EP1937625A1

EP1937625A1 - Method for preparing aminodiglycol (adg) and morpholine

Info

Publication number: EP1937625A1
Application number: EP06793775A
Authority: EP
Inventors: Bram Willem Hoffer; Holger Evers; Petr Kubanek; Till Gerlach; Johann-Peter Melder; Frank Funke; Matthias Frauenkron; Helmut Schmidtke
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2005-09-30
Filing date: 2006-09-25
Publication date: 2008-07-02
Also published as: WO2007036496A1; US20080255351A1; JP2009510018A; DE102005047458A1

Abstract

A method for preparing aminodiglycol (ADG) and morpholine by reaction of diethyleneglycol (DEG) with ammonia in the presence of a transition metal heterogeneous catalyst is characterised in that the catalytically active mass of the catalyst contains, before treatment with hydrogen, oxygen-containing compounds of aluminium and/or zirconium, copper, nickel and cobalt, and in that the catalyst moulding in pellet or strand form has a diameter of < 3 mm, in tablet form a height of < 3 mm and in all other geometrical shapes an equivalent diameter L=1/a' of < 0.70 mm, a' standing for the external surface per volume unit (mms2/mmp3), with the formula (AA) in which Ap stands for the external surface of the catalyst particle (mm22) and Vp stands for the volume of the catalyst particle (mmp3).

Description

Process for the preparation of aminodiglycol (ADG) and morpholine

description

The present invention relates to a process for the preparation of aminodiglycol (ADG) and morpholine by reaction of diethylene glycol (DEG) of the formula

with ammonia in the presence of a transition metal heterogeneous catalyst.

Aminodiglycol (ADG) and morpholine find inter alia. Use as solvents, stabilizers, for the synthesis of chelating agents, synthetic resins, pharmaceuticals, inhibitors and surfactants.

For the preparation of aminodiglycol (ADG) and morpholine numerous methods are described in the literature.

EP-A-36331 and US-A-4,647,663 describe a process for the preparation of morpholine and morpholine derivatives by reacting a dialkylene glycol with ammonia in the presence of H2 and a hydrogenation catalyst in a trickle bed reactor.

Khim. Prom-st. (Moscow) (1 1), 653-5 (1982) (Chem. Abstr. 98: 91383q) describes the preparation of morpholine by gas-phase cycloamination of diethylene glycol with ammonia in the presence of H2 and a Cu, Co or Ni. Cr2θ3 catalyst.

Zh. Vses. Khim. Obshchest. 14 (5), 589-90 (1969) (Chem. Abstr. 72: 66879m) describes the formation of morpholine in 70% yield by gas phase reaction of diethylene glycol with NH3 on a nickel catalyst in the presence of H2.

Ind. Eng. Chem. Prod. Res. Dev. 1981, 20, pages 399-407, (CM Barnes et al.) Describes the ammonolysis of monoethanolamine (MEOA) to ethylenediamine (EDA) on nickel catalysts on a SiO 2 -Al 2 O 3 mixed carrier. Addition of water and the powdered catalyst was reportedly beneficial in increasing the yield of EDA.

Disadvantages of these technologies arise in suspension catalysis, inter alia, from the necessary catalyst / product separation. In addition, the selectivities, in particular for the formation of ADG, could be improved. A parallel German patent application with the same filing date (BASF AG) relates to a process for the preparation of ethylene amines by reacting ethylenediamine (EDA) in the presence of specific heterogeneous catalyst molding.

A parallel German patent application with the same filing date (BASF AG) relates to a process for the preparation of ethylene amines by reacting monoethanolamine (MEOA) with ammonia in the presence of specific heterogeneous catalyst shaped bodies.

It is an object of the present invention to overcome the disadvantages of the prior art and to provide an improved economical process for the preparation of aminodiglycol (ADG) and morpholine.

The method is intended in particular the non-cyclic amine ADG of the formula

.0.

