EP0238958A2 - Method for the purification of tetraacetylethylenediamine - Google Patents

Method for the purification of tetraacetylethylenediamine Download PDF

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Publication number
EP0238958A2
EP0238958A2 EP87103737A EP87103737A EP0238958A2 EP 0238958 A2 EP0238958 A2 EP 0238958A2 EP 87103737 A EP87103737 A EP 87103737A EP 87103737 A EP87103737 A EP 87103737A EP 0238958 A2 EP0238958 A2 EP 0238958A2
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Prior art keywords
taed
drying
acetic acid
carried out
water
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German (de)
French (fr)
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EP0238958A3 (en
EP0238958B1 (en
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Klaus Dr. Köster
Franz-Josef Dr. Carduck
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/32—Amides; Substituted amides

Definitions

  • TAED tetraacetylethylenediamine
  • DAED acetylation of N, N'-diacetylethylenediamine
  • the reaction of DAED with acetic anhydride which is usually carried out at temperatures between 120 and 170 ° C with excess acetic anhydride, provides TAED in an equilibrium reaction, so that the reaction mixtures contain, in addition to the desired end product, unreacted DAED and triacetylethylenediamine. Furthermore, dark-colored by-products of unknown nature are formed during the reaction.
  • Raw TAED as it is isolated from these reaction mixtures, for example by crystallization, always contains a certain proportion of by-products and can generally not be used directly in this form, since a product that is as pure, colorless and odorless as possible is required for most fields of application becomes. The manufacture of the TAED must therefore be combined with a cleaning process.
  • the task was therefore still to develop a simple and effective cleaning process for TAED.
  • the task was to develop such a cleaning process that delivers a TAED in the purity suitable for use in detergents.
  • this object is achieved by a cleaning process which consists in first washing (a) the crude, crystalline TAED with acetic acid, then (b) washing with water and finally (c) drying. Partial drying is preferably also carried out between the two washing steps. In particularly preferred process variants, several successive substeps are carried out in the same apparatus and / or drying is achieved in one or both drying steps with the aid of gases, preferably air, which are blown through the product.
  • the process according to the invention surprisingly enables a colorless and odorless product to be obtained without significant losses of valuable materials with extremely small amounts of washing liquids.
  • the need for time, energy and equipment is also low, so that the process is faster and despite the need for three or four individual steps less expensive cleaning than other processes with the same effectiveness.
  • the cleaning process according to the invention is not tied to a specific TAED manufacturing process. In a particularly advantageous manner, however, it is used according to production processes in which acetic acid is a component of the reaction mixture, because then the first washing liquid can be worked up together with the mother liquors of the reaction and, if necessary, recycled.
  • the cleaning process according to the invention therefore preferably follows a manufacturing process in which TAED is obtained by acetylation using acetic anhydride.
  • the individual stages of the cleaning process according to the invention can be carried out individually in separate apparatuses, as are known per se for filtration, washing and drying processes. However, preferably several, in particular all, steps are carried out in the same apparatus. Examples of devices in which both washing operations and drying can be carried out are single-layer filters, such as pressure filters and filter driers, belt filters and drum filters.
  • the rotary pressure filters are preferred, which allow not only all stages of the cleaning process according to the invention to be carried out continuously in several successive working segments, but also on which the preceding last step of the production process, the filtering off of the crystalline TAED, can be carried out.
  • the design of the individual stages of the cleaning process depends on both the quality of the raw TAED and the desired quality of the cleaned material. At the process according to the invention can be adapted within wide limits to both circumstances.
  • the first wash cycle (a) is preferably carried out at temperatures between 17 and 30 ° C., but optionally also by using warm TAED and / or heated acetic acid, at elevated temperatures, but preferably not above 50 ° C.
  • the amounts of acetic acid which may also contain small amounts of water, are preferably from 0.2 to 2 l, in particular from 0.5 to 1.2 l, per kg of TAED (calculated as pure substance).
  • the washing can be supported by slurrying and moving the TAED in the acetic acid, but is preferably carried out on the more or less immobile filter cake of the TAED.
  • the contact times from the addition of acetic acid to the end of the filtering, or the flow times are between about 0.001 and 6, preferably between 0.01 and 2 seconds.
  • the drying step that follows the acetic acid wash in the preferred embodiment of the process is preferably carried out on the filter used for the previous step. If this drying can also be achieved in the usual way under vacuum, if necessary with heating, it has proven to be more advantageous to blow gases which are inert for drying, such as nitrogen or carbon dioxide, but preferably air, through the product under pressure. Moving the product during this process can be useful, but is not necessary. Gas quantities of 0.05 to 2 m3, preferably 0.1 to 1 m3 per kg TAED are generally sufficient for the partial drying required according to the invention.
  • the inlet temperatures of the gases are preferably 10 to 100 ° C, in particular between 15 and 70 ° C.
  • the second wash cycle (b) is carried out with water of preferably 5-50 ° C., in particular 10-30 ° C., and can also supported by slurrying and moving the TAED in the water.
  • the washing liquid is preferably also passed through the stationary filter cake.
  • the amounts of wash water are preferably between 0.5 and 8 l, in particular between 1 and 5 l per kg of TAED. They depend primarily, as do the contact or flow times, which are preferably between about 0.001 and 6 seconds, in particular between 0.01 and 2 seconds, on the acetic acid content of the TAED.
  • the final drying step (c) is generally carried out in a manner similar to the drying step after washing with acetic acid.
  • the conditions are chosen so that, in combination with the previous washing process, the acetic acid is removed as far as required, preferably until the product is odorless, and the water content of the material corresponds to the specified specification.
  • drying is preferably carried out with the aid of gases, in particular air, which are blown through the moist material at temperatures of preferably 10 to 100 ° C., in particular between 15 and 70 ° C.
  • the gas quantities required are preferably between 0.05 and 2 m3, in particular between 0.1 and 1 m3, per kg of TAED.
  • the cleaning method according to the invention allows the TAED obtained to be used directly for further use, in particular in detergents, bleaches and disinfectants.
  • the finely crystalline TAED is first converted into granules in an agglomeration process, for example according to DE 30 11 998.
  • the amount of water required in this process can already be passed on to the cleaned TAED by suitable control of stages b and c of the cleaning process according to the invention.
  • a total of 364 kg of a colorless and odorless TAED was obtained.
  • the water content was 5.4% by weight, based on dry matter, which in turn had a TAED content of 99.4%.
  • the TAED cleaned in this way was suitable for use in detergents and could easily be incorporated into a granulation process.
  • the loss of acetic acid with the wash water was carried out were low (acetic acid content of the washing water 4%).
  • Example 1 The procedure was the same as in Example 1, but the intermediate drying after washing with acetic acid was dispensed with. In order to obtain an odorless product, the filter cake had to be washed with 5 l of water per kg of TAED. The losses of acetic acid, which resulted from the discharge with the washing water, were three times as high as in Example 1. In addition, the cleaned TAED was just as suitable for use in detergents as that obtained in Example 1.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Crude tetraacetylethylenediamine (TAED), such as obtained in crystalline form during synthesis, is converted by successive washing with acetic acid and water and subsequent drying into a colourless and odourless form, such as is required for use in detergents and bleaching agents.

