EP0061599A1 - Granule of alkali metal aluminium silicate and pentasodium tripolyphosphate, and process for its preparation - Google Patents

Granule of alkali metal aluminium silicate and pentasodium tripolyphosphate, and process for its preparation Download PDF

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EP0061599A1
EP0061599A1 EP82101655A EP82101655A EP0061599A1 EP 0061599 A1 EP0061599 A1 EP 0061599A1 EP 82101655 A EP82101655 A EP 82101655A EP 82101655 A EP82101655 A EP 82101655A EP 0061599 A1 EP0061599 A1 EP 0061599A1
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weight
water
ammonium polyphosphate
pentasodium triphosphate
aluminosilicate
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French (fr)
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EP0061599B1 (en
EP0061599B2 (en
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Alexander Dr. Maurer
Renate Adrian
Horst Dieter Dr. Wasel-Nielen
Günter Sorbe
Joachim Dr. Kandler
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Hoechst AG
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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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites

Definitions

  • Alkaline aluminum silicates especially crystalline or amorphous zeolites, are becoming increasingly important as detergent builders.
  • these builders only reach in combination with other complexing agents for divalent cations such as Pentasodium triphosphate, abbreviated to NTPP, optimal washing properties.
  • NTPP Pentasodium triphosphate
  • alkali aluminum silicates are finely powdered, there is great interest in non-dusting, free-flowing granules which contain both alkali aluminum silicates and NTPP. These can then be dry-mixed with the other detergent components without the formation of dust, and hydrolysis of the triphosphate is also avoided.
  • DE-OS 27 14 604 describes a granulate consisting of ion-exchanging alkali aluminum silicate, a high polymer phosphate with a P 2 0 5 content of 64-69 and pentasodium triphosphate.
  • the high polymer phosphate is added in the form of alkali salts and in an amount of at least 5% by weight, based on the alkali aluminum silicate used, in powder form to the granulation mixture. The mixture is then granulated in the presence of water.
  • This method has the disadvantage that the water is bound by the NTPP so quickly that it is no longer able to dissolve enough polymer phosphate for better granulation. Therefore, either larger amounts of polymer phosphate and longer residence times are required, or more water has to be added, which means that the granules have to be subsequently dried at 50 ° C.
  • DE-OS 27.56 732 describes a granulate which also consists of alkali aluminum silicate and a partially or completely hydrated alkali polyphosphate. These granules are produced by spraying water in fine mists onto the powder mixture of the granulate components, with a maximum of 10% of the total amount of water being allowed to be added per minute, since otherwise too large granule particles are obtained in addition to a high dust content. This process therefore harbors the danger of producing granules with a very broad grain spectrum which still have to be sieved afterwards.
  • DE-OS 28 22 231 describes granules of hydrated pentasodium triphosphate and water-insoluble aluminosilicate ion exchange material. This is also produced by spraying water onto the powder mixture, the total amount of water used being at least that required to achieve a minimum hydrate water content of about 10% by weight in sodium tripolyphosphate and a water content in the aluminosilicate ion exchange material of 1.8 to 13.5 mol water per mol aluminosilicate corresponds.
  • the strength of the granulate particles obtained in this way can still be improved, as will be shown below with reference to the invention.
  • the proportion of the partially or fully hydrated pentasodium triphosphate is 30-70% by weight and the proportion of the ammonium polyphosphate is 0.03 to 1.6% by weight. At least 10% by weight of the pentasodium triphosphate is present as hexahydrate and at least 30% by weight of the aluminum silicate is present as a hydrate with a maximum of 13.5 moles of water per mole of aluminum silicate.
  • spraying is preferably carried out on an intimate powdery mixture of about 1 to 99% by weight of an anhydrous or, if appropriate, at most 5% by weight water containing sodium tripolyphosphate and about 99 to 1% by weight of a powdery, anhydrous or optionally bound water-containing aluminosilicate ion exchange material general formula (Kat 2 / n O) x ⁇ Me 2 O 3.
  • the powdery mixture can consist of 30 to 70% by weight of the sodium tripolyphosphate and 70 to 30% by weight of the aluminum silicate, the latter for example a zeolite of the formula Na 2 0. Al 2 O 3 . (SiO 2 ) 2 . Can be 4.5 H 2 0.
  • Products of the aforementioned formula composition are to be used as the aluminosilicate ion exchange material.
  • Preference is given to zeolites, such as zeolite A. Because of their use as detergent builder jossie in very finely divided form, for example having an average particle diameter of 3 - 5 / to before.
  • the P 2 0 5 content of the ammonium polyphosphate used for the granulation is more than 69%, polyphosphates with a P 2 0 5 content of over 71% being preferred.
  • the process according to the invention can be carried out, for example, by first mixing the pentasodium phosphate with the aluminosilicate material in a mixer and then spraying the aqueous ammonium polyphosphate solution onto the mixture via a nozzle.
  • the spraying can also be carried out, for example, in a rotary tube or on a granulating plate onto the premixed material. It is important to ensure that no more granulating liquid is sprayed on than is necessary for the complete hydration of the sodium triphosphate contained in the mixture.
  • a granulate produced in this way is not dusty, abrasion-resistant and stable in storage. It meets the requirements for further processing in detergents by dry admixing.
  • Example 2 The procedure was as in Example 1, but using a 4% aqueous APP solution.
  • the mixed granules obtained from sodium triphosphate and zeolite had the following properties:
  • a 4% by weight aqueous solution of an ammonium polyphosphate with an average chain length of 270 and a P 2 0 5 content of 72.4% was used.
  • the resulting mixed granules of sodium triphosphate and the zeolite had the following properties:

