and eluting the aluminum in the alloy with caustic soda (alloy method). Any known method may be used. In the case of an impregnation method or a coprecipitation method, after the metal has settled, the catalyst 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, 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, hehenyl alcohol, oleyl alcohol, etc. and their mixed alcohols, as well as Ziegler alcohol obtained by the Ziegler process. Alcohols with branched chains such as oxo alcohols and Guerbet alcohols obtained by oxo synthesis, and as aldehydes,
Examples 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, 116-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.

In the present invention, it is essential to take out the water produced by the reaction of these alcohols or aldehydes with ammonia out of the reaction system, and if the produced water is not taken out of the system, the catalyst performance of the present invention will deteriorate. I can't perform to my full potential.

That is, the catalyst activity and selectivity are reduced, and the amine yield is poor.

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 ammonia 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 previously reduced 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 hydrogen gas or a small amount of hydrogen gas is added. Reduction is carried out by raising the temperature to the reaction temperature while introducing a gas mixture with ammonia. That is, the copper-Nisochelium-8th group 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.

Alcohol or aldehyde as a raw material is placed in a reaction vessel equipped with a pipe for introducing hydrogen and ammonia, and a condenser and separator for condensing and separating the water produced in the reaction, excess ammonia, and distilled oil. Prepare the catalyst. Any amount of catalyst can be charged, but 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, temperature rise is started without introducing hydrogen alone or a mixed gas of hydrogen and a small amount of gaseous ammonia. 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, ammonia is introduced to start the reaction. During the reaction, the water produced is discharged from the reaction system together with gas-deficient substances (hydrogen and excess ammonia) and a small amount of oil, and is separated from the oil through a concentrator and a separator. The separated oil is returned to the reactor.

Furthermore, as a result of analyzing gaseous substances (excess hydrogen and ammonia), these gaseous substances contained almost no by-products, proving that the catalyst of the present invention has high selectivity. It was found that these gaseous substances could be reused without any special purification process by using the machine. After the reaction is complete, the reactant can be directly distilled or filtered to obtain it in 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 Using synthetic zeolite as a carrier, a three-way catalyst of copper-nisochelium-platinum group element was prepared by a coprecipitation method.

The precipitate was filtered, washed with water, dried at 80°C for 10 hours, and heated at 600°C.
It was fired in The amount of the obtained metal oxide supported on the support was 50%.

Next, using this catalyst, alcohol and ammonia were reacted. For comparison, copper-Esokel 2 was also obtained using the same method.
A similar reaction was carried out using a catalyst consisting of two components: copper and platinum group elements.

300 g of lauryl alcohol and 1.5 g of the above catalyst (0.5% based on alcohol) were charged into 11 flasks equipped with a condenser and a separator for separating reaction product water.
While stirring, the inside of the system was replaced with nitrogen, and the temperature was started to increase.

When the temperature reaches 100"C, add hydrogen gas to 10e/10cm using a flow meter.
The mixture was blown into the system at a flow rate of 100 h and the temperature was raised to 190°C. At this temperature, ammonia gas is 51! The reaction system was blown into the reaction system at a flow rate of /h, and the reaction was monitored using the amine value and gas chromatography. Note that the reaction was performed under atmospheric pressure.

The results are shown in Table-1.

Table 1 As a result, it was found that tertiary trialkylamine can be obtained in high yield by the catalyst of the present invention from the reaction between alcohol and ammonia.

Example 2, Comparative Example 3 In carrying out the same reaction as in Example 1, ammonia was introduced into the reaction system at a flow rate of 3072/h, and the reaction was monitored using the amine value and gas chromatography. As a comparative example, a similar reaction was conducted using a Cu/Ni two-component catalyst system. The results are shown in Table-2.

Table-2 Catalyst: 1. Owt% vs. alcohol reaction temperature: 20
0°C Cu/Ni/tertiary component 4/110.04 (mole ratio) As a result, the catalyst system of the present invention has higher selectivity than the Cu/Ni two-component catalyst by changing the flow rate of ammonia introduced. It has been found that secondary amines can be produced.