Description

Die Verbindung N,N,N',N′-Tetraacetylethylendiamin, im folgenden einfacher als Tetraacetylethylendiamin oder TAED bezeichnet, hat in jüngster Zeit praktische Bedeutung als Aktivator in peroxid­haltigen Bleichflotten und Waschmitteln gewonnen. Wichtigstes Herstellungsverfahren ist die Acetylierung von N,N′-Diacetyl­ethylendiamin (DAED) mit Hilfe von Acetanhydrid. Von diesem Verfahren, nach dem TAED im Jahre 1911 zum ersten Mal herge­stellt wurde, sind inzwischen zahlreiche Varianten bekannt ge­worden (z. B. DE 21 33 458, DE 21 18 281, DE 30 24 694, GB 2 096 133, EP 4 919, EP 51 739 und EP 79 671).The compound N, N, N ', N'-tetraacetylethylenediamine, hereinafter simply referred to as tetraacetylethylenediamine or TAED, has recently gained practical importance as an activator in peroxide-containing bleaching liquors and detergents. The most important manufacturing process is the acetylation of N, N'-diacetylethylenediamine (DAED) with the help of acetic anhydride. Numerous variants of this process, according to which TAED was manufactured for the first time in 1911, have now become known (e.g. DE 21 33 458, DE 21 18 281, DE 30 24 694, GB 2 096 133, EP 4 919 , EP 51 739 and EP 79 671).

Die Umsetzung von DAED mit Acetanhydrid, die üblicherweise bei Temperaturen zwischen 120 und 170 °C mit überschüssigem Acetan­hydrid durchgeführt wird, liefert TAED in einer Gleichgewichts­reaktion, so daß die Reaktionsgemische neben dem gewünschten Endprodukt noch unumgesetztes DAED und Triacetylethylendiamin enthalten. Weiterhin bilden sich während der Reaktion dunkel­farbige Nebenprodukte unbekannter Natur. Rohes TAED, wie es aus diesen Reaktionsgemischen, beispielsweise durch Kristalli­sation, isoliert wird, enthält stets einen gewissen Anteil an Beiprodukten und kann in dieser Form im allgemeinen nicht direkt weiterverwendet werden, da für die meisten Anwendungsgebiete ein möglichst reines, farb- und geruchloses Produkt benötigt wird. Die Herstellung des TAED muß deshalb mit einem Reinigungsverfahren verbunden werden.The reaction of DAED with acetic anhydride, which is usually carried out at temperatures between 120 and 170 ° C with excess acetic anhydride, provides TAED in an equilibrium reaction, so that the reaction mixtures contain, in addition to the desired end product, unreacted DAED and triacetylethylenediamine. Furthermore, dark-colored by-products of unknown nature are formed during the reaction. Raw TAED, as it is isolated from these reaction mixtures, for example by crystallization, always contains a certain proportion of by-products and can generally not be used directly in this form, since a product that is as pure, colorless and odorless as possible is required for most fields of application becomes. The manufacture of the TAED must therefore be combined with a cleaning process.