HO ^ ^ NH ₂

in high yields, space-time yields and selectivities. For example, the proportion of ADG to morpholine in the product mix should be increased compared to the prior art, especially at a high DEG conversion, in particular at a DEG conversion of greater than 85%.

[Space-time yields are given in .product quantity / (catalyst volume • time) '(kg / (l kat • h)) and / or .product quantity / (reactor volume • time)' (kg / (lR _ea ctor • h)] ,

Accordingly, a process for the preparation of aminodiglycol (ADG) and morpholine by reaction of diethylene glycol (DEG) with ammonia in the presence of a transition metal heterogeneous catalyst has been found, which is characterized in that the catalytically active material of the catalyst before treatment with hydrogen, oxygen-containing compounds of the Aluminum and / or zirconium,

Contains copper, nickel and cobalt and the shaped catalyst body in spherical or strand form each have a diameter of <3 mm, in tablet form a height of <3 mm and in all other geometries each having an equivalent diameter L = 1 / a 'of <0.70 mm where a 'is the external surface area by volume (mm _s ² / mm _p ³ ), with:

\,

where Ap is the external surface area of the catalyst particle (mm _s ² ) and V _{p is} the volume of the catalyst particle (mm _p ³ ). The surface area and the volume of the catalyst particle (of the catalyst molding) result from the geometric dimensions of the particle (of the molding) according to the known mathematical formulas.

The volume can also be calculated using the following method, where:

1. Determine the internal porosity of the molded article (e.g., by measuring water uptake in [ml / gm Cat] at room temperature and 1 bar total pressure),

2. determining the displacement of the shaped article when immersed in a liquid (for example, by gas displacement by helium pyknometer) and

3. forms the sum of both volumes.

The surface can also be calculated theoretically by the following method, in which one defines an envelope of the molding, the curve radii max. 5 μm (in order not to take the inner pore surface into the pores by "penetrating" the envelope) and which touches the mold body as intimately as possible (no cut surface with the support) and then creates a vacuum from the inside, so that the film lays as close as possible to the molding.

The diethylene glycol (DEG) required as starting material can be prepared by known processes, for example by reacting ethylene oxide (EO) with H 2 O or EO with monoethylene glycol.

The reaction according to the invention is generally carried out at an absolute pressure in the range of 1-260 bar, preferably 100-250 bar, in particular at 150-240 bar, especially at 175-225 bar, and generally at elevated temperature, e.g. in the temperature range of 100-300 ° C, in particular 130-240 ° C, preferably at 175-225 ° C.

DEG and ammonia are preferably used in a molar ratio in the range of NH ₃ : DEG = 1-15, especially in the range of NH ₃ : DEG = 4-13, especially in the range of NH ₃ : DEG = 5-12.

The ratio of morpholine: ADG is determined in the process according to the invention in particular by the DEG conversion and the molar ratio NH 3: DEG.

In general, in the process according to the invention, the catalysts are preferably used in the form of catalysts which either consist only of catalytically active material and optionally a molding assistant (such as graphite or stearic acid), or the catalytically active components on a substantially inactive Trägerma- material. After grinding, the catalytically active composition can be introduced into the reaction vessel as a powder or as a grit or, after milling, mixing with molding aids, shaping and heat treatment, as a shaped catalyst body - for example as tablets, spheres, rings, extrudates (eg strands, tubes) - in be introduced into the reactor.

The concentration data (in% by weight) of the components of the catalyst are in each case - unless stated otherwise - on the catalytically active composition of the catalyst prepared before treatment with hydrogen.

The catalytically active mass of the catalyst is defined as the sum of the masses of the catalytically active constituents and contains, prior to treatment with hydrogen, preferably substantially the catalytically active constituents oxygen-containing compounds of aluminum and / or zirconium, copper, nickel and cobalt.

The sum of the o.g. catalytically active constituents, calculated as Al 2 O 3, ZrO 2, CuO, NiO and CoO, in the catalytically active composition prior to treatment with hydrogen is for example 70 to 100 wt .-%, preferably 80 to 100 wt .-%, particularly preferably 90 to 100 wt .-%, in particular 95 to 100 wt .-%, most preferably> 99 to 100 wt .-%.