Abstract

The disclosure relates to a granulate with a particle size essentially of about 0.2 to 2 mm consisting of (a) about 2 to 95 weight % of a partially or completely hydrated pentasodium tripolyphosphate, (b) less than 3 weight % of an ammonium polyphosphate and the balance (c) being in the form of a water-insoluble aluminum silicate ion exchanging material. The granulate can be used in detergents.

Description

Alkalialuminiumsilikate, besonders kristalline oder amorphe Zeolithe, gewinnen als Waschmittelgerüststoffe zunehmend an Bedeutung. Diese Gerüststoffe erreichen allerdings erst in Kombination mit anderen Komplexbildnern für zweiwertige Kationen wie z.B. Pentanatriumtriphosphat, kurz NTPP genannt, optimale Wascheigenschaften. Da Alkalialuminiumsilikate feinpulvrig sind, besteht ein großes Interesse an nicht staubenden, gut rieselfähigen Granulaten, die sowohl Alkalialuminiumsilikate als auch NTPP enthalten. Diese können dann den übrigen Waschmittelkomponenten ohne Staubbildung trocken zugemischt werden, wobei auch eine Hydrolyse des Triphosphats vermieden wird.Alkaline aluminum silicates, especially crystalline or amorphous zeolites, are becoming increasingly important as detergent builders. However, these builders only reach in combination with other complexing agents for divalent cations such as Pentasodium triphosphate, abbreviated to NTPP, optimal washing properties. Since alkali aluminum silicates are finely powdered, there is great interest in non-dusting, free-flowing granules which contain both alkali aluminum silicates and NTPP. These can then be dry-mixed with the other detergent components without the formation of dust, and hydrolysis of the triphosphate is also avoided.

Es wurden bereits mehrfach Anstrengungen unternommen, Alkalialuminiumsilikate, vor allem Zeolithe, zusammen mit Alkalipolyphosphaten zu granulieren. So wird beispielsweise in der DE-OS 27 14 604 ein Granulat beschrieben, das aus ionenaustauschendem Alkalialuminiumsilikat, einem hochpolymeren Phosphat mit einem P205-Gehalt von 64 - 69 sowie Pentanatriumtriphosphat besteht. Das Hochpolymere Phosphat wird hierbei in Form von Alkalisalzen und in einer Menge von mindestens 5 Gew%, bezogen auf das eingesetzte Alkalialuminiumsilikat, in Pulverform dem Granuliergemisch zugesetzt. Anschließend wird das Gemisch in Gegenwart von Wasser granuliert. Dieses Verfahren hat den Nachteil, daß das Wasser vom NTPP so schnell gebunden wird, daß es nicht mehr in der Lage ist, genügend Polymerphosphat zur besseren Granulierung zu lösen. Daher benötigt man entweder größere Mengen Polymerphosphat und längere Verweilzeiten, oder man muß mehr Wasser zusetzen, was dazu führt, daß man das Granulat anschließend bei 50°C nachtrocknen muß.Efforts have been made several times to granulate alkali aluminum silicates, especially zeolites, together with alkali polyphosphates. For example, DE-OS 27 14 604 describes a granulate consisting of ion-exchanging alkali aluminum silicate, a high polymer phosphate with a P 2 0 5 content of 64-69 and pentasodium triphosphate. The high polymer phosphate is added in the form of alkali salts and in an amount of at least 5% by weight, based on the alkali aluminum silicate used, in powder form to the granulation mixture. The mixture is then granulated in the presence of water. This method has the disadvantage that the water is bound by the NTPP so quickly that it is no longer able to dissolve enough polymer phosphate for better granulation. Therefore, either larger amounts of polymer phosphate and longer residence times are required, or more water has to be added, which means that the granules have to be subsequently dried at 50 ° C.