Auch zur Reinigung des TAED sind zahlreiche Vorschläge gemacht worden, die von einer einfachen Wäsche mit Acetanhydrid (DE 21 33 458, DE 21 18 281) über die Anwendung von Adsorptions­mitteln vor der Kristallisation (EP 4 919) bis hin zur frakti­onierten Destillation des TAED (EP 8 369) reichen. Weiterhin ist vorgeschlagen worden (EP 70 432), das rohe TAED in einem Sus-­pensionsmittel fein zu dispergieren und nach längerer Verweilzeit wieder zu isolieren. Keines dieser Reinigungsverfahren ist jedoch frei von Nachteilen, seien es geringe Wirksamkeit oder Produkt­verluste oder aber hoher Energie- und/oder Geräteaufwand.Numerous proposals have also been made for cleaning the TAED, from simple washing with acetic anhydride (DE 21 33 458, DE 21 18 281) to the use of adsorbents prior to crystallization (EP 4 919) to fractional distillation of the TAED ( EP 8 369) are sufficient. Furthermore, it has been proposed (EP 70 432) to finely disperse the crude TAED in a suspension medium and to isolate it again after a relatively long residence time. However, none of these cleaning processes is free from disadvantages, be it low effectiveness or product losses or high energy and / or equipment expenditure.

Es bestand daher nach wie vor die Aufgabe, ein einfaches und wirksames Reinigungsverfahren für TAED zu entwickeln. Ins­besondere bestand die Aufgabe, ein solches Reinigungsverfahren zu entwickeln, das ein TAED in der für den Einsatz in Wasch­mitteln geeigneten Reinheit liefert.The task was therefore still to develop a simple and effective cleaning process for TAED. In particular, the task was to develop such a cleaning process that delivers a TAED in the purity suitable for use in detergents.

Diese Aufgabe wird erfingungsgemäß gelöst durch ein Reinigungs­verfahren, das darin besteht, das rohe, kristalline TAED zu­nächst (a) mit Essigsäure zu waschen, dann (b) mit Wasser zu waschen und schließlich (c) zu trocknen. Vorzugsweise wird auch zwischen den beiden Waschschritten eine partielle Trocknung vorgenommen. In besonders bevorzugten Verfahrensvarianten werden mehrere aufeinanderfolgende Teilschritte in derselben Apparatur durchgeführt und/oder die Trocknung in einem oder beiden Trocknungsschritten mit Hilfe von Gasen, vorzugsweise Luft, erreicht, die durch das Produkt geblasen werden.According to the invention, this object is achieved by a cleaning process which consists in first washing (a) the crude, crystalline TAED with acetic acid, then (b) washing with water and finally (c) drying. Partial drying is preferably also carried out between the two washing steps. In particularly preferred process variants, several successive substeps are carried out in the same apparatus and / or drying is achieved in one or both drying steps with the aid of gases, preferably air, which are blown through the product.

Das erfindungsgemäße Verfahren erlaubt es überraschenderweise, ohne wesentliche Verluste an Wertstoffen mit äußerst geringen Mengen an Waschflüssigkeiten ein farbloses und geruchsloses Produkt zu gewinnen. Der Bedarf an Zeit, Energie und Geräten ist ebenfalls gering, so daß das Verfahren trotz der Notwendig­keit von drei bzw. vier Einzelschritten eine schnellere und kostengünstigere Reinigung ermöglicht als andere Verfahren gleicher Wirksamkeit.The process according to the invention surprisingly enables a colorless and odorless product to be obtained without significant losses of valuable materials with extremely small amounts of washing liquids. The need for time, energy and equipment is also low, so that the process is faster and despite the need for three or four individual steps less expensive cleaning than other processes with the same effectiveness.

