DD206896A3 - PROCESS FOR PREPARING 1,4-DIAZA BICYCLO (2,2,2) OCTANE - Google Patents

Abstract

Process for the preparation of 1,4-diaza-bicyclo- (2,2,2) -octane by reaction of in particular N- (beta-aminoethyl) -piperazine and N- (beta-hydroxyethyl) -piperazine-containing polyamine fractions to predominantly Al ind 2 O ind 3 besides little SiO 2 containing catalysts in an ammonia stream in the temperature range from 520 to 670 K. The amine fractions are by-products of a polyamine synthesis or are prepared from such by reaction with ethylene oxide. The preparation of the catalysts is described.

Description

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VES Leuna-Werke Merseburg, 7. 4. 19S2

"Walter Ulbricht"

LP 8224

Title of the invention

Process for the preparation of 1,4-diazabicyclo [2.2.2] octane Field of application of the invention

The invention relates to a process for the preparation of '1,4-diaza-bicyclo- [2,2,2] octane (! Eriethylenediamine) from polyethylenepolyamines and / or hydroxethylethylenepolyamines. «

Characteristic of the known technical solutions

It is known, triethylenediamine from different di- and polyamines »such as ethylenediamine, diethylenetriamine triethylenetetramine and polyethylene polyamine in general and from S-aminoethylpiperazine (AEP), ß-Hydrosyethylpiperazin (HEP), ITjir ^ bia-iß-hydrozyethy-piperagin (BHEP), but For this purpose, these amines are preferably reacted in the gas phase over catalysts and the desired triethylenediamine is isolated from the reaction products. The conversion and selectivity of the reaction of the different starting amine products are essentially determined by the catalyst used »

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Are preferred for the implementation of a wide variety of amines synthetic aluminosilicates and silicate cracking catalysts, but also Haturprodukte such as kaolin and montmorillonite, used · Thus it is known, aluminosilicates with a SiOP content 60-90 Hasse% and an Al ₂ 0 ~ moiety from 40 to 10 pigs as catalysts for Triethylendiaminsynthese use (US-PS 3,231,573), but ^ the natural product kaolin (US-PS 3,166,558), but even with different starting materials only very small amounts of triethylenediamine in a complex composition reaction mixture The said aluminosilicates were therefore both acidic (DE-OS 1 445 418, US Patent 2,985,658) and alkaline (US Patent 2,985,658) set to improve their selectivity, with careful attention to an accurate compliance with the Aciditätsgrades (US-PS 120 526) must be taken into account if an improvement in selectivity in triethylenediamine synthesis is to be achieved tz the elaborate catalyst preparation and measures to maintain the acidity during the synthesis (DE-AS 1 745 627) remained the yields, even with AEP and HEP, which already contain a preformed piperazine ring, with 30- 35 mol% low and the requirements of the workup of the reaction products thus obtained high, especially when working with impure or mixtures of amines as feedstock.

It is furthermore known to add metal oxides and metals of the transition group (DE-AS 1 745 627) to the aluminosilicates, it being necessary to work by adding the latter in the presence of hydrogen, without it being possible to increase the yield in comparison with the acidic or alkaline dopings ·

In addition, active clay (Al ₂ O ₃ ) has also been used as a catalyst for the synthesis of triethylenediamine or its derivatives. * Depending on the starting material used for this synthesis, very different results are obtained. BHEP supplies in the reaction to AlpO, in the gas phase Yields up to 56 mol% and in relation to other

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Yerfahren knew small amounts of by-products (BS-OS 2 442 989), while AlgO ^ for the Triethylendlaminsyiithese from ΑΞ? and ΗΞΡ indicated as unsuitable and demonstrated by exemplary embodiments (US Pat. No. 3,157,657). But BHlP is compared to AEP and HEP as a starting material for the synthesis of triethylenediamine in the preparation and handling the much more expensive substance, because it is crystalline at room temperature, has a high Yerdampfungstemperatur and an ethylene group is lost ·

The previously known methods for the synthesis of triethylenediamine therefore provide only unsatisfactory yields when using aluminosilicates as catalysts with all conceivable starting materials, even in the modification of these catalysts by various additives. · Active clay catalysts provide triethylenediamine only if BHSP is used as the starting product In addition, due to the low selectivity of the catalysts for triethylenediamine synthesis, a complex reaction mixture is obtained from which the triethylenediamine can be isolated only with great effort.

