Method for Producing Aminoethylethanolamine

Europäisches Patentamt *EP000821664B1* (19) European Patent Ofﬁce

Ofﬁce européen des brevets (11) EP 0 821 664 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.7: C07C 213/04, C07D 295/088, of the grant of the patent: C07C 215/14 05.04.2000 Bulletin 2000/14 (86) International application number: (21) Application number: 96901303.6 PCT/EP96/00207

(22) Date of ﬁling: 11.01.1996 (87) International publication number: WO 96/24576 (15.08.1996 Gazette 1996/37)

(54) METHOD FOR PRODUCING AMINOETHYLETHANOLAMINE AND/OR HYDROXYETHYL PIPERAZINE VERFAHREN ZUR HERSTELLUNG VON AMINOETHYLETHANOLAMIN UND/ODER HYDROXYETHYLPIPERAZIN PROCEDE DE PRODUCTION D’AMINOETHYLETHANOLAMINE ET/OU D’HYDROXYETHYLPIPERAZINE

(84) Designated Contracting States: • FRANK, Magnus AT BE CH DE DK ES FR GB GR IE IT LI NL PT SE S-411 31 Göteborg (SE)

(30) Priority: 08.02.1995 SE 9500444 (74) Representative: Andersson, Rolf Akzo Nobel Surface Chemistry AB, (43) Date of publication of application: Patent, Trademark and Licensing Department 04.02.1998 Bulletin 1998/06 444 85 Stenungsund (SE)

(73) Proprietor: AKZO NOBEL N.V. (56) References cited: 6800 SB Arnhem (NL) EP-A- 0 354 993 DD-A- 206 670 DE-A- 2 013 676 (72) Inventors: • KÖLL, Juhan S-444 45 Stenungsund (SE)

Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 0 821 664 B1

Printed by Jouve, 75001 PARIS (FR) 1 EP 0 821 664 B1 2

Description The use of water as catalyst results in the formation of a high-boiling azeotrope of ethylenediamine and water, [0001] The present invention relates to a method for which is difficult to break. The ethoxylation of piperazine producing aminoethylethanolamine, hydroxyethyl pip- results in the formation of not only hydroxyethyl pipera- erazine or both these compounds by continuously 5 zine but also di-(hydroxyethyl)-piperazine. The resulting ethoxylating ethylenediamine, piperazine or a mixture product mixture is usually separated by vacuum distilla- thereof in an excess of ethylenediamine and piperazine. tion. If use is made of catalysts which wholly or partly The resulting ethoxylation product flow is then proc- are dissolved in the reactants, also these should be re- essed by distillation in a distillation plant for processing moved prior to the processing of the reaction mixture. an amination product flow obtained in the amination of 10 In reactions above 100°C, ethylene oxide reacts also monoethanolamine with ammonia. with the water present to form ethylene glycol, which re- [0002] It is long since known, for instance from Knorr sults in ethylene oxide losses and further separation et al, Ber. 35 (1902), p. 4470, to produce aminoethyleth- problems. anolamine by reacting ethylene oxide with ethylenedi- [0006] The object of the present invention is to pro- amine at room temperature and in the presence of con- 15 duce aminoethylethanolamine and/or hydroxyethyl pip- siderable amounts of water. The reaction is carried out erazine in such a manner as to simplify the purification in an excess of ethylenediamine in order to avoid the process. Another object of the invention is that the re- formation of higher adducts, such as N,N'-bis(2-hydrox- action should be carried out continuously, so as to avoid yethyl)-ethylenediamine. DE-A-2,716,946 discloses a the problems associated with a reaction batchwise. Fur- discontinuous method for producing aminoethyleth- 20 ther objects of the invention are to achieve high yields anolamine by reacting ethylenediamine with ethylene of the desirable compounds and to enable use of reac- oxide at a temperature of 100-120°C and in the pres- tants which are not necessarily pure. ence of water in a specially-developed reaction appara- [0007] It has now been found that these objects are tus. Patent Specification SU-A-1,512,967 discloses the attained by reacting ethylenediamine, piperazine or a production of N,N'-bis(2-hydroxyethyl)-ethylenedi- 25 mixture thereof with ethylene oxide in the presence of a amine by ethoxylating ethylenediamine with ethylene catalyst, the reaction process involving the steps of oxide in a molar ratio of 1:2 at a temperature of 40-50°C and in an approximately 20% aqueous solution. This re- i) continuously reacting ethylenediamine and/or action generates a great number of by-products. Patent piperazine with 0.05-0.5 mole of ethylene oxide, Publication EP-A-354 993 proposes that amines con- 30 preferably 0.1-0.3 mole, per mole of ethylenedi- taining reactive hydrogen atoms are reacted with ethyl- amine and/or piperazine in the presence of a cata- ene oxide and/or propylene oxide at an elevated tem- lyst, perature, conveniently a temperature of 130-180°C, at ii) introducing the resulting ethoxylation product a pressure above atmospheric and in the absence of flow into a distillation plant designed for processing any solvent but in the presence of a catalytic amount of 35 an amination product flow obtained by aminating alkali metal hydroxide and/or alkali metal alkoxide. monoethanolamine with ammonia, and [0003] It is known from DE-A-2,013,676 to react, in a iii) distilling the ethoxylation product flow in the dis- first step, ethylenediamine with ethylene oxide in the ab- tillation plant while recovering aminoethyleth- sence of a catalyst, and to react, in a second step, the anolamine and/or hydroxyethyl piperazine. formed higher condensation products in the presence 40 of hydrogen (and optionally ammonia) and a hydration Preferably, the catalyst employed consists of water or a catalyst to piperazine, hydroxyethyl piperazine and N- solid catalyst which is not dissolved during the ethoxy- aminoethyl piperazine. lation reaction. Conveniently, the ethoxylation product [0004] It is further known that the production of ethyl- flow is introduced into the distillation plant before the first enediamine by the amination of monoethanolamine with 45 column where, in the distillation of the amination product ammonia inter alia results in minor amounts of ethylen- flow, a compound or mixture is separated which con- ediamine and piperazine substituted with one or more tains a compound forming part of the ethoxylation prod- hydroxyethyl groups. The reaction mixture obtained in uct flow. As a result of the mode of implementation of the amination is then separated by multistep distillation. the method according to the invention, the reaction [0005] There are many difficulties associated with the 50 products can be processed in a plant intended for the production of aminoethylethanolamine and hydroxye- production of ethyleneamines by catalytic amination of thyl piperazine. Thus, one problem is that the ethoxyla- monethanolamine with ammonia, since the ethoxylated tion of ethylenediamine results in the formation of a products found in the ethoxylation product flow are number of undesirable by-products, such as di-, tri- or present also in the amination product flow obtained in tetra(hydroxyethyl)-ethylenediamine which, along with 55 catalytic amination of monoethanolamine with ammo- unreacted ethylenediamine and ethylene oxide as well nia. any water present, have to be separated from the ami- [0008] In one preferred mode of implementation, it noethylethanolamine, usually by vacuum distillation. has been found highly suitable to conduct amination and