Das erfindungsgemäße Reinigungsverfahren ist nicht an ein be­stimmtes Herstellungsverfahren des TAED gebunden. In besonders vorteilhafter Weise wird es aber nach solchen Herstellungsver­fahren, bei denen Essigsäure ein Bestandteil der Reaktions­mischung ist, angewendet, weil dann die erste Waschflüssigkeit ohne weiteres zusammen mit den Mutterlaugen der Reaktion auf­gearbeitet und ggf. zurückgeführt werden kann. Vorzugsweise schließt sich deshalb das erfindungsgemäße Reinigungsverfahren an ein Herstellungsverfahren an, bei dem TAED durch Acety­lierung mittels Acetanhydrid gewonnen wird.The cleaning process according to the invention is not tied to a specific TAED manufacturing process. In a particularly advantageous manner, however, it is used according to production processes in which acetic acid is a component of the reaction mixture, because then the first washing liquid can be worked up together with the mother liquors of the reaction and, if necessary, recycled. The cleaning process according to the invention therefore preferably follows a manufacturing process in which TAED is obtained by acetylation using acetic anhydride.

Die einzelnen Stufen des erfindungsgemäßen Reinigungsverfahrens können einzeln in getrennten Apparaturen, wie sie an sich für Filtrations-, Wasch- und Trockenprozesse bekannt sind, aus­geführt werden. Vorzugsweise werden aber mehrere, insbesondere alle Schritte in derselben Apparatur durchgeführt. Beispiele für Geräte, in denen sowohl Waschoperationen als auch die Trocknung durchgeführt werden können, sind Einschichtenfilter, wie Druck­nutschen und Filtertrockner, Bandfilter und Trommelfilter.The individual stages of the cleaning process according to the invention can be carried out individually in separate apparatuses, as are known per se for filtration, washing and drying processes. However, preferably several, in particular all, steps are carried out in the same apparatus. Examples of devices in which both washing operations and drying can be carried out are single-layer filters, such as pressure filters and filter driers, belt filters and drum filters.

Von diesen werden wiederum die Druckdrehfilter bevorzugt, die es gestatten, kontinuierlich in mehreren aufeinanderfolgenden Arbeitssegmenten nicht nur alle Stufen des erfindungsgemäßen Reinigungsverfahrens auszuführen, sondern auf denen auch der vorhergehende letzte Schritt des Herstellungsverfahrens, das Ab­filtrieren des kristallinen TAED, vorgenommen werden kann.Of these, the rotary pressure filters are preferred, which allow not only all stages of the cleaning process according to the invention to be carried out continuously in several successive working segments, but also on which the preceding last step of the production process, the filtering off of the crystalline TAED, can be carried out.

Die Ausgestaltung der einzelnen Stufen des Reinigungsverfahrens richtet sich sowohl nach der Qualität des rohen TAED als auch nach der gewünschten Qualität des gereinigten Materials. An beide Gegebenheiten läßt sich das erfindungsgemäße Verfahren in weiten Grenzen anpassen.The design of the individual stages of the cleaning process depends on both the quality of the raw TAED and the desired quality of the cleaned material. At the process according to the invention can be adapted within wide limits to both circumstances.

Der erste Waschgang (a) wird vorzugsweise bei Temperaturen zwischen 17 und 30 °C, gegebenenfalls aber auch, durch Ver­wendung von warmem TAED und/oder erwärmter Essigsäure, bei erhöhten Temperaturen, vorzugsweise aber nicht über 50 °C durch­geführt. Die Einsatzmengen an Esssigsäure, die gegebenenfalls auch kleine Mengen an Wasser enthalten kann, liegen vorzugs­weise bei 0,2 bis 2 l, insbesondere zwischen 0,5 bis 1,2 l pro kg TAED (gerechnet als Reinsubstanz). Die Wäsche kann durch Auf­schlämmen und Bewegen des TAED in der Essigsäure unterstützt werden, wird vorzugsweise aber am mehr oder weniger unbe­wegten Filterkuchen des TAED vorgenommen. Die Kontaktzeiten von der Zugabe der Essigsäure bis zum Ende des Abfiltrierens, beziehungsweise die Durchströmzeiten, liegen zwischen etwa 0,001 und 6, vorzugsweise zwischen 0,01 und 2 Sekunden.The first wash cycle (a) is preferably carried out at temperatures between 17 and 30 ° C., but optionally also by using warm TAED and / or heated acetic acid, at elevated temperatures, but preferably not above 50 ° C. The amounts of acetic acid, which may also contain small amounts of water, are preferably from 0.2 to 2 l, in particular from 0.5 to 1.2 l, per kg of TAED (calculated as pure substance). The washing can be supported by slurrying and moving the TAED in the acetic acid, but is preferably carried out on the more or less immobile filter cake of the TAED. The contact times from the addition of acetic acid to the end of the filtering, or the flow times, are between about 0.001 and 6, preferably between 0.01 and 2 seconds.

