EP4069418A1

EP4069418A1 - Process for preparing amines over a copper catalyst

Info

Publication number: EP4069418A1
Application number: EP20812021.2A
Authority: EP
Inventors: Martin Ernst; Ansgar Gereon Altenhoff; Hermann Luyken; Tatjana HUBER; Sebastian Haupt; Dieter Kolassa
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2019-12-03
Filing date: 2020-11-24
Publication date: 2022-10-12
Also published as: US20230025575A1; CN114746179A; WO2021110472A1; CA3163479A1; JP2023504629A

Abstract

A process for preparing an amine by reacting an aldehyde and/or ketone with a nitrogen compound selected from the group consisting of ammonia and primary and secondary amines, followed by hydrogenation of the resulting reaction product in the liquid phase and in the presence of hydrogen and a heterogeneous copper oxide hydrogenation catalyst at a temperature of 20 to 230°C, wherein the aldehyde and/or ketone is reacted with the nitrogen compound either together with the hydrogenation in the liquid phase and in the presence of hydrogen and of the catalyst (alternative 1) or in a step preceding the hydrogenation (alternative 2), and wherein the catalytically active composition of the catalyst, prior to reduction with hydrogen, contains at least 24% by weight of oxygen compounds of copper, calculated as Cu.

Description

Process for the preparation of amines over a copper-containing catalyst

description

BACKGROUND OF THE INVENTION

The present invention relates to a process for the preparation of an amine by reacting an aldehyde and / or ketone with a nitrogen compound selected from the group consisting of ammonia, primary and secondary amines and subsequent hydrogenation of the resulting reaction product in the liquid phase and in the presence of Hydrogen and a copper oxide-containing heterogeneous hydrogenation catalyst

STATE OF THE ART

The process products are used, inter alia, as intermediate products in the production of fuel additives (US-A-3,275,554; DE-A-21 25 039 and DE-A-36 11 230) and biologically active substances (Mokrov GV et al, Russian Chemical Bulletin, 59 (6), 1254-1266, 210) or as a crosslinker in polyurethane foams (US Pat. No. 8,552,078 B2).

WO 2004/085353 A1 (BASF Aktiengesellschaft) describes the production of hydrogenation catalysts which contain, inter alia, CuO, Al ₂ O ₃ , La ₂ 0 ₃ and elemental copper. Used who the such catalysts for the hydrogenation of organic compounds which have at least one carbonyl group.

WO 2007/006719 A1 (BASF Aktiengesellschaft) describes the production of hydrogenation catalysts which contain, inter alia, CuO, Al ₂ O ₃ , La ₂ 0 ₃ and elemental copper. To increase its stability, the catalyst is treated with boiling water and / or steam. Such catalysts are used for the hydrogenation of organic compounds which have at least one carbonyl group.

WO 2007/107477 A1 (BASF Aktiengesellschaft) describes the production of an amine by reacting an aldehyde and / or ketone with hydrogen and a nitrogen compound in the presence of a coated catalyst, which is preferably Pd / Ag / AhOs.

WO 2010/031719 A1 (BASF SE) describes the production of an amine by reacting an aldehyde and / or ketone with hydrogen and a nitrogen compound over a copper and aluminum oxide-containing catalyst. The copper oxide content, calculated as CuO, can be well over 50% by weight. The conversion takes place exclusively in the gas phase.

WO 2011/067199 A1 (BASF SE) describes the production of a catalyst by reacting an aldehyde and / or ketone with hydrogen and a nitrogen compound on a supported copper, nickel, cobalt and tin-containing catalyst, the carrier being aluminum Umoxid (AI ₂ O ₃ ) is. Disclosed is a catalyst with a copper oxide content, calculated as CuO, of a maximum of 20% by weight. No. 8,552,078 B2 (Air Products and Chemicals, Inc.) describes the reaction of polyamines with suitable aldehydes and ketones, for example the reaction of 1,2-EDA with benzaldehyde to give N-benzyl-1,2-ethylenediamine. Pd / C is used as the catalyst.

WO 2016/023839 A1 (Sika Technology AG) describes the conversion of 1, 2-PDA with a corresponding aldehyde or ketone (e.g. ^{the conversion with benzaldehyde to give N 1 -benzyl-}

1,2-propylenediamine). Pd / C is used as the catalyst.

WO 2017/037069 A1 (Sika Technology AG) describes the implementation of 1, 2-EDA with a corresponding aldehyde or ketone (e.g. the reaction with benzaldehyde to form N-benzyl

1.2-ethanediamine). Another product is mainly multiply alkylated 1,2-EDA (for example N, N‘-benzyl-1,2-ethylenediamine). Pd / C is used as the catalyst.

In the production of diamines, such as, for example, N-benzyl-1,2-ethylenediamine (NBEDA) or N-benzyl-1,2-propylenediamine (NBPDA), the prior art exclusively describes the use of Pd / C as being considered upcoming catalysts. The specifically disclosed processes relate to production on a laboratory scale. However, the catalysts used are not readily suitable for use in large-scale industrial processes. The disadvantage here is that the catalyst has to be used in correspondingly large quantities. However, Pd is a material that occurs only rarely on earth and is therefore difficult to obtain. The high procurement costs for such catalysts consequently reduce the profitability of a corresponding production process. Further problems arise with regard to the service life and mechanical stability of the catalysts, which are not sufficient for a large-scale industrial process. An activated carbon carrier, for example, does not have sufficient stability and therefore does not have a long service life.

TASK

The object of the present invention was to improve the economic viability of previous processes for the reductive amination of aldehydes and ketones and to remedy one or more disadvantages of the prior art, in particular the disadvantages mentioned above. The aim was to find catalysts which are technically simple to produce and which allow the abovementioned aminations to be carried out with high conversion, high yield, space-time yield (STY), selectivity and, at the same time, high mechanical stability of the shaped catalyst body low risk of run-through (triggering thermal run-through reactions). The catalysts should accordingly have a high activity and, under the reaction conditions, a high chemical and mechanical stability and a long service life.

[Space-time yields are given in 'amount of product / (catalyst _{volume · time)' (kg / (l cat.} _{· H)) and / or 'amount of} product / (reactor volume · time)' (kg / (l reactor r · h )]. DESCRIPTION OF THE INVENTION

Surprisingly, a process for the preparation of an amine by reacting an aldehyde and / or ketone with a nitrogen compound selected from the group consisting of ammonia, primary and secondary amines and subsequent hydrogenation of the resulting reaction product in the liquid phase and in the presence of hydrogen was found and a copper oxide-containing heterogeneous hydrogenation catalyst at a temperature of 20 to 230 ° C, the reaction of the aldehyde and / or ketone with the nitrogen compound either together with the hydrogenation in the liquid phase and in the presence of the hydrogen and the catalyst (alternative 1) or takes place in a step upstream of the hydrogenation (alternative 2), and where the catalytically active mass of the catalyst contains at least 24% by weight of oxygen-containing compounds of copper, calculated as Cu, before its reduction with hydrogen.

It has been found that such a catalyst can be used to prepare corresponding amines in high yield and selectivity. This is surprising for the person skilled in the art, at least because of the following consideration. According to WO 2004/085353 A1 and WO 2007/006719 A1 (both BASF Aktiengesellschaft), a corresponding catalyst is used exclusively for the hydrogenation of organic compounds containing carbonyl groups. The person skilled in the art would actually have expected that the aldehyde / ketone would be reduced to the corresponding alcohol under the given reaction conditions and thus could not react or only to a small extent with the nitrogen compound to give the desired product amine.

It was also surprising that such catalysts are at all suitable for amination in the liquid phase, or give better results in the liquid phase than in the gas phase. This is particularly surprising in the light of WO 2010/031719 A1. There it is taught on page 10, lines 22 to 26 that the procedure according to WO 2010/031719 A1 (amination in the gas phase on a catalyst containing oxygen-containing compounds of copper and aluminum) provides, inter alia, better selectivities than synthesis in the liquid phase.

CATALYST

According to the invention, a copper oxide-containing heterogeneous hydrogenation catalyst is used, the catalytically active composition of which contains at least 24% by weight, preferably at least 40% by weight, of oxygen-containing compounds of copper, calculated as Cu, before its reduction with hydrogen.

The catalytically active mass of the catalyst after its last heat treatment and before its reduction with hydrogen is defined as the sum of the masses of the catalytically active components. The catalytically active components are either metals in elemental form or their oxygen-containing compounds. The concentration data (in% by weight) of the catalytically active constituents of the catalyst relate in each case to the catalytically active mass of the finished catalyst after its last heat treatment (calcination) and before its reduction with hydrogen. They also refer to the mass of the corresponding metal, regardless of whether the metal is in elemental form or as an oxygen-containing compound, the mass of the corresponding metal being based on the total mass of all metals contained in the catalytically active mass. If the catalytically active component in question is not a metal (in elemental form), but an oxygen-containing compound of a metal, this is indicated by the addition “calculated as ...”. For example, "oxygen-containing compounds of copper, calculated as Cu" etc.