Preferred heterogeneous catalysts in the process according to the invention contain in their catalytically active composition prior to treatment with hydrogen

20 to 85 wt .-%, preferably 20 to 65 wt .-%, particularly preferably 22 to 40 wt .-%, Al ₂ O ₃ and / or ZrO ₂ ,

From 1 to 30% by weight, particularly preferably from 2 to 25% by weight, of oxygen-containing compounds of copper, calculated as CuO,

14 to 70 wt .-%, preferably 15 to 50 wt .-%, particularly preferably 21 to

45 wt .-%, oxygen-containing compounds of nickel, calculated as NiO, wherein preferably the molar ratio of nickel to copper greater than 1, in particular greater than 1, 2, very particularly 1, 8 to 8.5, and

15 to 50 wt .-%, particularly preferably 21 to 45 wt .-%, oxygen-containing compounds of cobalt, calculated as CoO.

The oxygen-containing compounds of copper, nickel and cobalt, each calculated as CuO, NiO and CoO, of the preferred catalysts are generally generally in amounts of 15 to 80 wt .-%, preferably 35 to 80 wt .-%, particularly preferred 60 to 78 wt .-%, in the catalytically active composition (before treatment with Hydrogen), wherein particularly preferably the molar ratio of nickel to copper is greater than 1.

Further heterogeneous catalysts in the process according to the invention are

in DE-A-19 53 263 (BASF AG) disclosed catalysts comprising cobalt, nickel and copper and alumina having a metal content of 5 to 80 wt .-%, in particular 10 to 30 wt .-%, based on the total catalyst, wherein the catalysts, calculated on the metal content, contain from 70 to 95% by weight of a mixture of cobalt and nickel and from 5 to 30% by weight of copper, and wherein the weight ratio of cobalt to nickel is 4: 1 to 1: 4, in particular 2: 1 to 1: 2, is, for example, the catalyst used in the examples there with the composition 10 wt .-% CoO, 10 wt .-% NiO and 4 wt .-% CuO to Al ₂ O ₃ ,

in EP-A-382 049 (BASF AG) disclosed or correspondingly preparable catalysts whose catalytically active composition prior to treatment with hydrogen 20 to 85 wt .-%, preferably 70 to 80 wt .-%, ZrO ₂ and / or AI ₂ O ₃ , 1 to 30 wt .-%, preferably 1 to 10 wt .-%, CuO, and in each case 1 to 40 wt .-%, preferably 5 to 20 wt .-%, CoO and NiO contains, for example, those in loc. cit. 76 wt% Zr calculated as ZrO ₂ , 4 wt% Cu, calculated as CuO, 10 wt% Co, calculated as CoO, and 10 wt% Ni, on page 6 calculated as NiO,

in EP-A-963 975 and EP-A-1 106 600 (both BASF AG), whose catalytically active composition before treatment with hydrogen contains from 22 to 40% by weight ZrO ₂ ,

1 to 30 wt .-% oxygen-containing compounds of copper, calculated as CuO, 15 to 50 wt .-% oxygen-containing compounds of nickel, calculated as NiO, wherein the molar Ni: Cu ratio is greater than 1, 15 to 50 wt. % oxygen-containing compounds of cobalt, calculated as CoO, 0 to 10 wt .-% oxygen-containing compounds of aluminum and / or manganese, calculated as Al ₂ O ₃ or MnO ₂ , and no oxygen-containing compounds of molybdenum, for example, in loc. cit., page 17, disclosed catalyst A having the composition 33% by weight Zr, calculated as ZrO ₂ , 28% by weight Ni, calculated as NiO, 11% by weight Cu, calculated as CuO and 28% by weight % Co, calculated as CoO.

Particularly preferred catalysts in the process according to the invention contain no chromium (Cr).