2 3 EP 0 821 664 B1 4 ethoxylation in parallel and to join the ethoxylation prod- ronment. It is also suitable to ethoxylate a mixture of eth- uct flow and the amination product flow in the distillation ylenediamine and piperazine, in which case the two plant. Owing to the higher content of aminoethyleth- amine compounds may have been obtained in the dis- anolamine and/or hydroxyethyl piperazine in the thus- tillation plant. Such a product mixture may contain joined product flows, it has, in addition, been found that 5 60-100% by weight of ethylenediamine, preferably the recovery of ethylenediamine from the azeotrope of 80-95% by weight, and 0-40% by weight of piperazine, ethylenediamine and water is facilitated. preferably 0-20% by weight. Use is preferably made of [0009] In another preferred mode of implementation, the ethylenediamine azeotrope formed when reacting ethylenediamine and/or piperazine are drawn off in the monoethanolamine and ammonia. Additional ethylene- form of a product flow from the distillation plant where 10 diamine and/or piperazine may also be added to the the ethoxylation product flow and the amination product azeotrope, as may additional amounts of water. Con- flow are being processed jointly. Such a product flow veniently, such a product mixture contains 55-95% by may wholly or partly consist of the azeotrope of ethylen- weight of ethylenediamine, preferably 70-90% by ediamine and water (optionally containing piperazine), weight; 1-30% by weight of water, preferably 10-20% by in which case the water will serve as catalyst in the 15 weight; and 0-40% by weight of piperazine, preferably ethoxylation reaction. An ethylenediamine-containing 0-10% by weight. fraction, which has not yet been fully processed, may [0013] By performing the ethoxylation of ethylene di- then be used as reactant. amine and/or piperazine in the special manner de- [0010] If water, wholly or partly, is used as catalyst, scribed and by performing the processing in a distillation the ethoxylation reaction is carried out at a temperature 20 plant for amination products obtained in the amination of 20-95°C, preferably 40-80°C. Under such conditions, of monoethanolamine with ammonia, a simple and cost- it has been found possible to attain a satisfactory ethox- effective mode of production of aminoethyleth- ylation rate as well as a high selectivity for ethoxylation anolamine and/or hydroxyethyl piperazine is obtained. of the reactive hydrogen atoms of the amine com- [0014] Appended Figs 1 and 2 schematically illustrate pounds, there being practically no formation of glycols 25 two examples of how the ethoxylation process can be or any ethoxylation of hydroxyl groups. If the reaction is integrated with a distillation plant for processing an am- carried out in the absence of water, the reaction temper- ination product flow obtained in the amination of mo- ature suitably is 20-150°C, preferably 40-120°C. If use noethanolamine with ammonia. The following abbrevi- is made of a solid ethoxylation catalyst which is not sol- ations are used in the description of the Figures as well uble during the reaction, additional process steps for re- 30 as in the Examples below. moving the catalyst can be avoided. Examples of suitable solid catalysts are acid ion exchangers, acid zeo- AEEA = Aminoethylethanolamine lites, acid clays and Lewis acids. The term solid cata- DETA = Diethylenetriamine lysts also includes liquid catalysts that are bound to a EDA = Ethylenediamine solid carrier. It is further possible to use a solid ethoxy- 35 EO = Ethylene oxide lation catalyst in combination with water. HEP = Hydroxyethyl piperazine [0011] The ethoxylation of ethylenediamine and pip- MEA = Monoethanolamine erazine to aminoethylethanolamine and hydroxyethyl PIP = Piperazine piperazine, respectively, implies that only one of the four and two reactive hydrogen atoms of ethylenediamine 40 [0015] Fig. 1 schematically illustrates an arrangement and piperazine, respectively, react with ethylene oxide. for integrated ethoxylation of EDA and/or PIP to AEEA According to the invention, this problem is solved by per- and/or HEP. A, B and D are columns in a distillation plant forming the reaction with an considerable excess of eth- for processing an amination product flow obtained in the ylenediamine and/or piperazine. In the method, use may amination of MEA with ammonia. C is a system of dis- also be made of ethylenediamine and/or piperazine con- 45 tillation columns for separating various products, and E taining minor amounts of other compounds with reactive is a reactor for ethoxylating EDA and/or PIP. An amina- hydrogen atoms obtained from the amination plant. The tion product flow 11 is introduced into the distillation col- ethoxylates formed from these compounds, as well as umn A, where ammonia is separated. In the distillation unreacted ethylenediamine and piperazine can be re- column B, the main part of the water present in the am- covered as pure products or as a high-boiling distillation 50 ination product flow is separated and drawn off through residue, optionally together with the corresponding a conduit 31. The remaining amines are conducted components of the amination flow. through a conduit 32 to the distillation system C, where [0012] A suitable starting product for ethoxylation is, an EDA-water azeotrope, EDA, PIP, DETA, AEP and for instance, an ethylenediamine fraction which contains HEP are separated via the conduits 41, 42, 43, 44, 45 at least 95% by weight of ethylenediamine and which 55 and 46, respectively. Usually, the azeotrope contains has been obtained from the distillation plant. If the frac- 80-90% by weight of EDA, 0-5% by weight of PIP and tion is water-free, the reaction is preferably carried out 10-20% by weight of water. A flow 46 of high-boiling in the presence of a solid catalyst in a water-free envi- amines leaves the system of columns C. In the column