Der Trocknungsschritt, der in der bevorzugten Ausführungsform des Verfahrens auf die Essigsäurewäsche folgt, wird vorzugsweise auf dem Filter, das für den vorangegangenen Schritt benutzt wurde, ausgeführt. Wenn diese Trocknung auch in üblicher Weise unter Vakuum gegebenenfalls unter Erwärmen erreicht werden kann, so hat es sich doch als vorteilhafter erwiesen, zur Trocknung inerte Gase, wie Stickstoff oder Kohlendioxid, vor­zugsweise aber Luft unter Druck durch das Produkt zu blasen. Eine Bewegung des Produktes während dieses Vorganges kann nütz­lich sein, ist aber nicht notwendig. Gasmengen von 0,05 bis 2 m³, vorzugsweise 0,1 bis 1 m³ pro kg TAED reichen im all­gemeinen für die erfindungsgemäß geforderte partielle Trocknung aus. Die Eintrittstemperaturen der Gase liegen vorzugsweise bei 10 bis 100 °C, insbesondere zwischen 15 und 70 °C.The drying step that follows the acetic acid wash in the preferred embodiment of the process is preferably carried out on the filter used for the previous step. If this drying can also be achieved in the usual way under vacuum, if necessary with heating, it has proven to be more advantageous to blow gases which are inert for drying, such as nitrogen or carbon dioxide, but preferably air, through the product under pressure. Moving the product during this process can be useful, but is not necessary. Gas quantities of 0.05 to 2 m³, preferably 0.1 to 1 m³ per kg TAED are generally sufficient for the partial drying required according to the invention. The inlet temperatures of the gases are preferably 10 to 100 ° C, in particular between 15 and 70 ° C.

Der zweite Waschgang (b) wird mit Wasser von vorzugsweise 5 - ­50 °C, insbesondere 10 - 30 °C durchgeführt und kann ebenfalls durch Aufschlämmen und Bewegen des TAED im Wasser unter­stützt werden. Vorzugsweise wird aber auch hier die Wasch­flüssigkeit durch den unbewegten Filterkuchen geleitet. Die Mengen an Waschwasser liegen vorzugsweise zwischen 0,5 und 8 l, insbesondere zwischen 1 und 5 l pro kg TAED. Sie richten sich in erster Linie, ebensowie die Kontakt- bzw. Durchströmzeiten, die vorzugsweise zwischen etwa 0,001 und 6 Sekunden, insbeson­dere zwischen 0,01 und 2 Sekunden liegen, nach dem Essigsäure­gehalt des TAED.The second wash cycle (b) is carried out with water of preferably 5-50 ° C., in particular 10-30 ° C., and can also supported by slurrying and moving the TAED in the water. However, the washing liquid is preferably also passed through the stationary filter cake. The amounts of wash water are preferably between 0.5 and 8 l, in particular between 1 and 5 l per kg of TAED. They depend primarily, as do the contact or flow times, which are preferably between about 0.001 and 6 seconds, in particular between 0.01 and 2 seconds, on the acetic acid content of the TAED.

Der abschließende Trocknungsschritt (c) wird im allgemeinen in ähnlicher Weise durchgeführt wie der Trocknungsschritt nach der Wäsche mit Essigsäure. Die Bedingungen werden so gewählt, daß in Kombination mit dem vorausgegangenen Waschprozeß die Essig­säure soweit wie gefordert, vorzugsweise bis zur Geruchslosigkeit des Produktes, entfernt wird und der Wassergehalt des Materials der vorgegebenen Spezifikation entspricht. Vorzugsweise wird auch in diesem Trocknungsschritt mit Hilfe von Gasen, insbesondere Luft, getrocknet, die mit Temperaturen von vorzugsweise 10 bis 100 °C, insbesondere zwischen 15 und 70 °C durch das feuchte Material geblasen werden. Die benötigten Gasmengen liegen wie im ersten Trocknungsschritt vorzugsweise zwischen 0,05 bis 2 m³, insbesondere zwischen 0,1 und 1 m³ pro kg TAED.The final drying step (c) is generally carried out in a manner similar to the drying step after washing with acetic acid. The conditions are chosen so that, in combination with the previous washing process, the acetic acid is removed as far as required, preferably until the product is odorless, and the water content of the material corresponds to the specified specification. In this drying step, too, drying is preferably carried out with the aid of gases, in particular air, which are blown through the moist material at temperatures of preferably 10 to 100 ° C., in particular between 15 and 70 ° C. As in the first drying step, the gas quantities required are preferably between 0.05 and 2 m³, in particular between 0.1 and 1 m³, per kg of TAED.

Das erfindungsgemäße Reinigungsverfahren erlaubt es, das an­fallende TAED direkt der weiteren Verwendung, insbesondere in Wasch-, Bleich- und Desinfektionsmitteln zuzuführen. In der Re­gel wird das feinkristalline TAED jedoch, um die Lagerstabilität in Gegenwart alkalischer Materialien zu erhöhen, zunächst in einem Agglomerationsprozeß, beispielsweise nach DE 30 11 998 in ein Granulat übergeführt. Die bei diesem Prozeß notwendige Wassermenge kann durch geeignete Führung der Stufen b und c des erfindungsgemäßen Reinigungsverfahrens ohne weiteres be­reits dem gereinigten TAED mitgegeben werden.The cleaning method according to the invention allows the TAED obtained to be used directly for further use, in particular in detergents, bleaches and disinfectants. As a rule, however, in order to increase the storage stability in the presence of alkaline materials, the finely crystalline TAED is first converted into granules in an agglomeration process, for example according to DE 30 11 998. The amount of water required in this process can already be passed on to the cleaned TAED by suitable control of stages b and c of the cleaning process according to the invention.