Object of the invention

The aim of the present invention is a cost-effective technical Yerfahren for the production of triethylenediamine, which wel¬ 'ches high yields and thus only a small effort in the isolation of the product ensures ·

Explanation of the essence of the invention

It was therefore the task of the technical, to influence the reaction so that the raw material to be used without voringe consuming separation operations with high selectivity to the desired end product is implemented, the main proportion

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the resulting lifting products can be recycled to the synthesis path. .

This object is achieved by a process for the preparation of 1,4-diaza-bicyclo [1,2,2} octanoctane by reacting ε- (β-aminoethyl) -piperazine and / or 1β-hydroxypropyl) Piperazine or mixtures containing these, as they are obtained as by-products of the synthesis of polyamine or by reacting such piperazine-containing by-products with ethylene oxide, in vapor form on a porous SiOg and -Α-ί · 2 ^Ο 3 ^Θη ^ ^α3ΐ ^ ^8ηαοη catalyst using of gaseous ammonia as accompanying gas at temperatures of 523 to 673 K and recycling of the piperazine formed as a lifting product according to the invention achieved in that a catalyst is used, which consists of 5 to 25 mass SiO ₂ containing active clay.

Surprisingly, it has been found that it is completely immaterial how the SiO _{2 is introduced} into the catalyst. Thus, it can be done in a known manner by co-precipitation of both components, but also by admixing silica or aluminosilicates to the active clay, as the latter z. B. unactivated natural clay minerals, such as illite, mon-tmorillonit or kaolinite own "zweckmäöigerweise one works at the reaction with a catalyst whose SiO ₂ content is from 10 to 20% by mass. The activated toner used in the catalyst in the reaction is preferably .alpha.-alumina.

It is particularly advantageous if the catalysts according to the invention have such a pore structure in which the proportion of pores with Hadien ^ 50 nm exceeds a pore volume of Ξ2 0.15 cyrir / g.

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Exemplary experimental apparatus

From a reservoir, a "" Amingeraisch was introduced from above through a metering pump in an evaporation tube (W-1, diameter 80 mm, length 900 mm), which was filled with porcelain saddles (diameter '6 mm) and electrically heated from above and evaporated there Ammonia and the vaporized amine mixture exited at the top of the evaporator and were in another, also electrically heated and with saddles (diameter 6 mm) filled heat exchanger (W-2, Diameter 80 mm, length 500 mm) to the temperature required for entry into the reactor.

The gaseous feed product mixture leaving the heat exchanger W-2 was immediately introduced from above into the catalyst-filled reaction tube (RI, diameter 80 mm, lice 2000 mm) and at the lower end of the reactor the liquid or solidified at room temperature reaction products in a Template collected. The ammonia and the first gaseous reaction products were passed through a condenser to separate 'other liquid may be crystallized reaction products · - ^

The combined liquid or crystalline reaction products were analyzed by gas chromatography and then worked up in known manner by distillation and / or crystallization to triethylenediamine. The temperature was measured at the following points:

T - 1 middle W-1

T - 2 output W-2

T - 3 catalyst layer R-I (500 mm from above)

T - 4 catalyst layer R-I (1500 mm from above)

catalysts

Catalyst A according to the invention)

Consisting of ' f - clay with an SiO 2 content of 15.3 Ma .-? 5, based on anhydrous material, prepared by admixing natural kaolin clay to active clay and deformed in a known manner by means of screw press to strand pellets.

Pore volume for pore radii "2:50 mn: 0.01 cm / g Catalyst B (according to the invention)

Consisting of monobasic earth with an SiO 2 content of 20.5 mass%, based on anhydrous material, prepared by co-precipitation of the components in a known manner from aluminum nitrate and waterglass solution by means of ammonia. The dried mixture was converted into cylindrical moldings by means of a pill press deformed and 4 ta. annealed at 723 K in the air.

3 pore volumes for pore radii S50 nm: 0.27 cm / g

Catalyst (C) according to the invention

Consisting of Jf-alumina with an SiO 2 content of 6.2 Ma .%, Based on anhydrous material, prepared by mixing the aquosides in a known manner, shaping of the dry mixture and shaping as in the case of catalyst B, also at 723 K for 4 h annealed in the air.