The catalytically active composition of the catalyst prior to its reduction with hydrogen contains preferably in the range from 24 to 98% by weight, particularly preferably 50 to 90% by weight, very particularly preferably 55 to 85% by weight or even 60 to 80% by weight of oxygen-containing compounds of copper, calculated as Cu.

The catalytically active composition of the catalyst prior to its reduction with hydrogen contains preferably in the range from 0.5 to 75% by weight, particularly preferably 0.5 to 40% by weight, very particularly preferably 1 to 35% by weight or even 1.5 to 30% by weight or 1.5 to 20% by weight of oxygen-containing compounds of aluminum, calculated as AI.

For example, the catalytically active mass of the catalyst before its reduction with hydrogen can also be 24 to 98% by weight, preferably 40 to 95% by weight or even 50 to 90% by weight, oxygen-containing compounds of copper, calculated as Cu and 0 , 5 to 75 wt .-%, preferably 4 to 59 wt .-% or even 9 to 49 wt .-% oxygen-containing compounds of aluminum, calculated as AI, contain.

According to the invention it is possible to use a catalyst whose main constituent is oxygen-containing compounds of Cu and Al. In this case, the sum of these two components, calculated as Cu or Al, of the catalytically active mass of the catalyst is usually 70 to 100% by weight, preferably 75 to 100% by weight, particularly preferably 80 to 100% by weight . Further components can, as explained below, be oxygen-containing compounds of lanthanum, tungsten, molybdenum, titanium and zirconium and elemental copper.

With regard to mechanical stability, it is advantageous if the catalyst according to the invention contains the components specified on the following pages (in particular oxygen-containing compounds of lanthanum, tungsten, molybdenum, titanium and zirconium, elemental copper and oxygen-containing compounds of magnesium, calcium, silicon and iron ) included. The catalytically active composition of the catalyst prior to its reduction with hydrogen contains preferably in the range from 0.5 to 40% by weight, particularly preferably 1 to 35% by weight and very particularly preferably 1.5 to 30% by weight or even 1.5 to 20% by weight of at least one oxygen-containing compound selected from the group consisting of oxygen-containing compounds of lanthanum, tungsten, molybdenum, titanium and zirconium, calculated as La, W, M,

Ti, and Zr, with oxygen-containing compounds of lanthanum being preferred.

In particular, the catalytically active composition of the catalyst before its reduction with hydrogen preferably contains in the range from 0.5 to 40% by weight, particularly preferably 1 to 35% by weight and very particularly preferably 1.5 to 30% by weight or even 1.5 to 20% by weight of oxygen-containing compounds of lanthanum, calculated as La, the total concentration of oxygen-containing compounds of lanthanum and any oxygen-containing compounds of tungsten, molybdenum, titanium and zirconium, each calculated as W, M, Ti, and Zr, are in the above ranges. If, for example, the upper limit of 40% by weight of oxygen-containing compounds of lanthanum is achieved, this means that the catalyst does not contain any oxygen-containing compounds of tungsten, molybdenum, titanium and / or zirconium.

The catalytically active composition of the catalyst prior to its reduction with hydrogen contains preferably in the range 0.1 to 40% by weight, particularly preferably 1 to 35% by weight and very particularly preferably 1.5 to 30% by weight or even 1.5 to 20% by weight of elemental copper and / or in the range from 0.1 to 40% by weight, 0.5 to 35% by weight and particularly preferably 1 to 30% by weight or even 1 , 5 to 20 wt .-%, at least one oxygen-containing compound selected from the group consisting of oxygen-containing compounds of magnesium, calcium, silicon and iron, calculated as Mg, Ca, Si and Fe, elemental copper being particularly preferred. The catalyst very particularly preferably contains elemental copper but none of the oxygen-containing compounds of magnesium, calcium, silicon and iron mentioned here.

According to step (ii) of the production process described below, elemental copper can become part of the catalyst. The same applies to the above-mentioned oxygen-containing compounds of magnesium, calcium, silicon and iron if cement is used in step (ii).

In particular, the catalytically active mass of the catalyst can be reduced with hydrogen in a proportion of at most 10 wt .-%, preferably at most 8 wt .-%, particularly preferably at most 5 wt .-% or even at most 4 or at most 3 wt. -%, have at least one further component selected from the group consisting of the elements Re, Fe, Ru, Co, Rh, Ir, No, Pd and Pt. Such further components can be part of the oxidic material described below and can thus become part of the catalyst according to step (i) of the manufacturing process described below.

The catalytically active composition of the catalysts according to the invention and the catalysts used in the process according to the invention preferably contains no silver, either in metallic (oxidation state = 0) or in an ionic (oxidation state * 0), in particular oxidized, form.

The catalytically active composition of the catalyst preferably does not contain any oxygen-containing compounds of chromium.

In a particularly preferred embodiment, the catalytically active composition of the catalysts used in the process according to the invention contains no further catalytically active components than those explicitly mentioned above, neither in elemental (oxidation state = 0) nor in ionic (oxidation state * 0) form.

The catalytically active material is usually not doped with other metals or metal compounds. However, it is preferred to exclude the usual trace elements from the metal extraction of copper, aluminum, lanthanum, tungsten, molybdenum, titanium and zirconium and possibly magnesium, calcium, silicon and iron.

In the process according to the invention, the catalysts are preferably used in the form of catalysts which are composed only of catalytically active material and, if appropriate, a deformation aid (such as, for example, graphite or stearic acid) that does not belong to the catalytically active material, if the catalyst is used as a shaped body, exist, i.e. do not contain any other catalytically active accompanying substances.

In a preferred embodiment, the catalytically active composition of the catalyst contains before its reduction with hydrogen in the range of

50 to 90% by weight, particularly preferably 55 to 85% by weight and very particularly preferably 60 to 80% by weight of oxygen-containing compounds of copper, calculated as Cu,

0.5 to 40% by weight, particularly preferably 1 to 35% by weight and very particularly preferably 1.5 to 30% by weight or even 1.5 to 20% by weight of oxygen-containing compounds of aluminum, calculated as AI

0.5 to 40% by weight, particularly preferably 1 to 35% by weight and very particularly preferably 1.5 to 30% by weight or even 1.5 to 20% by weight of at least one oxygen-containing compound from the group consisting of oxygen-containing compounds of lanthanum, tungsten, molybdenum, titanium and zirconium, calculated as La, W, Mo, Ti, and Zr, and

0.1 to 40% by weight, particularly preferably 0.5 to 35% by weight and very particularly preferably 1 to 30% by weight or even 1 to 20% by weight of elemental copper. In a particularly preferred embodiment, the catalytically active composition of the catalyst contains before its reduction with hydrogen in the range of

0.5 to 40% by weight, particularly preferably 1 to 35% by weight and very particularly preferably 1.5 to 30% by weight or even 1.5 to 20% by weight of oxygen-containing compounds of lanthanum, calculated as La, and

0.1 to 40% by weight, particularly preferably 0.5 to 35% by weight and very particularly preferably 1 to 30% by weight or even 1 to 20% by weight of elemental copper.

In this particularly preferred embodiment, the total concentration of oxygen-containing compounds of lanthanum and any oxygen-containing compounds of tungsten, molybdenum, titanium and zirconium, calculated as W, M, Ti and Zr, is usually in the above-mentioned ranges.

The sum of the constituents of the catalytically active composition mentioned above in the preferred and particularly preferred embodiment is usually 70 to 100% by weight, preferably 80 to 100% by weight, particularly preferably 90 to 100% by weight, particularly> 95 % By weight, very particularly> 98% by weight, in particular> 99% by weight, e.g. B. particularly preferably 100 wt .-%.

The catalyst according to the invention can preferably be prepared by a process in which

(i) an oxidic material comprising oxygen-containing compounds of copper, aluminum, and at least one oxygen-containing compound selected from the group consisting of oxygen-containing compounds of lanthanum, tungsten, molybdenum, titanium and zirconium, oxygen-containing compounds of lanthanum being preferred, provided,

(ii) powdered metallic copper, copper flakes, powdery cement or a mixture thereof, preferably powdered metallic copper, copper flakes or a mixture thereof, is added to the oxidic material,

(iii) the mixture resulting from (ii) is shaped to give the copper oxide-containing catalyst and is then preferably calcined at least once.

The amount of the materials used in steps (i) and (ii) is to be selected so that the catalyst according to the invention is composed as described above. Accordingly, preference is also given to a process in which, in a process step preceding the amination, the catalyst is first prepared in accordance with the process described above. A catalyst produced in this way is distinguished by a particularly high mechanical stability.