Beispiel 1example 1

In einem Rührkessel mit Rückflußkühler und Bodenablaß wurden 360 kg Diacetylethylendiamin mit 1275 kg Acetanhydrid 3 Stunden auf Rückflußtemperatur erhitzt. Die entstandene braune Lösung wurde unter Rühren rasch auf etwa 30 °C abgekühlt, wobei TAED in kristalliner Form ausfiel. Die Kristallsuspension wurde auf ein Druckdrehfilter mit sechs Segmenten abgelassen, auf dem kontinu­ierlich nacheinander folgende Prozesse abliefen (Angaben bezogen auf 1 kg TAED-Reinsubstanz):

- Weitgehende Abtrennung der Mutterlauge,

- Waschen des rohen TAED mit 0,8 l Essigsäure (Wassergehalt 0,6 Gew.-%, Temperatur 25 °C, Druck 0,8 - 1 bar) bei einer Kontaktzeit von ca. 0,05 sec,

- Durchblasen von 0,2 m³ Luft (Temperatur 20 °C, Druck 1,5 bar), die über einen Flüssigkeitsabscheider recyclisiert wurde,

- Waschen mit 1,8 l Wasser (Temperatur 15 °C, Druck 1 bar) bei einer Kontaktzeit von ca. 0,05 sec,

- Durchblasen von 0,3 m³ Luft (Temperatur 20 °C, Druck 1,8 bar),

- Mechanisches Austragen des Endproduktes.In a stirred kettle with reflux condenser and bottom drain, 360 kg of diacetylethylenediamine with 1275 kg of acetic anhydride were heated to reflux temperature for 3 hours. The resulting brown solution was rapidly cooled to about 30 ° C. with stirring, whereby TAED precipitated out in crystalline form. The crystal suspension was drained onto a rotary pressure filter with six segments, on which the following processes were carried out continuously in succession (data based on 1 kg of pure TAED substance):

- extensive separation of the mother liquor,

- washing the raw TAED with 0.8 l acetic acid (water content 0.6% by weight, temperature 25 ° C, pressure 0.8 - 1 bar) with a contact time of approx. 0.05 sec,

Blowing through 0.2 m³ of air (temperature 20 ° C., pressure 1.5 bar), which was recycled via a liquid separator,

- washing with 1.8 l water (temperature 15 ° C, pressure 1 bar) with a contact time of approx. 0.05 sec,

- blowing through 0.3 m³ of air (temperature 20 ° C, pressure 1.8 bar),

- Mechanical discharge of the end product.

Insgesamt fielen 364 kg eines farb- und geruchlosen TAED an. Der Wassergehalt lag bei 5,4 Gew.-%, bezogen auf Trockenmasse, die ihrerseits einen TAED-Gehalt von 99,4 % aufwies. Das so ge­reinigte TAED eignete sich für den Einsatz in Waschmitteln und konnte ohne weiteres in einen Granulationsprozeß eingebracht werden. Die Verluste an Essigsäure, die mit dem Waschwasser ausgetragen wurde, waren gering (Essigsäuregehalt des Waschwassers 4 %).A total of 364 kg of a colorless and odorless TAED was obtained. The water content was 5.4% by weight, based on dry matter, which in turn had a TAED content of 99.4%. The TAED cleaned in this way was suitable for use in detergents and could easily be incorporated into a granulation process. The loss of acetic acid with the wash water was carried out were low (acetic acid content of the washing water 4%).

Beispiel 2Example 2

Es wurde ebenso verfahren, wie im Beispiel 1, doch wurde auf das Zwischentrocknen nach der Essigsäurewäsche verzichtet. Um ein geruchsfreies Produkt zu erhalten, mußte der Filterkuchen mit 5 l Wasser pro kg TAED gewaschen werden. Die Essigsäurever­luste, die durch Abgang mit dem Waschwasser entstanden, waren dabei drei mal so hoch wie in Beispiel 1. Im übrigen eignete sich das gereinigte TAED aber ebenso gut für den Einsatz in Wasch­mitteln wie das in Beispiel 1 erhaltene.The procedure was the same as in Example 1, but the intermediate drying after washing with acetic acid was dispensed with. In order to obtain an odorless product, the filter cake had to be washed with 5 l of water per kg of TAED. The losses of acetic acid, which resulted from the discharge with the washing water, were three times as high as in Example 1. In addition, the cleaned TAED was just as suitable for use in detergents as that obtained in Example 1.