In der DE-OS 27.56 732 ist ein Granulat beschrieben, das ebenfalls aus Alkalialuminiumsilikat und einem teilweise oder vollkommen hydratisierten Alkalipolyphosphat besteht. Die Herstellung dieses Granulates erfolgt durch Aufsprühen von Wasser in feinen Nebeln auf das Pulvergemisch der Granulatkomponenten,wobei pro Minute höchstens 10 % der Gesamtwassermenge zugegeben werden dürfen, da sonst zu große Granulatteilchen neben hohem Staubanteil erhalten werden. Dieses Verfahren birgt somit die Gefahr, daß ein Granulat mit sehr breitem Kornspektrum erzeugt wird, das nachträglich noch gesiebt werden muß.DE-OS 27.56 732 describes a granulate which also consists of alkali aluminum silicate and a partially or completely hydrated alkali polyphosphate. These granules are produced by spraying water in fine mists onto the powder mixture of the granulate components, with a maximum of 10% of the total amount of water being allowed to be added per minute, since otherwise too large granule particles are obtained in addition to a high dust content. This process therefore harbors the danger of producing granules with a very broad grain spectrum which still have to be sieved afterwards.

Weiterhin ist es gemäß DE-OS 27 36 903 bekannt, Zeolithteilchen mit Wasser und Stärke als Bindemittel zu granulieren. Dabei können auch bestimmte Anteile von NTPP mitgranuliert werden. Die Verwendung von Stärke oder ähnlichen Stoffen als Bindemittel bedeutet jedoch, daß ein für den Waschprozeß nutzlose Substanz in das Granulat eingebracht wird.Furthermore, according to DE-OS 27 36 903 it is known to granulate zeolite particles with water and starch as a binder. Certain portions of NTPP can also be granulated. However, the use of starch or similar substances as binders means that a substance useless for the washing process is introduced into the granules.

Schließlich wird in der DE-OS 28 22 231 ein Granulat aus hydratisiertem Pentanatriumtriphosphat und wasserunlöslichem Aluminosilicationenaustauschmaterial beschrieben. Dieses wird ebenfalls durch Aufsprühen von Wasser auf das Pulvergemisch hergestellt, wobei die eingesetzte Gesamtwassermenge zumindest der zur Erzielung eines Mindesthydratwassergehaltes von etwa 10 Gew% im Natriumtripolyphosphat sowie eines Wassergehaltes im Alumosilicationenaustauschmaterial von 1,8 bis 13,5 Mol Wasser pro Mol Alumosilicat entspricht. Die Festigkeit der hierbei erhaltenen Granulatteilchen läßt sich noch , wie im folgenden anhand der Erfindung gezeigt wird, verbessern.Finally, DE-OS 28 22 231 describes granules of hydrated pentasodium triphosphate and water-insoluble aluminosilicate ion exchange material. This is also produced by spraying water onto the powder mixture, the total amount of water used being at least that required to achieve a minimum hydrate water content of about 10% by weight in sodium tripolyphosphate and a water content in the aluminosilicate ion exchange material of 1.8 to 13.5 mol water per mol aluminosilicate corresponds. The strength of the granulate particles obtained in this way can still be improved, as will be shown below with reference to the invention.

Es wurde nunmehr gefunden, daß die Nachteile der bekannten Granulate und deren Herstellungsverfahren vermieden werden können, wenn man zur Granulierung eines wasserunlöslichen Alumosilikats und Pentanatriumtriphosphat eine verdünnte wäßrige Lösung eines Ammoniumpolyphosphates als Bindemittel einsetzt.It has now been found that the disadvantages of the known granules and their production processes can be avoided if a dilute aqueous solution of an ammonium polyphosphate is used as the binder for granulating a water-insoluble aluminosilicate and pentasodium triphosphate.