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D, these high-boiling amines are, by distillation, sepa- in accordance with Fig. 1, the additions of both AEEA rated into AEEA, which is drawn off through a conduit and HEP were found in the amounts expected from the 51, and a bottom fraction, which is drawn off through a analysis. conduit 52. The azeotrope 41 is, wholly or partly and after optional cooling to a suitable reaction temperature 5 Example 2 in a cooler K, conducted through a conduit 61 to the ethoxylation reactor E. If so desired, more water can be [0020] An EDA-containing flow (more than 99.5% by added to the azeotrope through a conduit 64, and more weight of EDA; cooled to 50°C) in accordance with Fig. piperazine may be added through a conduit 63. Ethyl- 2 was introduced into an ethoxylation reactor which con- ene oxide is introduced into the reactor E through a con- 10 tained a solid catalyst consisting of an ion exchanger in duit 65, suitably in several places. The reaction mixture sulphonic-acid form. In addition, 0.105 mole of ethylene formed in the ethoxylation reactor E, which in addition oxide per mole of EDA was supplied to the reactor in to EDA and water contains EDA adducts and/or PIP ad- several steps, and the reaction was carried out at about ducts, is joined with the ammonia-free amination prod- 75°C. The ethoxylation flow leaving the reactor con- uct flow 22 for distillation. 15 tained 85% of EDA, 14% of AEEA and 1% of other re- [0016] Fig. 2 shows an alternative arrangement, action products. All the EO had reacted. More than 99% which enables the production of more AEEA than is pos- of the EDA spent had reacted to AEEA. The resulting sible when using the EDA-water azeotrope only. Like ethoxylation product flow was joined with the amination components as in Fig. 1 are identified by like designa- product flow for distillation. In processing in accordance tions. In view of the ethoxylation, part of the flow 42, 20 with Fig. 2, the addition of AEEA was found in the which consists of EDA, is conducted, via a conduit 62, amount expected from the analysis. to an ethoxylation reactor J, which contains an acid ion exchanger as catalyst. No water need be added. Since the reaction mixture contains EO and an excess of EDA, Claims only EDA ethoxylates are, apart from EDA, obtained in 25 the ethoxylation product flow 71. Then, the ethoxylation 1. A method for producing aminoethylethanolamine product flow 71 is joined with a flow 32 from the distilla- and/or hydroxyethyl piperazine by ethoxylating eth- tion column B, which as a result is subjected to less load. ylenediamine and/or piperazine with ethylene oxide [0017] A great number of arrangements of the distil- in the presence of a catalyst, lation plant and its integration with the ethoxylation re- 30 characterised by actor are conceivable within the scope of the invention. For instance, the flow 41 in Fig. 2, i.e. the azeotrope of - continuously reacting ethylenediamine and/or ethylenediamine and water, may wholly or partly be in- piperazine with 0.05-0.5 mole of ethylene ox- troduced into the ethoxylation reactor J. If so, the ethox- ide, preferably 0.1-0.3 mole, per mole of ethyl- ylation product flow should, however, be joined with the 35 enediamine and/or piperazine, ammonia-free amination product flow 22 from the col- - introducing the resulting ethoxylation product umn A. flow into a distillation plant designed for [0018] The invention will now be further illustrated processing an amination product flow obtained with the aid of two Examples. by aminating monoethanolamine with ammo- 40 nia, and Example 1 - distilling the ethoxylation product flow in the distillation plant while recovering aminoethyleth- [0019] A flow leaving a distillation plant according to anolamine and/or hydroxyethyl piperazine. Fig. 1 and containing 72% of EDA, 4% of PIP and 23% of water was cooled to 40°C and introduced into an 45 2. A method as claimed in claim 1, characterised by ethoxylation reactor with a static mixer. Ethylene oxide being performed in the presence of water as cata- in a molar ratio of EDA to EO of 1:0.17 was then added lyst at a temperature of 20-95°C, preferably to the reactor in several steps. In the reaction, the tem- 40-80°C. perature rose to 90-95°C. The ethoxylation product flow from the reactor contained 56.5% of EDA, 2.5% of PIP, 50 3. A method as claimed in claim 1, characterised by 19.5% of water, 17% of AEEA, 3% of HEP and 1.5% of being performed in the absence of water but in the other reaction products. All the ethylene oxide had re- presence of a solid catalyst, which is not dissolved acted. 95% of the EDA spent and 93% of the PIP spent during the reaction, and at a temperature of had reacted to AEEA and HEP. 79% of the EO supplied 20-150°C, preferably 40-120°C. had reacted to AEEA, while 11% thereof had reacted to 55 HEP and 10% thereof had reacted to other products. 4. A method as claimed in claim 1, 2 or 3, character- The resulting ethoxylation product flow was joined with ised by introducing the ethoxylation product flow in- the amination product flow for distillation. In processing to the distillation plant before the first column where,