The catalysts prepared can be stored as such. Before being used as catalysts in the process according to the invention, they are treated by treatment with Hydrogen pre-reduced (= activation of the catalyst). However, they can also be used without prereduction, in which case they are reduced (= activated) under the conditions of the process according to the invention by the hydrogen present in the reactor.

For activation, the catalyst is preferably at a temperature in the range of 100 to 500 ° C, especially 150 to 400 ° C, especially 180 to 300 ° C, over a period of at least 25 min., Particularly at least 60 min., A hydrogen - exposed to a living atmosphere or a hydrogen atmosphere. The period of activation of the catalyst may be up to 1 h, especially up to 12 h, in particular up to 24 h.

In this activation, at least a portion of the oxygen-containing metal compounds present in the catalysts is reduced to the corresponding metals, so that they are present together with the various oxygen compounds in the active form of the catalyst.

The catalyst used preferably has a bulk density in the range of 0.6 to 1.2 kg / l.

According to the invention, it was recognized that particularly high ADG selectivities are obtained when the catalyst is used in the form of small shaped articles. With a small shaped body are meant those whose diameter in spherical shape in each case below 3 mm, in particular below 2.5 mm, e.g. in the range of 1 to 2 mm.

Correspondingly, with a small shaped body, those are also meant whose diameter in strand form (strand length >> strand diameter) or their height in the case of tablet form (tablet diameter >> tablet height) is in each case below 3 mm, in particular below 2.5 mm, e.g. in the range of 1 to 2 mm.

In all other geometries, the catalyst molding in the process according to the invention in each case has an equivalent diameter L = 1 / a 'of <0.70 mm, in particular of <0.65 mm, for example in the range of 0.2 to 0.6 mm, wherein a 'is the external surface area by volume (mm _s ² / mm _p ³ ), with:

where Ap is the external surface area of the catalyst particle (mm _s ² ) and V _{p is} the volume of the catalyst particle (mm _p ³ ). (L = specific dimension of a catalyst mold body). In the process according to the invention, the diffusion paths of the reactants and also of the products are lower due to the small specific dimension of the catalyst particles. The mean residence time of the molecules in the pores and the likelihood of an undesired subsequent reaction are thereby reduced. As a consequence of the defined residence time, an increased selectivity, in particular in the direction of the desired ADG, can thus be achieved.

The catalyst is preferably present as a fixed bed in a reactor. The reactor is preferably a tube reactor or tube bundle reactor. The reaction of DEG in the reactor preferably takes place in a straight pass.

The catalyst bed is preferably surrounded by an inert material both at the inlet and at the outlet of the reactor. As an inert material, e.g. Pall rings, balls of an inert material (e.g., ceramic, steatite, aluminum) can be used.

The reactor can be operated in both bottom and trickle mode. In the preferred trickle mode, a liquid distributor for the reactor feed is preferably used at the inlet of the reactor.

To maintain the catalyst activity are preferably 0.01 to 1, 00 wt .-%, especially 0.20 to 0.60 wt .-%, hydrogen (based on the reactor feed DEG + NH3) in the reactor.

In the preferably continuous operation, at a weight hourly space velocity (WHSV) of 0.25-2.0, especially 0.5-1.5 kg / kg ^* h (kg of DEG per kg of catalyst per hour) in the conversion range of 85 - 95% selectivities (S) with respect to ADG and morpholine of preferably> 60%, in particular 70-85%, achieved. The molar selectivities for ADG + morpholine are especially at 90 - 92%.

Typically, at a DEG conversion of> 90%, ADG and morpholine will be in a weight ratio ADG: morpholine greater than 0.20, especially greater than 0.24, especially greater than 0.27, e.g. in the range of 0.28 to 0.36.

As further products fall in the process according to the invention small amounts of morpholine derivatives and higher amines, in particular higher linear polyalkyl amines.