Pore volume for pore radii ">: 50 nm: 0.16 cm / g of catalyst D (comparative catalyst)

Consisting of an X-ray amorphous aluminosilicate with a content of 83.6% by mass (balance Al ₉ OO, a Grackkataly-

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in the form of spheres, diameter 2-4 mm «pore volume for p-radii> 50 nm: 0.25 cm / g catalyst Ξ (comparative catalyst)

Consisting of a sulfuric acid-activated kaolin with 52.3 mass% SiO ₂ , deformed on the screw extruder into pellets and annealed at 773 to 823 K for 5 hours in air.

Pore volume for pore radii ^ 50 nm: 0.03 cm / g amine mixtures (composition in% by mass)

ΑΞΡ HSP ΑΞΡ / ΗΕΡ

ethylenediamine 0.1 0.1 0.1 piperazine 0,2 - 13.5 4.2 Monoethanolamine - 3.6 2.1 diethylenetriamine 4.2 - 1.9 aminoethylpiperazine 95.3 0.5 40.6 Hydroxyethylpiperaain 0.4 ' 82.3 51.1

Example 12 3 4 5 6

Catalyst Art & AA BB C

Amine mixture ASP ΑΞΡ HSP HEP HSP HSP

Reaction conditions:

Load 0.18 0.35 0.17. 0.22 0.35 0.25

Amine mixture g / mlxh

3SEi Im / h 3 3 3 3 3 3 Temperatures T-1 478 483 505 508 507 507 K T-2 553 553 553 553 553 553 T-3 582 593 565 573rd 593 577 T-4 621 ' 622 593 597 629 605

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Result: Result: 70.2 64.7 95.0 80.4 98, 3 8th 9 88.6 Sales % Sales % D D Selectivity ' Selectivity ' 45.2 52.8 62.3 65.1 59, 0 HEP AEP 62.3 to triethylenediamine to triethylenediamine 37.9 30.4 31.3 24.5 32, 7 28.1 piperazine piperazine 7 for comparison! 0.20 0.20 example 10 C 3 3 e Catalyst Art AEP / HSP 509 501 HBP amine mixture 553 553 Reaction conditions: 0.25 625 621 0.15 burden 663 661 Amine mixture g / mlxh ^J 3 3 M ₃ At ³ / h 501 92.4 86.1 508 Temperatures T-1 553 553 K T-2 571 35.4 28.9 618 T-3 608 26.8 25.3 669 T-4 80.4 78.5 58.4 31.7 30.1 28.4

Load in g of amine mixture per ml of catalyst and hour

Selectivity based on reacted aminoethyl or _o Hydroxyethylpiperaζin

Claims (6)

OIL U Inquiry ia 1. A process for the preparation of 1,4-diaza-bicyclo [2,2,2] octane by reaction of IT- (ß-aminoethyl) piperazine and / or U- (ß-hydroxyethyl) piperazine or these containing Mixtures obtained as by-products of polyamine synthesis or by reaction of such piperazine-containing lifting products with ethylene oxide, in vapor form on a porous catalyst containing SiO ₂ and Al ₂ Oo using gaseous ammonia as accompanying gas at temperatures of 523 to 673 K and reecyclization of the piperazine formed as a lifting product, characterized in that a catalyst is used, which consists of 5 to 25 Biassed SiO ₂ containing active clay. 2 * Method according to item 1, characterized in that the reaction is carried out on a catalyst, in which the SiO ₂ content was introduced by co-precipitation. 3 * Method according to item 1, characterized in that the reaction is carried out on a catalyst in which the SiO ₂ content was introduced in the form of a non-activated natural clay mineral » 4 »method according to item 1 to 3, characterized in that the reaction is carried out on a catalyst having a SiO ₂ content of 10 to 20% by mass» 5 · The method of item 1 to 4 »characterized in that \ the reaction is carried out over a catalyst, in which f as activated alumina alumina employed. 6 »method according to item 1 to 5, characterized in that the reaction is carried out on a catalyst having a pore volume of>: 0.15 Qisr / g for pores with Hadien ΞΞ50 nm *