A high-alumina cement is preferably used as the cement. The high-alumina cement particularly preferably consists essentially of aluminum oxide and calcium oxide, and particularly preferably it consists of 75 to 85% by weight of aluminum oxide and 15 to 25% by weight of calcium oxide. Furthermore, a cement based on magnesium oxide / aluminum oxide, calcium oxide / silicon oxide and calcium oxide / aluminum oxide / iron oxide can be used.

The oxidic material can have at least one further component selected from the group consisting of the elements Re, Fe, Ru, Co, Rh, Ir, No, Pd and Pt. The respective amount of these components in the oxidic material is to be chosen so that the corresponding amount in the catalytically active material of the catalyst is in the abovementioned range.

In a particularly preferred embodiment, the catalytically active composition of the catalyst contains before its reduction with hydrogen in the range of

0.1 to 40 wt .-%, particularly preferably 0.5 to 35 wt .-% and very particularly preferably 1 to 30 wt .-% or even 1 to 20 wt .-% elemental copper, and can be produced according to a Procedure in the

(i) an oxidic material comprising oxygen-containing compounds of copper, aluminum, and at least one oxygen-containing compound selected from the group consisting of oxygen-containing compounds of lanthanum, tungsten, molybdenum, titanium and zirconium, is provided,

(ii) powdered metallic copper, copper flakes or a mixture thereof is added to the oxidic material,

(iii) the mixture resulting from (ii) is shaped to give the copper oxide-containing catalyst and is then preferably calcined at least once. In a particularly preferred embodiment, the catalytically active composition of the catalyst contains before its reduction with hydrogen in the range of

(i) an oxidic material comprising oxygen-containing compounds of copper, aluminum and oxygen-containing compounds of lanthanum is provided,

In this particularly preferred embodiment, the total concentration of oxygen-containing compounds of lanthanum and any oxygen-containing compounds of tungsten, molybdenum, titanium and zirconium, each calculated as W, M, Ti, and Zr, is usually in the above-mentioned ranges .

The sum of the constituents of the catalytically active composition mentioned above in the particularly and very particularly preferred embodiment is usually 70 to 100% by weight, preferably 80 to 100% by weight, particularly preferably 90 to 100% by weight, Particularly> 95 wt .-%, very particularly> 98 wt .-%, in particular> 99 wt .-%, z. B. particularly preferably 100 wt .-%.

In preferred embodiments, the catalysts of the invention are used as full, impregnated, shell and precipitated catalysts. The catalyst according to the invention is given before being unsupported.

The catalyst used in the process according to the invention can in particular be characterized in that the copper component, the aluminum component and the component of at least one oxygen-containing compound of lanthanum, tungsten, molybdenum, titanium or zirconium, preferably precipitated with a soda solution, simultaneously or in succession is then dried, calcined, tabletted and calcined again.

In particular, the following precipitation method comes into consideration: A) A copper salt solution, an aluminum salt solution and a solution of at least one salt of lanthanum, tungsten, molybdenum, titanium or zirconium or a solution containing copper, aluminum and at least one of the salts of lanthanum, tungsten, molybdenum, titanium or zirconium , is precipitated in parallel or one after the other with a soda solution. The precipitated material is then dried and, if necessary, calcined.

B) Precipitation of a copper salt solution and a solution of at least one salt of lanthanum, tungsten, molybdenum, titanium or zirconium or a solution containing copper salt and at least one salt of lanthanum, tungsten, molybdenum, titanium or zirconium on a prefabricated aluminum oxide carrier. In a particularly preferred embodiment, this is present as a powder in an aqueous suspension. The carrier material can, however, also be in the form of spheres, strands, grit or tablets.

B1) In one embodiment (I), a copper salt solution and a solution of at least one salt of lanthanum, tungsten, molybdenum, titanium or zirconium or a solution containing copper salt and at least one salt of lanthanum, tungsten, molybdenum, titanium or zirconium is used , preferably with soda solution. An aqueous suspension of the support material aluminum oxide is used as a template.

Precipitated precipitates resulting from A) or B) are filtered in the usual way and preferably washed alkali-free, as is described, for example, in DE 198 09418.3.

Both the end products from A) and those from B) are dried at temperatures of 50 to 150 ° C., preferably at 120 ° C. and then optionally preferably for 2 hours at generally 200 to 600 ° C., in particular at 300 to 500 Calcined ° C.

In principle, all Cu (I) and / or Cu (II) salts, such as nitrates, carbonates, acetates, oxalates or ammonium complexes, which are soluble in the solvents used during application, can be used as starting substances for A) and / or B) Aluminum salts and salts of lanthanum, tungsten, molybdenum, titanium or zirconium can be used. Copper nitrate is used with particular preference for processes according to A) and B).

In the process according to the invention, the dried and optionally calcined powder described above is preferably processed into tablets, rings, ring tablets, extrudates, honeycomb bodies or similar shaped bodies. All suitable methods known from the prior art are conceivable for this.

The catalysts produced in this way are distinguished by the fact that the addition of lanthanum, tungsten, molybdenum, titanium or zirconium during the precipitation leads to a high stability of the catalyst. A further increase in the stability of the catalyst is achieved by adding powdery metallic copper or copper flakes and cement according to step (ii).

Preferably, graphite is added to the oxidic material and / or the mixture resulting from (ii) in a total amount of 0.5 to 5% by weight, based on the total weight of the oxidic material. This is to be understood as meaning that the total added amount is in the range mentioned, that is to say, for example, 1% by weight of the oxidic material and a further 2% by weight of graphite are added to the mixture resulting from (ii) (cf. also in this regard Example 1).

After adding the copper powder, the copper flakes or optionally the cement powder or the mixture thereof and optionally graphite to the oxidic material, the catalyst obtained after the deformation is usually calcined at least once for a period of generally 0.5 to 10 hours, preferably 0.5 to 2 hours. The temperature in this at least one calcination step is generally in the range from 200 to 600.degree. C., preferably in the range from 250 to 500.degree. C. and particularly preferably in the range from 270 to 400.degree.

In the case of shaping with cement powder, it can be advantageous to moisten the shaped body obtained before the calcination with water and then to dry it.

In order to further improve the stability of the catalyst, in an additional step (iv) the copper oxide-containing catalyst obtained in step (iii), as described in WO 2007/006719 A1 (BASF Aktiengesellschaft), can be treated with boiling water and / or steam .

According to the invention, it is also possible to use a catalyst which consists essentially of oxygen-containing compounds of Cu and Al. In this case, the sum of these two components, calculated as Cu or Al, of the catalytically active composition of the catalyst is usually 90 to 100% by weight, preferably 98 to 100% by weight, particularly preferably> 99% by weight, very particularly preferably 100% by weight.

Such catalysts, which essentially consist of oxygen-containing compounds of Cu and Al, can be produced by various processes. They can be obtained, for example, by peptizing powdery mixtures of the hydroxides, carbonates, oxides and / or other salts of the aluminum and copper components with water and then extruding and tempering the resulting mass.

The catalysts used in the process according to the invention can also be impregnated with aluminum oxide (Al2O3), for example in the form of powder or tablet shaped bodies present, are produced. Aluminum oxide can be used in various modifications, a- (alpha), y- (gamma) or O-AhCh (theta-AhCh) are preferred. Y-AI203 is particularly preferred.

Moldings of aluminum oxide can be produced by the customary processes. The catalyst preferably has a tablet shape with a diameter in the range from 1 to 4 mm and a height in the range from 1 to 4 mm.

In principle, the production of such catalysts, which consist essentially of oxygen-containing compounds of Cu and Al, is known to the person skilled in the art and is described, for example, in WO 2010/031719 A1 (BASF SE).

To activate the catalyst according to the invention with hydrogen, preferably hydrogen-inert gas mixtures, in particular hydrogen / nitrogen mixtures, at temperatures in the range from 100 to 500 ° C, preferably in the range from 150 to 350 ° C and in particular in the range from 180 to 200 ° C pre-reduced. Preference is given to using a mixture with a hydrogen content in the range from 1 to 100% by volume, particularly preferably in the range from 1 to 50% by volume.

In a preferred embodiment, the catalyst according to the invention is activated in a manner known per se by treatment with hydrogen before it is used. It is activated either beforehand in a reduction furnace or after installation in the reactor. If the reactor has previously been activated in the reduction furnace, it is installed in the reactor and charged directly under hydrogen pressure with the other starting materials nitrogen compound and aldehyde and / or ketone. If it has been reduced in the reduction furnace and its surface passivated, it can be treated with the starting materials either without further reductive treatment with hydrogen or after a further treatment with hydrogen in the reactor.

PROCEDURE

Unless otherwise stated, all pressure data relate to the absolute pressure.

The process according to the invention can be carried out continuously or batchwise, with a continuous procedure being preferred.