Beispiel 3Example 3

Die Ausführung dieses Beispiels entsprach ebenfalls Beispiel 1, doch wurde in der ersten Waschstufe Acetanhydrid anstelle von Essigsäure als Waschflüssigkeit verwendet. Trotz Erhöhung der Wassermenge im folgenden Waschprozeß auf über 8 l pro kg TAED enthielt das Endprodukt mehr als 1 % Essigsäure, so daß es nicht für den Einsatz in Waschmitteln geeignet war. Zur Entfernung der Essigsäure mußte das TAED einem weiteren, intensiven Trocknungsprozeß unterworfen werden.The execution of this example also corresponded to example 1, but in the first washing stage acetic anhydride was used as the washing liquid instead of acetic acid. Despite increasing the amount of water in the following washing process to over 8 l per kg TAED, the end product contained more than 1% acetic acid, so that it was not suitable for use in detergents. To remove the acetic acid, the TAED had to be subjected to a further, intensive drying process.

Claims (10)

1. Verfahren zur Reinigung von kristallinem N,N,N′,N′-Tetraace­tylethylendiamin (TAED), gekennzeichnet durch folgende Ver­fahrensschritte: a) Wäsche mit Essigsäure b) Wäsche mit Wasser c) Trocknung. 1. Process for the purification of crystalline N, N, N ', N'-tetraacetylethylenediamine (TAED), characterized by the following process steps: a) Wash with acetic acid b) Wash with water c) drying. 2. Verfahren nach Anspruch 1, bei dem zwischen den Verfahrens­schritten a und b eine partielle Trocknung vorgenommen wird.2. The method according to claim 1, in which a partial drying is carried out between process steps a and b. 3. Verfahren nach einem der Ansprüche 1 oder 2, bei dem einer oder beide Trocknungsschritte darin bestehen, Gase durch das feuchte Produkt zu blasen.3. The method according to any one of claims 1 or 2, wherein one or both drying steps consist in blowing gases through the moist product. 4. Verfahren nach Anspruch 3, bei dem als Gas Luft verwendet wird.4. The method according to claim 3, in which air is used as gas. 5. Verfahren nach einem der Ansprüche 1 bis 4, bei dem mehrere aufeinander folgende Schritte in derselben Apparatur durchgeführt werden.5. The method according to any one of claims 1 to 4, in which several successive steps are carried out in the same apparatus. 6. Verfahren nach Anspruch 5, bei dem alle Verfahrensschritte kontinuierlich in einem Druckdrehfilter ausgeführt werden.6. The method according to claim 5, in which all process steps are carried out continuously in a rotary pressure filter. 7. Verfahren nach einem der Ansprüche 1 bis 6, bei dem pro kg TAED 0,2 - 2 l Essigsäure als Waschflüssigkeit verwendet werden.7. The method according to any one of claims 1 to 6, in which 0.2-2 l acetic acid are used as washing liquid per kg of TAED. 8. Verfahren nach einem der Ansprüche 1 bis 7, bei dem pro kg TAED 0,5 - 8 l Wasser als Waschflüssigkeit verwendet werden.8. The method according to any one of claims 1 to 7, in which 0.5 - 8 l of water are used as washing liquid per kg of TAED. 9. Verfahren nach einem der Ansprüche 1 bis 8, bei dem zur Trocknung 0,05 bis 2 m³ Luft mit einer Eintrittstemperatur von 10 bis 100 °C verwendet werden.9. The method according to any one of claims 1 to 8, in which 0.05 to 2 m³ of air with an inlet temperature of 10 to 100 ° C are used for drying. 10. Verwendung eines nach einem der Verfahren gemäß An­sprüchen 1 bis 9 gereinigten TAED in Wasch-, Bleich- oder Desinfektionsmitteln.10. Use of a TAED cleaned according to one of the processes according to claims 1 to 9 in detergents, bleaches or disinfectants.
EP87103737A 1986-03-22 1987-03-14 Method for the purification of tetraacetylethylenediamine Expired - Lifetime EP0238958B1 (en)

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AT87103737T ATE64410T1 (en) 1986-03-22 1987-03-14 METHOD OF PURIFICATION OF TETRAACETYLETHYLENE DIAMINE.