The workup of the product streams obtained in the process according to the invention, which contain, in particular, the particularly desired ADG but also morpholine, morpholine derivatives, higher polyalkylamines and unreacted DEG, can be carried out by distillation processes known to the person skilled in the art. The distillation columns required for the pure distillation of the individual products, above all the particularly desired ADGs and also morpholines, can be designed by methods familiar to the person skilled in the art (eg number of separation stages, reflux ratio, etc.).

The separation of the reaction product resulting from the reaction takes place in particular by multi-stage distillation.

For example, the separation of the reaction effluent resulting from the reaction into two separation sequences is carried out by multistage distillation, wherein in the first separation sequence ammonia and optionally present hydrogen are separated off and in the second separation sequence a separation into unreacted DEG and ADG, morpholine, Morpholine derivatives and higher polyalkylamines takes place.

In the separation of the resulting from the reaction reaction effluent ammonia and / or accumulating DEG are preferably recycled to the reaction.

Examples

A catalyst preparation

A1 precursor preparation

For precipitation, an aqueous solution of nickel nitrate, copper nitrate, cobalt nitrate and zirconium acetate was added simultaneously with a 20% aqueous solution of sodium carbonate into a stirring vessel at a temperature of 70 ° C. in a constant flow so that the pH was within a range of 5.5 - 6.0 was maintained. After the addition of the metal salt solution and the sodium carbonate solution was stirred for a further hour at 70 ° C and then the pH was increased by the addition of some sodium carbonate solution to a value of 7.4.

The suspension obtained was filtered and the filter cake was washed with demineralized water. Thereafter, the filter cake was dried at a temperature of 200 ° C in a drying oven or a spray dryer. The hydroxide carbonate mixture obtained in this way was then tempered at a temperature of 400 ° C over a period of 2 hours. The catalyst powder thus obtained had the composition:

28.1% by weight of Ni, calculated as NiO 27.7% by weight of Co, calculated as CoO

13.1% by weight of Cu, calculated as CuO

.1, 2 wt .-% Zr, calculated as ZrO ₂

A2 Catalyst A (comparative catalyst)

The catalyst powder of A1 was mixed with 2% by weight of graphite and shaped into 5 × 3 mm tablets. After tabletting, the tablets were post-calcined for 2 h at 350 ° C in a muffle furnace. Before installation in the test reactor, it was reduced and then passivated. For the reduction, the catalyst was heated in a hydrogen / nitrogen stream to temperatures between 100 and 200 ° C. This temperature was maintained until no more water has formed. It was then heated to a final temperature of 280 ° C and held this temperature for 90-120 hours. The catalyst was cooled to room temperature under a nitrogen stream and then passivated with a dilute oxygen stream. During passivation, care was taken that the temperature in the reactor did not rise above 50 ° C at any point.

A3 Catalyst B (according to the invention)

The catalyst powder of A1 was mixed with 2% by weight of graphite and shaped into 1.5 × 2 mm tablets. The post-calcination, reduction and passivation was carried out as described in A2.

B Hydrogenating aminations using catalysts according to A

Example 1: small shaped article (catalyst B), according to the invention

DEG (700 g / h), NH ₃ (730 g / h) and H ₂ (90 Nl / h) (Nl = standard liters = volume converted to standard conditions) were continuously pumped into a stainless steel tube in the upflow mode (length 2 m, Diameter 3 cm). The reactor was filled with the amination catalyst (500 ml as a 1.5 x 2 mm molding) and the reaction was carried out at 200 bar. The catalyst loading was 1.4 kg / l ^* h. At 192 ° C was obtained: DEG: 29.6 wt .-%

ADG: 31, 4% by weight of morpholine: 32.1% by weight

At 195 ° C was obtained: DEG: 19.3 wt .-%

ADG: 28.7% by weight of morpholine: 43.7% by weight

At 198 ° C., the following were obtained: DEG: 9.1% by weight.