The method according to the invention can be operated in one (alternative 1) or in two stages (alternative 2). The resulting reaction product is usually an imine or enamine. This is hydrogenated in the presence of hydrogen and the catalyst.

According to alternative 1, the aldehyde and / or ketone is reacted with the nitrogen compound together with the hydrogenation in the liquid phase and in the presence of the hydrogen and the catalyst. Accordingly, the reaction of the aldehyde and / or ketone with the nitrogen compound and the hydrogenation take place under the same reaction conditions. In other words, everything that has been said with regard to the hydrogenation conditions also applies to the reaction of the aldehyde and / or ketone with the nitrogen compound.

According to alternative 2, the aldehyde and / or ketone is reacted with the nitrogen compound in a step preceding the hydrogenation. In this case, the aldehyde and / or ketone are reacted with the nitrogen compound in the absence of hydrogen and catalyst to give the resulting reaction product. This is hydrogenated in a subsequent step in the presence of hydrogen and the catalyst.

According to alternative 2, the aldehyde or ketone is reacted with the nitrogen component generally at pressures of 0.1 to 30 MPa, preferably 0.1 to 25 MPa, particularly preferably 0.1 to 21 MPa, and temperatures generally 10 to 250 ° C, particularly 15 to 240 ° C, preferably 20 to 230 ° C, particularly preferably 25 to 220 ° C, in particular 30 to 210 ° C. For the hydrogenation of the resulting reaction product, the temperatures and pressures mentioned below in connection with the work according to the invention in the liquid phase are preferred.

According to alternative 1, the amine is prepared by reacting the aldehyde and / or the ketone and the nitrogen compound together with the hydrogenation in the liquid phase and in the presence of the hydrogen and the catalyst. The hydrogenation of the resulting reaction product from the reaction of the aldehyde or ketone with the nitrogen compound takes place in situ. A procedure according to alternative 1 is preferred. The reaction and subsequent hydrogenation take place under the same conditions.

When working according to the invention in the liquid phase, the starting materials (aldehyde or ketone plus nitrogen component) (alternative 1) or the reaction product according to the invention from the reaction of aldehyde and / or ketone with the nitrogen components (alternative 2) are brought into the liquid phase simultaneously at pressures of generally 1 to 30 MPa (10-300 bar), preferably 2 to 25 MPa, particularly preferably 3 to 20 MPa, and temperatures of 20 to 230 ° C, particularly 30 to 220 ° C, preferably 40 to 210 ° C , particularly preferably 50 to 200 ° C, in particular 60 to 190 ° C, including hydrogen in contact with the catalyst. The catalyst is usually located in an adiabatic or an externally cooled reactor, in particular a fixed bed reactor, for example a tube bundle reactor in the case of a continuous reaction or an autoclave in the case of a discontinuous reaction. In the case of a continuous reaction procedure, both a trickle mode and a sump mode are possible. When the reaction is carried out continuously, the space velocity over the catalyst is generally in the range from 0.05 to 5, preferably 0.1 to 2, particularly preferably 0.2 to 0.6, kg of aldehyde or ketone (alternative 1) or reaction product (alternative 2) per Liters of catalyst (bulk volume) and hour. Both in the continuous and in the discontinuous reaction procedure, if appropriate, a dilution of the reaction product or the starting materials with a suitable solvent, such as tetrahydrofuran, dioxane, N-methylpyrro- lidone, methanol, isopropanol or ethylene glycol dimethyl ether. If the reaction is carried out continuously, it is advantageous to heat the reactants before they are fed into the reaction vessel, preferably to the reaction temperature. The reaction is preferably carried out in the continuous reaction procedure without a solvent.

In the case of a continuous procedure, the hydrogenation can be carried out in a reactor, usually a fixed bed reactor, for example isothermally or adiabatically, in the case of an isothermal reaction procedure for both alternatives usually the temperature in the range from 100 to 230 ° C, preferably 105 to 220 ° C, particularly preferably 110 to 210 ° C and very particularly preferably 115 to 200 ° C. In the case of an adiabatic reaction regime, the temperature on entry into the reactor for alternative 1 is usually in the range from 20 to 140 ° C., preferably 60 to 140 ° C., particularly preferably 65 to 130, very particularly preferably 70 to 120 ° C., or even 75 to 110 ° C, and for alternative 2 in the range from 80 to 140 ° C, preferably 90 to 130, particularly preferably 95 to 120 ° C, very particularly preferably 100 to 110 ° C and on the exit for both alternatives usually in the range from 130 to 230 ° C., preferably from 140 to 220 ° C., particularly preferably from 150 to 210 ° C., the temperature at the exit always being greater than at the entry.

Alternative 1 is preferred in an isothermal or adiabatic reaction procedure. If the reaction is carried out in an adiabatic manner, the heat released during the reaction of the aldehyde / ketone with the amine can lead to a significant increase in temperature. It is therefore possible to feed the starting materials into the reactor at very low temperatures. For example, in a continuous mode of operation, a feed stream having a temperature of 20 ° C. can rise significantly (for example to 80 or 100 ° C.) as a result of the heat released from said reaction and thus reach the temperature required for a hydrogenation.

The process according to the invention is preferably carried out continuously, the catalyst preferably being arranged as a fixed bed in the reactor. A flow of water onto the fixed catalyst bed from above as well as from below is possible.

The nitrogen component can be used in stoichiometric, under- or over-stoichiometric amounts with respect to the aldehyde group or keto group to be aminated.

In the case of the amination of aldehydes or ketones with primary or secondary amines, the amine is preferably used in an approximately stoichiometric amount or a slightly more stoichiometric amount per mole of aldehyde group and / or keto group to be aminated.

The amine component (nitrogen compound) is preferably used in 0.50 to 100 times the molar amount, in particular in 1.0 to 10 times the molar amount, or particularly preferably 1.1 to 5 times, very particularly preferably 1 , 5 to 4 times or even 2 to 3 times the molar amount, based in each case on the aldehyde groups and / or keto groups to be aminated. Ammonia in particular is generally used with a 1.5 to 250-fold, preferably 2 to 100-fold, in particular 2 to 10-fold molar excess per mole of aldehyde group and / or keto group to be converted.

Larger excesses of both ammonia and primary or secondary amines are possible.

When the reaction is carried out continuously, an amount of waste gas of 5 to 800 standard cubic meters / m ³ _reactor / h, in particular 20 to 300 standard cubic meters / m ³ _reactor / h, is preferably run. (Standard cubic meter = converted to standard conditions Volume, m ³ = _Re actuator reactor volume).

Hydrogen is generally used in a 1 to 50-fold, preferably 1 to 20-fold, particularly preferably 1.5 to 15-fold and very particularly preferably 2 to 10-fold molar excess per mole of aldehyde group and / or keto group to be converted .

In the hydrogenation, it is in principle also possible to use higher temperatures and higher total pressures and space velocity over the catalyst. The pressure in the reaction vessel, which results from the sum of the partial pressures of the nitrogen component, the aldehyde or ketone and the reaction products formed and possibly the solvent used at the specified temperatures, is expediently increased to the desired reaction pressure by forcing hydrogen.

When working continuously in the liquid phase according to alternative 1, the excess aminating agent can be circulated together with the hydrogen. When the reaction is carried out adiabatically, the increase in temperature is correspondingly lower, the greater the ratio of recycle stream to educt stream.

If the catalyst is arranged as a fixed bed, it can be advantageous for the selectivity of the reaction to mix the shaped catalyst bodies in the reactor with inert packing, so to speak "dilute" them. The proportion of packing in such catalyst preparations can be 20 to 80, especially 30 to 60 and in particular 40 to 50 parts by volume.

The water of reaction formed in the course of the reaction (in each case one mole per mole of converted aldehyde group or keto group) generally does not interfere with the degree of conversion, the reaction rate, the selectivity and the catalyst life and is therefore expediently only used when the resulting crude is worked up Amine removed from this sem, z. B. by distillation.

After it has expediently been depressurized, the excess hydrogen and the excess amine which may be present are removed from the reaction discharge. approximately removed and the amine crude product obtained is purified, for. B. by a fractionating rectification. Suitable work-up methods are, for. B. in EP 1 312 600 A and EP 1 312 599 A (both BASF AG). The excess aminating agent and the hydrogen are advantageously returned to the reaction zone. The same applies to any aldehyde or ketone components that may not have been fully converted.

Unreacted starting materials and any suitable by-products which may be obtained can be returned to the synthesis. Unreacted starting materials can be flowed again over the catalyst bed in a batchwise or continuous procedure.

EDUCTS

Of the possible starting materials aldehyde and ketone, aldehydes, in particular mono-aldehydes (aldehydes with only one aldehyde group), are preferred.