Examples 3-6. Comparative Examples 4 to 9 Next, using a catalyst consisting of Cu, Ni, and a third component metal, the type of the third component metal in the catalyst was changed in a reaction system of octylalcofur and ammonia in the same manner as in Example-■. We investigated its effect. The third component-containing catalyst was produced in the same manner as in Example-1.

The results are shown in Table-3.

Table-3 Cu/Ni/Third component-8/210.08 (metal molar ratio 150% supported) As a result of reaction temperature = 190°, the third component of the catalyst used in the reaction between octyl alcohol and ammonia. as Fe, Z
In the system to which n+ Zr, Cr, Co, etc. were added, or the catalyst without the addition of a third component, the activity and selectivity were sufficient, but the yield of the corresponding tertiary amine was poor.

On the other hand, in a system in which a platinum group element (Pd, Pt, Ru, Rh) is added as the third component metal of the catalyst of the present invention,
It was found that extremely high activity and high selectivity were exhibited due to the interaction between Cu, Ni, and the third component.

Examples 7 to 10 and Comparative Example-10 Next, using a copper/nickel/platinum group element three-component catalyst of the present invention that exhibits high activity, a reaction between a branched oxo alcohol and ammonia was carried out as an alcohol. The same procedure as in Example-1 was performed.

As the alcohol, an oxo alcohol having 9 carbon atoms (branching rate of 90% or more) was used. The catalyst was produced in the same manner as in Example-1.

The results are shown in Table 4.

Table-4 Reaction temperature: 180-200°C Ammonia flow rate = 5β/h vs. alcohol 300g Catalyst amount: 1w% vs. alcohol Cu/Ni/third component = 4/110.04 (molar ratio) Examples-11-12 Next, using the catalyst of the present invention and controlling the flow rate of ammonia in the same manner as in Example 2, oxo alcohol (carbon number 12-13°, branching rate 94%) and gel alcohol consisting of carbon number 20 were prepared. (branching rate 100%
) was reacted with ammonia.

The results are shown in Table-5.

Table-5 Catalyst = 1.0 t% vs. alcohol reaction temperature: 220°C Ammonia flow rate: 31/h vs. alcohol 300 gCu
/Ni/Cu/Ni/tertiary composition 0.04 (molar ratio) or more,
From the results of Examples 7 to 12, the catalyst of the present invention can react with a highly branched alcohol and ammonia to convert the corresponding secondary and tertiary amines by controlling the flow rate of ammonia. It has been found that it can be produced selectively with high yields.

Examples 13 to 19 Next, amines were synthesized by reacting various alcohols or aldehydes with ammonia using the catalyst of the present invention.

Regarding the platinum group element components used as catalysts, palladium was supported at 5% on activated carbon, and ruthenium was prepared using dodecacarbonyl triruthenium as a complex. Compounded under atmosphere. The results are shown in Table-6.

From the above results, platinum group elements (Pd,
By using the catalyst of the present invention in which one of Pt, Ru, Rh) is combined with two components of copper and nickel, alcohols having branched chains, polyhydric alcohols, alcohols having polyoxyalkylene chains, and aromatic alcohols can be produced. It has been found that the corresponding N-substituted amines can be produced in high yields by reaction with ammonia using N-substituted amines or aldehydes as starting materials.

Claims (1)

[Claims] 1. Alcohol or aldehyde and ammonia are reacted in the presence of a copper-nickel-group 8 platinum group element catalyst at atmospheric pressure or 5 atm (gauge pressure) while removing water produced by the reaction. ) A method for producing N-substituted amines, characterized in that the reaction is carried out at a temperature of 150°C to 250°C under the following pressure. 2. The method for producing N-substituted amines 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 Group 8 platinum group element has a molar ratio of 0.001 to 0.1 with respect to the total of copper and nickel. manufacturing method.