ADG: 20.6% by weight of morpholine: 60.2% by weight

Comparative Example 1: Classic Molded Body (Catalyst A)

DEG (700 g / h), NH ₃ (730 g / h) and H ₂ (90 Nl / h) were run continuously in the upflow mode into a stainless steel tube (length 2 m, diameter 3 cm). The reactor was filled with the amination catalyst (500 ml as a 5 x 3 mm molding) and the reaction was carried out at 195 ° C and 200 bar. The catalyst loading was 1.4 kg / l ^* h.

The following product mix was obtained: DEG: 22.8% by weight

ADG: 22.5% by weight

Morpholine: 46.9% by weight

Claims

claims

1. A process for the preparation of aminodiglycol (ADG) and morpholine by reaction of diethylene glycol (DEG) with ammonia in the presence of a transition metal heterogeneous catalyst, characterized in that the catalytically active material of the catalyst prior to treatment with hydrogen, oxygen-containing compounds of the Aluminum and / or zirconium, copper, nickel and cobalt and the shaped catalyst body in spherical or strand form each have a diameter of <3 mm, in tablet form a height of <3 mm and in all other geometries each have an equivalent diameter

L = 1 / a 'of <0.70 mm, where a' is the external surface area by volume (mm _s ² / mm _p ³ ), with:

\,

where A _{p is} the external surface area of the catalyst particle (mm _s ² ) and V _{p is} the volume of the catalyst particle (mm _p ³ ).

2. The method of claim 1 for the preparation of ADG and morpholine in a weight ratio ADG: morpholine greater 0.20.

3. The method according to any one of the preceding claims, characterized in that the shaped catalyst body with spherical shape or strand shape each have a diameter of <2.5 mm, in tablet form a height of <2.5 mm and in all other geometries each have an equivalent diameter L = 1 / a 'of <0.65 mm.

4. The method according to any one of the preceding claims, characterized in that the reaction of DEG is carried out in the presence of hydrogen.

5. The method according to any one of the preceding claims, characterized in that the reaction of DEG is carried out at a temperature in the range of 100 to 300 ° C.

6. The method according to any one of the preceding claims, characterized in that the reaction of DEG at an absolute pressure in the range of 1 to

260 bar is performed.

7. The method according to any one of the preceding claims, characterized in that the reaction of DEG in the gas phase, liquid phase or in supercritical phase is performed.

8. The method according to any one of the preceding claims, characterized in that the catalytically active material of the catalyst prior to treatment with hydrogen 20 to 65 wt .-% zirconia (Zrθ2), 1 to 30 wt .-%, oxygen-containing compounds of copper calculated as CuO, 15 to 50 wt .-%, oxygen-containing compounds of nickel, calculated as NiO, and 15 to

50 wt .-% oxygen-containing compounds of cobalt, calculated as CoO contains.

9. The method according to any one of the preceding claims, characterized in that the catalyst used has a bulk density in the range of 0.6 to

1, 2 kg / l.

10. The method according to any one of the preceding claims, characterized in that the catalyst is present as a fixed bed in a reactor.

1 1. A method according to the preceding claim, characterized in that it is the reactor is a tubular reactor or tube bundle reactor.

12. The method according to any one of the preceding claims, characterized in that the reaction of DEG in the reactor takes place in a straight pass.

13. The method according to any one of the three preceding claims, characterized in that the reactor is operated in the upflow mode or in trickle mode.

14. The method according to any one of the preceding claims, characterized in that one uses DEG and ammonia in a molar ratio in the range of NH3: DEG = 1-15.

15. The method according to any one of the preceding claims, characterized in that the separation of the reaction resulting from the reaction takes place by multi-stage distillation.

16. The method according to the preceding claim, characterized in that the separation of the reaction resulting from the reaction takes place in two separation sequences by multi-stage distillation, wherein in the first separation sequence first ammonia and optionally present hydrogen are separated and in the second separation sequence separation into unreacted DEG, ADG, morpholine, morpholine derivatives and higher polyalkylamines takes place.

17. The method according to any one of the preceding claims, characterized in that in the separation of the resulting reaction from the reaction resulting ammonia and / or accumulating DEG is recycled to the reaction.