Preference is given to aliphatic (including cycloaliphatic) or aromatic aldehydes or ketones having at least 7 carbon atoms (in the case of an aldehyde) or at least 8 carbon atoms (in the case of a ketone), preferably 7 to 15 or 8 to 16 carbon atoms. Said compounds can contain further fleteroatoms, such as, for example, O, N or S, preference being given to corresponding aliphatic or aromatic hydrocarbons which do not contain any fleteroatoms. Corresponding aromatic compounds are also preferred, and corresponding aromatic aldehydes are particularly preferred.

In addition to ammonia, aminating agents in the process according to the invention are primary and secondary amines. Diamines, in particular primary diamines, are particularly preferred.

The process according to the invention is particularly suitable for the preparation of an amine by reacting an aldehyde and / or ketone with a primary diamine (for example 1,2-ethylenediamine (EDA) or 1,2-propylene diamine (1,2-PDA) but also diethylenetriamine (DETA ) or triethylenetetraamine (TETA)).

The process according to the invention is suitable, for example, for the preparation of amines of the formula (A) by reaction of an aldehyde and / or ketone of the formula (a) with an amine of the formula where in the formulas (A), (a) and (b) n 0 to 7,

R ^a substituted or unsubstituted phenyl R ^A CHR'R ³ ,

R ^B , R ^c , R ^D , R ^E independently of one another R ^A or H,

R ^F and R ^G (if n = 1 to 7) both H, or (if n = 0) both H or one of the two radicals H and the other methyl,

R 'H or Ci to C ₄ alkyl. mean.

For n = 0, the amine of formula (b) corresponds to either 1, 2-EDA or 1, 2-PDA, for n = 1 for example DETA and for n = 2 TETA.

^{R a} is preferably unsubstituted phenyl.

The reaction with an aldehyde is preferred. In this case, R 'H.

How many of the radicals R ^B , R ^c , R ^D and R ^{E are} Fl or R ^A depends essentially on the molar ratio of amine to ketone or aldehyde. The higher the excess of amine, the more of the radicals R ^B , R ^c , R ^D and R ^E mean Fl. What has been said above with regard to the molar amount of the amine component applies accordingly. N is preferably from 0 to 4.

For n = 0, corresponding mixtures of amines in which R ^B and R ^{D are} H and R ^{c are} either H or R ^{A are} preferred. This corresponds to a mixture of amines in which only one amino group or both amino groups of the 1,2-EDA or 1,2-PDA have reacted with an aldehyde or ketone and consequently the formulas (Ia) and (Ib) shown below.

For n = 1 to 7 or 1 to 4, R ^B , R ^D and R ^{E are} preferably H. Particularly preferred is the formation of corresponding mixtures of amines in which R ^B , R ^D and R ^E Fl and R ^{c are} either Fl or R ^A mean. In this context, the preparation of benzyl diethylenetriamine (benzyl DETA) and N, N'-benzyl diethylenetriamine (dibenzyl DETA) by conversion of diethylenetriamine (DETA) and benzaldehyde and the preparation of benzyltriethylenetetramine (benzyl -TETA) and N, N'-benzyl-triethylenetetramine (dibenzyl-TETA) through the reaction of triethylenetetramine (TETA) and benzaldehyde.

R ¹ is preferably H or methyl, particularly preferably (because aldehydes are preferred) H.

The inventive method is particularly suitable for the preparation of amines of the formula (la) or (Ib) and (lb ‘)

1. and by reacting an aldehyde and / or ketone of the formula (II) and 1,2-ethylenediamine (EDA) or 1,2-propylene diamine (1,2-PDA) where in the formulas (Ia), (Ib), (Ib ') and (II) n for 0 or 1 or 2 or 3,

R stands for a hydrogen radical or for a hydrocarbon radical with 1 to 6 carbon atoms, X for identical or different radicals selected from the group consisting of alkyl, alkoxy and dialkylamino with 1 to 18 carbon atoms each, and Y for a hydrogen Radical or a radical of the formula in which case the amines of the formula (Ib) and (Ib ') are identical. The preparation of amines of the formula (Ia) is preferred.

With regard to amines of the formula (la), the following features and combinations of features are preferred: R preferably stands for a hydrogen radical or for methyl or for phenyl. R is particularly preferably a hydrogen radical or methyl, in particular a hydrogen radical.

N is preferably 0 or 1 or 2, particularly preferably 0 or 1, very particularly preferably 0.

X preferably represents identical or different radicals selected from the group consisting of alkyl, alkoxy and dialkylamino each having 1 to 12, in particular 1 to 4, carbon atoms. X is particularly preferably methyl or isopropyl or tert-butyl or methoxy or dimethylamino. X is very particularly preferably methoxy or dimethylamino.

The radical X is preferably in the meta and / or para position. In the case of n = 1, the radical X is in particular in the para position.

An amine of the formula (Ia) in which R is a hydrogen radical and n is 0 is particularly preferred.

Particularly preferred is also an amine of the formula (Ia) in which R is a hydrogen radical, n is 1 and X is methoxy or dimethylamino in the para position.

The reaction of EDA with the corresponding aldehyde or ketone of the formula (II) always results in both corresponding amines of the formula (Ia) in which Y is hydrogen and those in which Y is a corresponding radical according to the above formula. Their ratio can be adjusted by the molar ratio of EDA to aldehyde / ketone of the formula (II). Since the following applies, the higher the excess of EDA, the higher the proportion of amines of the formula (Ia) in which Y is hydrogen. Corresponding preferred ratios of amine to aldehyde / ketone in general are specified above.

Particularly preferred is the formation of amines of the formula (Ia) which are selected from the group consisting of N-benzyl-1,2-ethanediamine and N, N'-dibenzyl-1,2-ethanediamine, N- (4-methylbenzyl ) -1, 2-ethanediamine and N, N'-di (4-methylbenzyl) -1, 2-ethanediamine, N- (4-isopropylbenzyl) -1, 2-ethanediamine and N, N'-di (4 -Isopropylbenzyl) -1, 2-ethanediamine, N- (4-tert-butylbenzyl) -1, 2-ethanediamine and N, N'-di (4-tert-butylbenzyl) -1, 2-ethanediamine, N- (4 -Methoxybenzyl) -1, 2-ethanediamine and N, N'-di (4-methoxybenzyl) -1, 2-ethanediamine, N- (4- (dimethylamino) benzyl) -1, 2-ethanediamine and N, N'-di (4- (dimethylamino) benzyl) -1, 2-ethanediamine, N- (1-phenylethyl) -1, 2-ethanediamine and NN'-di (1-phenylethyl) -1, 2-ethanediamine, N-benzhydryl-1,2-ethanediamine and N, N'-dibenzhydryl-1,2-ethanediamine, N- (1- (4'-methyl) phenylethyl) -1, 2-ethanediamine and N , N'-di (1- (4'-methyl) phenylethyl) -1, 2-ethanediamine and N- (1- (4'-methoxy) phenylethyl) -1, 2-ethanediamine and N, N'-di ( 1- (4'-methoxy) phenylethyl) -1, 2-ethanediamine, a Us the correspond to the aldehydes or ketones and 1, 2-EDA. Of these, preference is given to N-benzyl-1, 2-ethanediamine and N, N'-dibenzyl-1, 2-ethanediamine, N- (4-methoxybenzyl) -1, 2- ethanediamine and N, N'-di (4-methoxybenzyl) -1, 2- ethanediamine and N- ( 4- (dimethylamino) benzyl) -1, 2-ethanediamine and N, N'-di (4- (dimethylamino) benzyl) -1, 2-ethanediamine, in particular N-benzyl-1,2-ethanediamine and N, N ' - Dibenzyl-1,2-ethanediamine.

Particularly suitable aldehydes of the formula (II) are benzaldehyde, 2-methylbenzaldehyde (o-tolualdehyde), 3-methylbenzaldehyde (m-tolualdehyde), 4-methylbenzaldehyde (p-tolualdehyde),

2,5-dimethylbenzaldehyde, 4-ethylbenzaldehyde, 4-isopropylbenzaldehyde (cuminaldehyde), 4-tert.-butylbenzaldehyde, 2-methoxybenzaldehyde (o-anisaldehyde), 3-methoxybenzaldehyde (m-anisaldehyde), 4-methoxybenzaldehyde (anisaldehyde), 2 , 3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde (veratrumaldehyde),

3,5-dimethoxybenzaldehyde, 2,4,6-trimethylbenzaldehyde, 2,4,5-trimethoxybenzaldehyde (asaronaldehyde), 2,4,6-trimethoxybenzaldehyde, 3,4,5-trimethoxybenzaldehyde or 4-dimethylaminobenzaldehyde. Benzaldehyde, 4-isopropylbenzaldehyde (cuminaldehyde), 4-tert-butylbenzaldehyde, 4-methoxybenzaldehyde (anisaldehyde) or 4-dimethylaminobenzaldehyde are preferred.