Somit betrifft der Gegenstand der Erfindung ein Granulat mit einer Teilchengröße von im wesentlichen etwa-0,2 - 2-mm, - bestehend aus

  • a) etwa 2 - 95 Gew% eines teilweise oder vollkommen hydratisierten Pentanatriumtriphosphates,
  • b) weniger als 3 Gew% eines Ammoniumpolyphosphates der allgemeinen Formel (I)
    Figure imgb0001
    in welcher n einen ganzzahligen Durchschnittswert von 100 bis 1000, m eine ganze Zahl bis maximal n+2 bedeutet und m/n einenwert von etwa 1 darstellt und dem Rest
  • c) in Form eines wasserunlöslichen Aluminiumsilikationenaustauschmaterials der allgemeinen Formel (II)
    Figure imgb0002
    in welcher Kat ein mit Calcium austauschbares Kation der Wertigkeit n, x eine Zahl von 0,7 - 1,5, Me gleich Bor oder Aluminium, y eine Zahl von 0,8 - 6 und z eine Zahl von 1,8 - 13,5 ist.
Thus, the subject matter of the invention relates to granules with a particle size of approximately approximately 0.2-2 mm, consisting of
  • a) about 2-95% by weight of a partially or fully hydrated pentasodium triphosphate,
  • b) less than 3% by weight of an ammonium polyphosphate of the general formula (I)
    Figure imgb0001
     in which n is an integer average value from 100 to 1000, m is an integer up to a maximum of n + 2 and m / n is a value of approximately 1 and the rest
  • c) in the form of a water-insoluble aluminum silicate exchange material of the general formula (II)
    Figure imgb0002
     in which cat a cation exchangeable with calcium of the valence n, x a number from 0.7 to 1.5, Me is boron or aluminum, y a number from 0.8 to 6 and z a number from 1.8 to 13, 5 is.

Gemäß einer bevorzugten Granulatkomposition beträgt der Anteil des teilweise oder vollkommen hydratisierten Pentanatriumtriphosphates 30 - 70 Gew% und der Anteil des Ammoniumpolyphosphates 0,03 bis 1,6 Gew%. Hierbei liegen mindestens 10 Gew% des Pentanatriumtriphosphates als Hexahydrat und mindestens 30. Gew% des Aluminiumsilikates als Hydrat mit höchstens 13,5 Mol Wasser pro Mol Aluminiumsilikat vor.According to a preferred granulate composition, the proportion of the partially or fully hydrated pentasodium triphosphate is 30-70% by weight and the proportion of the ammonium polyphosphate is 0.03 to 1.6% by weight. At least 10% by weight of the pentasodium triphosphate is present as hexahydrate and at least 30% by weight of the aluminum silicate is present as a hydrate with a maximum of 13.5 moles of water per mole of aluminum silicate.

Zur Herstellung des erfindungsgemäßen Granulats sprüht man vorzugsweise auf ein inniges pulverförmiges Gemisch aus etwa 1 bis 99 Gew% eines wasserfreien oder gegebenenfalls höchstens 5.Gew% Wasser enthaltenden Natriumtripolyphosphates und etwa 99 bis 1 Gew% eines pulverförmigen, wasserfreien oder gegebenenfalls gebundenes Wasser enthaltenden Alumosilicationenaustauschmaterials der allgemeinen Formel (Kat2/nO)x · Me2O3 . (SiO2)y, in welcher Kat, Me, x und y die genannte Bedeutung haben, unter intensivem Durchmischen eine wäßrige, 0,5 - 20 gewichts%ige Lösung eines Ammoniumpolyphosphates der allgemeinen Formel I in einem feinen Nebel auf und granuliert das Gemisch unter teilweise oder vollkommener Hydratisierung des Pentanatriumtriphosphates bzw. des Alumosilicationenaustauschmaterials.To produce the granules according to the invention, spraying is preferably carried out on an intimate powdery mixture of about 1 to 99% by weight of an anhydrous or, if appropriate, at most 5% by weight water containing sodium tripolyphosphate and about 99 to 1% by weight of a powdery, anhydrous or optionally bound water-containing aluminosilicate ion exchange material general formula (Kat 2 / n O) x · Me 2 O 3. (SiO 2 ) y , in which Kat, Me, x and y have the meaning given, with vigorous mixing, an aqueous 0.5-20% by weight solution of an ammonium polyphosphate of the general formula I in a fine mist and granulates the mixture with partial or complete hydration of the pentasodium triphosphate or the aluminosilicate ion exchange material.