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in the distillation of the amination product flow, a 3. Verfahren wie in Anspruch 1 beansprucht, dadurch compound or mixture is separated which contains gekennzeichnet, daß es in Abwesenheit von Was- a compound forming part of the ethoxylation prod- ser, aber in Anwesenheit eines festen Katalysators, uct flow. der sich während der Umsetzung nicht löst, und bei 5 einer Temperatur von 20 bis 150°C, bevorzugt 40 5. A method as claimed in any one of claims 1-4, char- bis 120°C, durchgeführt wird. acterised by joining the ethoxylation product flow with the amination product flow and jointly distilling 4. Verfahren wie in Anspruch 1, 2 oder 3 beansprucht, them in the distillation plant. dadurch gekennzeichnet, daß der Ethoxylierungs- 10 produktstrom vor der ersten Kolonne, in der bei der 6. A method as claimed in any one of claims 1-5, char- Destillation des Aminierungsproduktstromes eine acterised by ethoxylating an ethylenediamine frac- Verbindung oder eine Mischung getrennt wird, die tion which contains at least 95% by weight of ethyl- eine Verbindung enthält, die einen Bestandteil des enediamine and which has been obtained from the Ethoxylierungsproduktstromes bildet, in die Destil- distillation plant. 15 lationsanlage eingespeist wird.

7. A method as claimed in any one of claims 1, 2, 4 5. Verfahren wie in irgendeinem der Ansprüche 1 bis and 5, characterised by ethoxylating a product 4 beansprucht, dadurch gekennzeichnet, daß der mixture which contains 55-95% by weight of ethyl- Ethoxylierungsproduktstrom mit dem Aminierungs- enediamine, preferably 70-90% by weight; 1-30% 20 produktstrom vereinigt wird und sie gemeinsam in by weight of water, preferably 10-20% by weight; der Destillationsanlage destilliert werden. and 0-20% by weight of piperazine, preferably 0-10% by weight. 6. Verfahren wie in irgendeinem der Ansprüche 1 bis 5 beansprucht, dadurch gekennzeichnet, daß eine 8. A method as claimed in claim 3, 4 or 5, character- 25 Ethylendiaminfraktion ethoxyliert wird, die minde- ised by ethoxylating a product mixture which con- stens 95 Gew.-% Ethylendiamin enthält und die aus tains 60-100% by weight of ethylenediamine, pref- der Destillationsanlage erhalten wurde. erably 80-95% by weight; and 0-40% by weight of piperazine, preferably 5-20% by weight. 7. Verfahren wie in irgendeinem der Ansprüche 1, 2, 30 4 und 5 beansprucht, dadurch gekennzeichnet, daß eine Produktmischung ethoxyliert wird, die 55 bis Patentansprüche 95 Gew.-%, bevorzugt 70 bis 90 Gew.-% Ethylen- diamin; 1 bis 30 Gew.-%, bevorzugt 10 bis 20 Gew.- 1. Verfahren zur Herstellung von Aminoethylethanola- % Wasser; und 0 bis 20 Gew.-%, bevorzugt 0 bis min und/oder Hydroxyethylpiperazin durch Ethoxy- 35 10 Gew.-% Piperazin enthält. lierung von Ethylendiamin und/oder Piperazin mit Ethylenoxid in Gegenwart eines Katalysators, da- 8. Verfahren wie in Anspruch 3, 4 oder 5 beansprucht, durch gekennzeichnet, daß dadurch gekennzeichnet, daß eine Produktmi- schung ethoxyliert wird, die 60 bis 100 Gew.-%, be- - Ethylendiamin und/oder Piperazin mit 0,05 bis 40 vorzugt 80 bis 95 Gew.-% Ethylendiamin; und 0 bis 0,5 Mol, bevorzugt 0,1 bis 0,3 Mol, Ethylenoxid 40 Gew.-%, bevorzugt 5 bis 20 Gew.-% Piperazin pro Mol Ethylendiamin und/oder Piperazin kon- enthält. tinuierlich umgesetzt wird/werden, - der sich ergebende Ethoxylierungsprodukt- strom in eine Destillationsanlage eingespeist 45 Revendications wird, die für die Verarbeitung eines Aminie- rungsproduktstromes, der durch Aminierung 1. Procédé de production d'aminoéthyléthanolamine von Monoethanolamin mit Ammoniak erhalten et/ou d'hydroxyéthylpipérazine par éthoxylation wird, ausgelegt ist, und d'éthylènediamine et/ou de pipérazine avec de - der Ethoxylierungsproduktstrom in der Destilla- 50 l'oxyde d'éthylène en présence d'un catalyseur, ca- tionsanlage destilliert wird, während Aminoe- ractérisé par les étapes consistant : thylethanolamin und/oder Hydroxyethylpipera- zin gewonnen wird/werden. - à faire réagir en continu de l'éthylènediamine et/ou de la pipérazine avec 0,05-0,5 mole 2. Verfahren wie in Anspruch 1 beansprucht, dadurch 55 d'oxyde d'éthylène, de préférence 0,1-0,3 mo- gekennzeichnet, daß es in Gegenwart von Wasser le, par mole d'éthylénediamine et/ou de pipéra- als Katalysator bei einer Temperatur von 20 bis zine, 95°C, bevorzugt 40 bis 80°C, durchgeführt wird. - à introduire le ﬂux de produit d'éthoxylation ob-