Particularly suitable ketones of the formula (II) are acetophenone, benzophenone, 2'-methyl acetophenone, 3'-methylacetophenone, 4'-methylacetophenone, 2'-methoxyacetophenone, 3'-methoxyacetophenone, 4'-methoxyacetophenone, 2 ' , 4'-dimethylacetophenone, 2 ', 5'-dimethylacetophenone, 3', 4'-dimethylacetophenone, 3 ', 5'-dimethylacetophenone, 2', 4'-dimethoxyacetophenone, 2 ', 5'-dimethoxyacetophenone, 3' , 4'-dimethoxyacetophenone, 3 ', 5'-dimethoxyacetophenone,

2 ', 4', 6'-trimethylacetophenone or 2 ', 4', 6'-trimethoxyacetophenone. Acetophenone, benzophenone, 4'-methylacetophenone or 4'-methoxyacetophenone are preferred. Acetophenone is particularly preferred.

Benzaldehyde, 4-methoxybenzaldehyde (anisaldehyde) or 4-dimethylaminobenzaldehyde is particularly preferred as the aldehyde or ketone of the formula (II). Benzaldehyde is most preferred.

In one embodiment, a mixture of two or more different aldehydes or ketones of the formula (II) is used for the reaction, in particular a mixture of benzaldehyde and 4-methoxybenzaldehyde or 4-dimethylaminobenzaldehyde.

With regard to amines of the formula (Ib) and (lb ‘), the following features and combinations of features are preferred:

X preferably represents identical or different radicals selected from the group consisting of alkyl, alkoxy and dialkylamino, each with 1 to 12, in particular 1 to 4, carbon atoms. X particularly preferably represents methyl or methoxy or dimethylamino. R is preferably a hydrogen radical or methyl, in particular a hydrogen radical.

An amine of the formula (Ib) and (Ib ‘) in which n is 0 is particularly preferred.

Also particularly preferred is an amine of the formula (Ib) in which n is 1 and X is methoxy or dimethylamino.

The methoxy group or the dimethylamino group is preferably in the para position.

The reaction of 1, 2-PDA with the corresponding aldehyde or ketone of the formula (II) always results in both corresponding amines of the formula (Ib) and (Ib ') in which Y is hydrogen and those in which Y is a corresponding radical is according to the above formula. Their ratio can be adjusted by the molar ratio of 1,2-PDA to aldehyde / ketone of the formula (II). The following applies here: the higher the excess of 1,2-PDA, the higher the proportion of amines of the formula (Ib) and (Ib l) in which Y is hydrogen. Corresponding preferred ratios of amine to aldehyde / ketone in general are specified above.

If Y is not hydrogen, then the amines of the formula (Ib) and (Ib l) are identical. With regard to such amines in which Y is hydrogen, more amine of the formula (Ib) than amine of the formula (Ib ‘) is usually formed. This is due to the fact that the amino group further away from the methyl group can react more easily with an aldehyde or ketone.

The position of amines of the formula (Ib) and (Ib und) which are selected from the group consisting of is very particularly preferred

N ¹ -benzyl-1, 2-propanediamine, N ² -benzyl-1, 2-propanediamine and N ¹ , N ² -dibenzyl-1, 2-propanediamine,

N ¹ - (4-isopropylbenzyl) -1,2-propanediamine, N ² - (4-isopropylbenzyl) -1,2-propanediamine and N ¹ , N ² -di (4-isopropylbenzyl) -1,2-propanediamine

N ¹ - (4-tert.-butylbenzyl) -1, 2-propanediamine, N ² - (4-tert.-butylbenzyl) -1, 2-propanediamine and N1, N2-di (4-tert.-butylbenzyl) - 1,2-propanediamine

N ¹ - (4-methoxy-benzyl) -1, 2-propanediamine, N ² - (4-methoxy-benzyl) -1, 2-propanediamine and N ¹ , N ² -di (4-methoxy-benzyl) -1 , 2-propanediamine

N ¹ - (4- (dimethylamino) benzyl) -1, 2-propanediamine, N ² - (4- (dimethylamino) benzyl) -1, 2-propanediamine and N ¹ , N ² -di (4- (dimethylamino ) benzyl) -1, 2-propanediamine N ¹ - (1-phenylethyl) -1, 2-propanediamine, N ² - (1-phenylethyl) -1, 2-propanediamine and N ¹ , N ² - di (1-phenylethyl ) -1, 2-propanediamine

N ¹ -benzhydryl-1,2-propanediamine, N ² -benzhydryl-1,2-propanediamine and N ¹ , N ² -dibenzhydryl-1,2-propanediamine N ¹ - (1- (4'-methyl) phenylethyl) -1, 2-propanediamine, N ² - (1- (4'-methyl) phenylethyl) -1, 2-propanediamine and N ¹ , N ² -Di (1- (4'-methyl) phenylethyl) -1, 2-propanediamine and N ¹ - (1- (4'-methoxy) phenylethyl) -1, 2-propanediamine, N ² - (1- (4'-methoxy ) phenylethyl) - ^{1,2-propanediamine and N 1} , N ² -Di (1- (4'-methoxy) phenylethyl) - 1,2-propanediamine from the corresponding aldehydes or ketones and 1,2-PDA.

Of these, N ¹ -benzyl-1,2-propanediamine, N ² -benzyl-1,2-propanediamine and N ¹ , N ² -dibenzyl-1,2-propanediamine are very particularly preferred.

Of these, N ¹ - (4-methoxybenzyl) -1, 2-propanediamine, N ² - (4-methoxybenzyl) -1, 2-propanediamine and N ¹ , N ¹ -di (4-methoxybenzyl) -1 are very particularly preferred , 2-propanediamine.

Of these, N ¹ - (4- (dimethylamino) benzyl) -1, 2-propanediamine, N ² - (4- (dimethylamino) benzyl) -1, 2-propanediamine and N ¹ , N ² - (4 - (Dimethylamino) benzyl) -1, 2-propanediamine.

According to the above nomenclature, N ^{1 is} bound to the primary and N ² to the secondary carbon atom of the 1,2-PDA.

2,5-dimethylbenzaldehyde, 4-ethylbenzaldehyde, 4-isopropylbenzaldehyde (cuminaldehyde), 4-tert-butylbenzaldehyde, 2-methoxybenzaldehyde (o-anisaldehyde), 3-methoxybenzaldehyde (m-anisaldehyde), 4-methoxybenzaldehyde (anisaldehyde), 2,3 -Dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde (veratrumaldehyde),

Particularly suitable ketones of the formula (II) are acetophenone, benzophenone, 2'-methyl acetophenone, 3'-methylacetophenone, 4'-methylacetophenone, 2'-methoxyacetophenone, 3'-methoxyacetophenone, 4'-methoxyacetophenone, 2 ' , 4'-dimethylacetophenone, 2 ', 5'-dimethylacetophenone, 3', 4'-dimethylacetophenone, 3 ', 5'-dimethylacetophenone, 2', 4'-dimethoxyacetophenone, 2 ', 5'-dimethoxyacetophenone, 3' , 4'-dimethoxyacetophenone, 3 ', 5'-dimethoxyacetophenone, 2', 4 ', 6'-trimethylacetophenone or 2', 4 ', 6'-trimethoxyacetophenone. Acetophenone, benzophenone, 4'-methylacetophenone or 4'-methoxyacetophenone are preferred. Acetophenone is particularly preferred

Benzaldehyde, 4-methoxybenzaldehyde or 4-dimethylaminobenzaldehyde are particularly preferred as the aldehyde or ketone of the formula (II). Benzaldehyde is most preferred.

The following examples serve to illustrate the invention without restricting it in any way.

EXAMPLES

Example 1a: Production of a catalyst containing Cu, Al and La

A mixture of 12.41 kg of a 19.34% copper nitrate solution, and 14.78 kg of an 8.12% aluminum nitrate solution and 1.06 kg of a 37.58% lanthanum nitrate solution x 6H ₂ O were in 1, 5 I dissolved water (solution 1). Solution 2 contains 60 kg of a 20% anhydrous Na ₂ CC> ₃ . Solution 1 and solution 2 are passed through separate lines into a precipitation vessel which is provided with a stirrer and contains 10 l of water heated to 60 ° C. The pH value was brought to 6.2 by setting the feed rates of solution 1 and solution 2 accordingly.

While keeping the pH constant at 6.2 and the temperature at 60 ° C, the entire solution was reacted with soda. The suspension thus formed was then stirred for 1 hour, the pH being raised to 7.2 by the occasional addition of dilute nitric acid or soda solution 2. The suspension is filtered and washed with distilled water until the nitrate content of the wash water was <10 ppm.