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DE19863609735 DE3609735A1 (en) 1986-03-22 1986-03-22 METHOD FOR PURIFYING TETRAACETYLETHYLENE DIAMINE
DE3609735 1986-03-22

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EP0238958A3 EP0238958A3 (en) 1988-08-17
EP0238958B1 EP0238958B1 (en) 1991-06-12

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DE (2) DE3609735A1 (en)
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IE (1) IE59879B1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0484634A1 (en) * 1990-11-09 1992-05-13 CAFFARO S.p.A. Process for the purification of tetraacetylethylene diamine (TAED)
CN103121960A (en) * 2013-02-22 2013-05-29 浙江金科日化原料有限公司 Efficient recrystallization method of tetraacetylethylenediamine

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DE2133458A1 (en) 1970-07-07 1972-02-03 Unilever Nv Process for the preparation of polyacetylalkylene diamines
DE2118281A1 (en) 1971-04-15 1972-11-02 Badische Anilin- & Soda-Fabrik Ag, 6700 Ludwigshafen Process for the continuous production of N, N, N, N-tetraacetylethylenediamine
EP0004919A1 (en) 1978-04-14 1979-10-31 Hoechst Aktiengesellschaft Process for preparing N,N,N',N'-tetra-acetylethylene diamine
EP0008369A1 (en) 1978-07-21 1980-03-05 BASF Aktiengesellschaft Process for preparing N,N,N',N'-tetraacetylethylene diamine
DE3011998A1 (en) 1980-03-28 1981-10-08 Henkel KGaA, 4000 Düsseldorf METHOD FOR THE PRODUCTION OF STORAGE-STABLE, EASILY DETACHABLE GRANULATES WITH A CONTENT OF BLEACHING ACTIVATORS
DE3024694A1 (en) 1980-06-30 1982-01-28 Warwick Chemicals Ltd., Leeds Tetra:acetyl ethylene di:amine prodn. from ethylene di:amine - by reaction with acetic acid and anhydride in several cycles, useful in detergent as perborate activator
EP0051739A1 (en) 1980-11-08 1982-05-19 BASF Aktiengesellschaft Process for the preparation of tetraacetylethylene diamine
GB2096133A (en) 1981-04-03 1982-10-13 Croda Chemicals Ltd Production of tetraacetylethylene diamine
EP0070432A1 (en) 1981-07-11 1983-01-26 Bayer Ag Process for the preparation of purified tetraacetylethylene diamine (TAED)
EP0079671A2 (en) 1981-09-28 1983-05-25 Albright & Wilson Limited Process for preparing tetraacetyl alkylene diamines

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Publication number Priority date Publication date Assignee Title
DE2133458A1 (en) 1970-07-07 1972-02-03 Unilever Nv Process for the preparation of polyacetylalkylene diamines
DE2118281A1 (en) 1971-04-15 1972-11-02 Badische Anilin- & Soda-Fabrik Ag, 6700 Ludwigshafen Process for the continuous production of N, N, N, N-tetraacetylethylenediamine
EP0004919A1 (en) 1978-04-14 1979-10-31 Hoechst Aktiengesellschaft Process for preparing N,N,N',N'-tetra-acetylethylene diamine
EP0008369A1 (en) 1978-07-21 1980-03-05 BASF Aktiengesellschaft Process for preparing N,N,N',N'-tetraacetylethylene diamine
DE3011998A1 (en) 1980-03-28 1981-10-08 Henkel KGaA, 4000 Düsseldorf METHOD FOR THE PRODUCTION OF STORAGE-STABLE, EASILY DETACHABLE GRANULATES WITH A CONTENT OF BLEACHING ACTIVATORS
DE3024694A1 (en) 1980-06-30 1982-01-28 Warwick Chemicals Ltd., Leeds Tetra:acetyl ethylene di:amine prodn. from ethylene di:amine - by reaction with acetic acid and anhydride in several cycles, useful in detergent as perborate activator
EP0051739A1 (en) 1980-11-08 1982-05-19 BASF Aktiengesellschaft Process for the preparation of tetraacetylethylene diamine
GB2096133A (en) 1981-04-03 1982-10-13 Croda Chemicals Ltd Production of tetraacetylethylene diamine
EP0070432A1 (en) 1981-07-11 1983-01-26 Bayer Ag Process for the preparation of purified tetraacetylethylene diamine (TAED)
EP0079671A2 (en) 1981-09-28 1983-05-25 Albright & Wilson Limited Process for preparing tetraacetyl alkylene diamines

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0484634A1 (en) * 1990-11-09 1992-05-13 CAFFARO S.p.A. Process for the purification of tetraacetylethylene diamine (TAED)
CN103121960A (en) * 2013-02-22 2013-05-29 浙江金科日化原料有限公司 Efficient recrystallization method of tetraacetylethylenediamine
CN103121960B (en) * 2013-02-22 2015-04-01 浙江金科日化原料有限公司 Efficient recrystallization method of tetraacetylethylenediamine

Also Published As

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DE3609735A1 (en) 1987-09-24
ES2022182B3 (en) 1991-12-01
EP0238958A3 (en) 1988-08-17
IE870734L (en) 1987-09-22
EP0238958B1 (en) 1991-06-12
IE59879B1 (en) 1994-04-20
DE3770666D1 (en) 1991-07-18
ATE64410T1 (en) 1991-06-15

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