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tenu dans une installation de distillation conçue pour traiter un ﬂux de produit d'amination obte- nu en aminant de la monoéthanolamine avec de l'ammoniac, et - à distiller le ﬂux de produit d'éthoxylation dans 5 l'installation de distillation tout en récupérant de l'aminoéthyléthanolamine et/ou de l'hydroxyé- thylpipérazine.

2. Procédé selon la revendication 1, caractérisé en ce 10 qu'il est effectué en présence d'eau comme catalyseur à une température de 20-95°C, de préférence 40-80°C.

3. Procédé selon la revendication 1, caractérisé en ce 15 qu'il est effectué en l'absence d'eau, mais en pré- sence d'un catalyseur solide, qui n'est pas dissous au cours de la réaction, et à une température de 20-150°C, de préférence 40-120°C. 20 4. Procédé selon la revendication 1, 2 ou 3, caracté- risé en ce qu'on introduit le flux de produit d'éthoxy- lation dans l'installation de distillation avant la pre- mière colonne où, dans la distillation du flux de produit d'amination, on sépare un composé ou un mé- 25 lange qui contient un composé faisant partie du flux de produit d'éthoxylation.

5. Procédé selon l'une quelconque des revendications 1-4, caractérisé en ce qu'on joint le ﬂux de produit 30 d'éthoxylation au ﬂux de produit d'amination et on les distille conjointement dans l'installation de distillation.

6. Procédé selon l'une quelconque des revendications 35 1-5, caractérisé en ce qu'on éthoxyle une fraction d'éthylènediamine qui contient au moins 95% en poids d'éthylènediamine et qui a été obtenue dans l'installation de distillation. 40 7. Procédé selon l'une quelconque des revendications 1, 2, 4 et 5, caractérisé en ce qu'on éthoxyle un mé- lange de produits qui contient 55-95% en poids d'éthylènediamine, de préférence 70-90% en poids; 1-30% en poids d'eau, de préférence 10-20% en 45 poids; et 0-20% en poids de pipérazine, de préfé- rence 0-10% en poids.

8. Procédé selon la revendication 3, 4 ou 5, caracté- risé en ce qu'on éthoxyle un mélange de produits 50 qui contient 60-100% en poids d'éthylènediamine, de préférence 80-95% en poids; et 0-40% en poids de pipérazine, de préférence 5-20% en poids.

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