The filter cake was dried at 120 ° C. for 16 hours and then calcined at 300 ° C. for 2 hours. The catalyst powder obtained in this way is precompacted with 18.9 g (1% by weight) of graphite. The compacted material obtained is mixed with 94.6 g of Cu flakes Unicoat and then with 37.8 g (2% by weight) of graphite and compressed to form tablets 3 mm in diameter and 3 mm in height. The tablets were finally calcined at 350 ° C. for 2 hours.

The catalyst produced in this way has the chemical composition:

Oxygen-containing compounds of copper, calculated as Cu: 68% by weight

Oxygen-containing compounds of aluminum, calculated as Al: 13% by weight Oxygen-containing compounds of lanthanum, calculated as La: 11% by weight

Elemental copper: 8% by weight

The above concentration data (in% by weight) relate to the total mass of the metals (Cu, Al, La). Example 1b: Production of a catalyst containing Cu and Al

The catalyst was produced by impregnating gamma-A ^ Os powder with an aqueous copper nitrate solution and then calcining it. Tableting took place according to the customary method.

The catalyst produced in this way has the chemical composition:

Oxygen-containing compounds of copper, calculated as Cu: 64.8% by weight

Oxygen-containing compounds of aluminum, calculated as AI: 35.2% by weight

The above concentration data (in% by weight) relate to the total mass of the metals (Cu, Al).

Example 2 - Continuous production of N-Benzyl-1,2-ethylenediamine (NBEDA)

A 6 L miniplant reactor was used. This was filled from bottom to top with 1000 mL ceramic rings, 3500 mL catalyst according to Example 1a (hereinafter referred to as catalyst) and 1600 mL ceramic rings. The catalyst was activated under normal pressure at a starting temperature of 180 ° C. with hydrogen diluted with nitrogen. After 12 hours the temperature was increased to 200 ° C. Activation was then continued for a further 6 hours at a temperature of 200 ° C. using pure hydrogen. The reactor was then cooled down to 70 ° C., hydrogen was injected up to a pressure of 100 bar and 1,2-ethylenediamine (1,2-EDA) was added. After the catalyst was completely soaked with 1,2-EDA, it was heated to the desired temperature. 1, 2-EDA and benzaldehyde (BA) were fed into a mixing chamber in the desired ratio and fed into the reactor via a preheater. Benzaldehyde was completely converted. Further reaction parameters are listed in Table 1.

Samples were examined by gas chromatography. For this purpose, a DB1 column from Agilent (length: 30 m, inner diameter: 0.32 mm, layer thickness: 3.0 μm) and a flame ionization detector were used. The temperature program was as follows: start at 80 ° C., heating to 280 ° C. at 10 ° C./min, maintaining this temperature for 35 min. The respective peaks were identified by means of GC-MS (gas chromatography with mass spectrometry coupling). The molar selectivity based on BA was calculated for the individual components from the respective GC area percentages. belle 1

Temperature: molar ratio I: dibenzylethylene diimine and dibenzylethyleneimine OH: benzyl alcohol H ₂ : benzylamine

Benzaldehyde benzyl-EDA: N, N'-dibenzyl-1,2-ethylenediamine EDA N-benzyl-1,2-ethylenediamine

Discussion of the results:

According to Table 1, the products of value N-benzyl-1,2-ethylenediamine (NBEDA) and N, N‘-di-benzyl-1,2-ethylenediamine are obtained in high yield and selectivity. At the same time, even after a running time of 1924 hours, the catalytic converter still has sufficient activity and thus high stability and service life. Accordingly, the catalyst is also suitable for a large-scale industrial process.

Comment on the following Examples 3 to 5: An activated catalyst is understood to mean its reduction in a hydrogen stream at about 200.degree.

Example 3 - Batch Production of NBEDA and Dibenzyl-EDA:

Example 3a:

In a beaker, 20.2 g (0.34 mol) of 1,2-ethylenediamine were dissolved in 30 g of methanol and 17.8 g (0.16 mol) of benzaldehyde were added with cooling. This mixture was divided into two electrically heated 160 mL autoclaves with a catalyst basket made of wire mesh, which had a recess in the middle for a mechanical propeller stirrer. The catalyst basket was filled with activated catalyst (5 g of 3 × 3 mm tablets) according to Example 1b and the autoclave was closed. After flushing with nitrogen, 20 bar of hydrogen were injected. Now one autoclave was heated to 110 ° C. and the other to 130 ° C. and the hydrogen pressure was increased to 90 bar at the respective end temperature. After 12 hours, the autoclaves were cooled and let down. The product mixture was analyzed by GC as described in Example 2.

Excess ethylenediamine was eliminated. At 110 ° C the selectivity to N-benzyl-1,2-ethylenediamine was 47% and to N, N'-dibenzylethylenediamine 48%, at 130 ° C the selectivity to N-benzyl-1,2-ethylenediamine was 49% and to N, N'-dibenzyl-1,2-ethylenediamine 45%. The conversion of benzaldehyde was 100% in each case.

Example 3b:

Using the same procedure as in Example 3a, a mixture of ethylenediamine and benzaldehyde in MeOH was hydrogenated over an activated catalyst (5 g 3 × 3 mm tablets) according to Example 1a at 110 ° and 130 ° C. and analyzed. Excess ethylenediamine was calculated out. At 110 ° C. the selectivity for N-benzyl-1,2-ethylenediamine was 47% and for N, N'-di-benzylethylenediamine, and at 130 ° C. the selectivity for N-benzyl-1,2-ethylenediamine was 50% % and to N, N'-dibenzyl-1,2-ethylenediamine 44%. The conversion of benzaldehyde was 100% in each case.

Example 4 - discontinuous production of N-benzyl-diethylenetriamine (benzyl-DETA) and N, N‘-benzyl-diethylenetriamine (dibenzyl-DETA) with two different molar ratios:

In a beaker, 20.0 g (0.19 mol) of diethylenetriamine (DETA) were dissolved in 15 g of MeOH and 20.6 g (0.19 mol) of benzaldehyde were added dropwise. This mixture was poured into an autoclave according to Example 3a, and the catalyst basket with 10 g of activated catalyst according to Example 1a filled. It was hydrogenated as described for 12 h at 90 bar and 130 ° C. The raw mixture was analyzed by gas chromatography.

For this purpose, an RTX-5 amine column from Agilent (length: 30 m, inner diameter: 0.32 mm, layer thickness: 1.5 μm) and a flame ionization detector were used. The temperature program was as follows: start at 60 ° C., heating to 280 ° C. at 6 ° C./min, maintaining this temperature for 28 min. The respective peaks were identified by means of GC-MS (gas chromatography with mass spectrometry coupling) . The molar selectivity based on DETA was calculated for the individual components from the respective GC area percentages.

The conversion was 83%, the selectivity for benzyl-DETA based on DETA was 72% and for dibenzyl-DETA 23%.

In a beaker, 15 g (0.15 mol) of diethylenetriamine (DETA) were dissolved in 15 g of MeOH and 30.9 g (0.29 mol) of benzaldehyde were added dropwise. This mixture was poured into an autoclave according to Example 3a, and the catalyst basket was filled with 10 g of activated catalyst according to Example 1a. It was hydrogenated as described for 12 h at 90 bar and 130 ° C. The raw mixture was analyzed by gas chromatography as described above. The conversion was 99%, the selectivity for benzyl-DETA based on DETA was 41% and for dibenzyl-DETA 49%.

Example 5 - discontinuous production of N-benzyl-triethylenetetramine (benzyl-TETA) and N, N‘-benzyl-triethylenetetramine (dibenzyl-TETA) with two different molar ratios:

In a beaker, 23 g (0.16 mol) of triethylenetetramine (TETA) were dissolved in 15 g of MeOH and 17 g (0.16 mol) of benzaldehyde were added dropwise. This mixture was poured into an autoclave according to Example 3a, and the catalyst basket was filled with 10 g of activated catalyst according to Example 1a. It was hydrogenated as described for 12 h at 90 bar and 130 ° C. The raw mixture was analyzed.

For this purpose, an RTX-5 amine column from Agilent (length: 30 m, inner diameter: 0.32 mm, layer thickness: 1.5 μm) and a flame ionization detector were used. The temperature program was as follows: start at 120 ° C., heating to 280 ° C. at 8 ° C./min, maintaining this temperature for 50 min. The respective peaks were identified by means of GC-MS (gas chromatography with mass spectrometry coupling) . The molar selectivity based on TETA was calculated for the individual components from the respective GC area percentages.

The conversion was 77%, the selectivity for benzyl-TETA based on TETA was 68% and for dibenzyl-TETA 18%. In a beaker, 21 g (0.14 mol) of triethylenetetramine (TETA) were dissolved in 15 g of MeOH and 23 g (0.22 mol) of benzaldehyde were added dropwise. This mixture was poured into an autoclave according to Example 3a, and the catalyst basket was filled with 10 g of activated catalyst according to Example 1a. It was hydrogenated as described for 12 h at 90 bar and 130 ° C. The raw mixture was analyzed by gas chromatography as above. The conversion was 91%, the selectivity for benzyl-TETA based on TETA was 59% and for dibenzyl-TETA 27%.

Example 6 - Continuous production of N-benzyl-1, 2-ethylenediamine and N.N‘-dibenzylethylenediamine in the gas phase (comparative experiment)

It should be noted that a discontinuous conversion in the gas phase is technically not realizable. Accordingly, the implementation takes place here continuously.

A vertically arranged oil-heated jacketed glass reactor 1 m long and 40 mm in diameter was filled with 200 mL steel mesh rings with a 5 mm diameter, then 100 mL of a catalyst according to Example 1b (3x3 mm tablets) and a further 700 mL mesh rings. The catalyst was reduced in a stream of hydrogen at up to 230 ° C. for 12 h. At the lower end of the reactor, a flask with an attached reflux condenser was attached, which was equipped with a tap for discharging the liquid reaction product. The reactor was equipped with a pump for liquid starting material and a line for blowing in heated hydrogen. The feeds were led to the reactor inlet at the upper end and brought to the desired temperature on the first bed of mesh rings and mixed thoroughly.

The reactor was heated to 180 ° C. and charged with 593 l / h of hydrogen. Now a mixture of 29.7% ethylenediamine and 26.1% benzaldehyde in MeOH, corresponding to the composition of the mixture that had been hydrogenated batchwise in Example 3a, was pumped in at a metering rate of 19 g / h, which was a load of 0.05 kg / L / h benzaldehyde corresponded. Samples were taken every 1 hour. After sampling after 2 hours, the reactor temperature was lowered to 175 ° C.

The sample after 2 hours was analyzed as described in Example 2. Excess ethylene diamine was calculated out. The conversion of benzaldehyde was 100%. The molar selectivity to N-benzyl-1,2-ethylenediamine was approximately 2%, the selectivity to N, N‘-dibenzyl-1,2-ethylenediamine was approximately 0%. Numerous, partly unidentified by-products were formed, so that the molar selectivity cannot be given with the same accuracy as above.

After the temperature had been reduced to 175 ° C., a sample was taken after 2 hours, which showed a selectivity for N-benzyl-1,2-ethylenediamine of about 13% and a selectivity for N, N'-dibenzyl-1,2- Ethylenediamine of about 0.2%. The conversion of benzaldehyde was 100%. Thereupon the temperature was lowered to 170 ° C. However, condensation of intermediate products or products occurred in the catalyst bed and the experiment was terminated. Obviously, the production in the gas phase does not give satisfactory results. In contrast, the results according to Example 3a show that a reaction in the liquid phase gives very good selectivities for the products of value N-benzyl-1,2-ethylenediamine and N, N'-di-benzyl-1,2-ethylenediamine.

Claims

1. A process for the preparation of an amine by reacting an aldehyde and / or ketone with a nitrogen compound selected from the group consisting of ammonia, primary and secondary amines and subsequent hydrogenation of the resulting reac tion product in the liquid phase and in the presence of hydrogen and a copper feroxide-containing heterogeneous hydrogenation catalyst at a temperature of 20 to 230 ° C, the reaction of the aldehyde and / or ketone with the nitrogen compound either together with the hydrogenation in the liquid phase and in the presence of the hydrogen and the catalyst (alternative 1) or in a step upstream of the hydrogenation (alternative 2) takes place, and the catalytically active mass of the catalyst, prior to its reduction with hydrogen, contains at least 24% by weight of oxygen-containing compounds of copper, calculated as Cu.

2. The method according to claim 1, characterized in that the catalytically active mass of the catalyst before its reduction with hydrogen in the range of

Contains 24 to 98% by weight, preferably 50 to 90% by weight, of oxygen-containing compounds of copper, calculated as Cu.

3. The method according to claim 2, characterized in that the catalytically active mass of the catalyst prior to its reduction with hydrogen in the range of 0.5 to 75 wt .-%, preferably 0.5 to 40 wt .-% oxygen-containing compounds of aluminum, calculated as AI, contains.

4. The method according to any one of claims 2 and 3, characterized in that the catalytically active mass of the catalyst before its reduction with hydrogen in the range of 0.5 to 40 wt .-% of at least one oxygen-containing compound selected from the group consisting of Oxygen-containing compounds of lanthanum, tungsten, molybdenum, titanium and zirconium, calculated as La, W, Mo, Ti, and Zr, contains, with oxygen-containing compounds of lanthanum being preferred.

5. The method according to any one of the preceding claims, characterized in that the catalytically active mass of the catalyst in the range 0.1 to 40 wt .-% elemental copper and / or in the range from 0.1 to 40 wt .-%, at least one oxygen-containing compound, selected from the group consisting of oxygen-containing compounds of magnesium, calcium, silicon and iron, calculated as Mg, Ca, Si and Fe, contains, elemental copper being preferred.

6. The method according to claims 2 to 5, characterized in that the copper oxide-containing catalyst can be produced before its reduction with hydrogen according to a process in which (i) an oxidic material comprising oxygen-containing compounds of copper, aluminum, and at least one oxygen-containing compound selected from the group consisting of oxygen-containing compounds of lanthanum, tungsten, molybdenum, titanium and zirconium, oxygen-containing compounds of lanthanum being preferred, provided,

(ii) powdery metallic copper, copper flakes, powdery cement or a mixture thereof, preferably powdery metallic copper, copper flakes or a mixture thereof, is added to the oxidic material,

7. The method according to the preceding claim, characterized in that the oxidic material and / or the mixture resulting from (ii) graphite in a total amount of 0.5 to 5 wt .-%, based on the total weight of the oxidic materi as , is admitted.

8. The method according to any one of the preceding claims, characterized in that the amine is prepared by reacting the aldehyde and / or ketone and the stick material compound together with the hydrogenation in the liquid phase and in the presence of hydrogen and the catalyst.

9. The method according to any one of the preceding claims, characterized in that it is carried out continuously and the catalyst loading in the range from 0.05 to 5 kg of aldehyde and / or ketone (alternative 1) or reaction product (alternative 2) per liter of catalyst (bulk volume) and hour lies.

10. The method according to any one of the preceding claims, characterized in that the nitrogen compound is used in 0.9 to 100 times the molar amount based on the aldehyde groups and / or keto groups to be aminated.

11. The method according to any one of the preceding claims, characterized in that the hydrogenation is carried out at an absolute pressure in the range from 1 to 30 MPa.

12. The method according to any one of the preceding claims, characterized in that it is carried out continuously and the hydrogenation is carried out either isothermally or adiabatically in a reactor, the temperature in the range from 100 to 230 ° C for both alternatives in the case of an isothermal reaction procedure and in the case of an adiabatic reaction, the temperature on entry into the reactor for alternative 1 in the range from 20 to 140 ° C and for alternative 2 in the range from 80 to 140 ° C and at the exit for both alternatives in the range from 130 to 230 ° C, whereby the temperature at the exit is always higher than at the entry.

13. The method according to any one of the preceding claims, for the preparation of amines of the formula (A) by reaction of an aldehyde and / or ketone of the formula (a) with an amine of formula (b) where in the formulas (A), (a) and (b) n 0 to 7,

R ^a substituted or unsubstituted phenyl R ^A CHR'R ³ ,

R ^B , R ^c , R ^D , R ^E independently of one another R ^A or H,

R ^F and RG (if n = 1 to 7) both H, or (if n = 0) both H or one of the radicals H and the other methyl,

R 'is H or Ci to C ₄ alkyl.

14. The method according to the preceding claim, for the preparation of amines of the formula (la) or (Ib) and or by reacting an aldehyde and / or ketone of the formula (II) and 1,2-ethylenediamine (EDA) or 1,2-propylene diamine (1,2-PDA) where in the formulas (Ia), (Ib), (Ib ') and (II) n for 0 or 1 or 2 or 3, R stands for a hydrogen radical or for a hydrocarbon radical with 1 to 6 carbon atoms, X for identical or different radicals selected from the group consisting of alkyl, alkoxy and dialkylamino with 1 to 18 carbon atoms each, and Y for a hydrogen Radical or a radical of the formula in which case the amines of the formula (Ib) and (Ib ') are identical.

Process according to the preceding claim for the preparation of N-benzyl-1,2-ethylenediamine (NBEDA) and N, N'-dibenzyl-1,2-ethylenediamine or N-benzyl-1,2-propylenediamine (NBPDA ), N'-benzyl-1,2-propylenediamine and N, N'-dibenzyl-1,2-propylenediamine by reaction of benzaldehyde and EDA or 1,2-PDA.