Das pulverförmige Gemisch kann dabei aus 30 bis 70 Gew% des Natriumtripolyphosphates und 70 bis 30 Gew% des Alumösilicates bestehen, wobei letzteres beispielsweise ein Zeolith der Formel Na20 . Al2O3 . (SiO2)2. 4,5 H20 sein kann.The powdery mixture can consist of 30 to 70% by weight of the sodium tripolyphosphate and 70 to 30% by weight of the aluminum silicate, the latter for example a zeolite of the formula Na 2 0. Al 2 O 3 . (SiO 2 ) 2 . Can be 4.5 H 2 0.

Es hat sich weiterhin als vorteilhaft erwiesen, wenn im fertigen Granulat mindestens 10 Gew% des Pentanatriumtriphosphates als Hexahydrat und mindestens 30 Gew% des Alumosilikates als Hydrat mit höchstens 13,5 Mol Wasser pro Mol Alumosilikat vorliegen. Das Besprühen des Gemisches erfolgt im allgemeinen mit einer wäßrigen 1 - 10 gewichts%igen Lösung von Ammoniumpolyphosphat.It has further proved to be advantageous if at least 1 0% by weight of the pentasodium triphosphate as hexahydrate and at least 30% by weight of the aluminosilicate be present as a hydrate having at most 13.5 mols water per mol aluminosilicate in the finished granulate. The mixture is generally sprayed with an aqueous 1-10% by weight solution of ammonium polyphosphate.

Im einzelnen ist zum Verfahren der Erfindung noch folgendes zu bemerken:

  • Als Natriumtriphosphat kann sowohl ein feingemahlenes Produkt, das beispielsweise maximal 2 % einer Kornfraktion über 0,4 mm besitzt, als auch ein gröberes Produkt, dessen Anteil >0,15 mm mindestens 70 % beträgt, eingesetzt werden. Die Verteilung der Modifikationen I und II im NTPP ist variabel, jedoch werden schneller hydratisierende Typen mit einem Gehalt an Modifikation I von 20 - 60 % mit Vorteil eingesetzt.
In particular, the following should be noted regarding the method of the invention:
  • Sodium triphosphate can be either a finely ground product, which has, for example, a maximum of 2% of a grain fraction larger than 0.4 mm, or a coarser product, the proportion of which> 0.15 mm is at least 70%. The distribution of Modifications I and II in NTPP is variable, but faster hydrating types with a Modification I content of 20 - 60% are used with advantage.

Als Alumosilicat-Ionenaustauschmaterial sind Produkte der erwähnten formelmäßigen Zusammensetzung zu verwenden. Bevorzugt eingesetzt werden Zeolithe, wie z.B. Zeolith A. Wegen ihrer Verwendung als Waschmittelgerüststoff liegensie in sehr feinteiliger Form, beispielsweise mit einem mittleren Teilchendurchmesser von 3 - 5/um, vor.Products of the aforementioned formula composition are to be used as the aluminosilicate ion exchange material. Preference is given to zeolites, such as zeolite A. Because of their use as detergent builder liegensie in very finely divided form, for example having an average particle diameter of 3 - 5 / to before.

Der P205-Gehalt des zur Granulierung eingesetzten Ammoniumpolyphosphates beträgt mehr als 69 %, wobei Polyphosphate mit einem P205-Gehalt von über 71 % bevorzugt werden.The P 2 0 5 content of the ammonium polyphosphate used for the granulation is more than 69%, polyphosphates with a P 2 0 5 content of over 71% being preferred.

Die Durchführung des erfindungsgemäßen Verfahrens kann beispielsweise derart erfolgen, daß man in einem Mischer das Pentanatriumphosphat mit dem Alumosilikatmaterial zunächst mischt und dann auf die Mischung über eine Düse die wäßrige Ammoniumpolyphosphatlösung aufsprüht. Das Aufsprühen kann auch beispielsweise in einem Drehrohr oder auf einem Granulierteller auf das vorgemischte Material erfolgen. Es ist darauf zu achten, daß man nicht mehr Granulierflüssigkeit aufsprüht,als zur vollständigen Hydratation des im Gemisch enthaltenen Natriumtriphosphats notwendig ist. Ein derart hergestelltes Granulat ist nicht staubend, abriebfest und lagerstabil. Es erfüllt die Anforderungen, die für eine Weiterverarbeitung in Waschmitteln durch trockenes Zumischen gestellt werden.The process according to the invention can be carried out, for example, by first mixing the pentasodium phosphate with the aluminosilicate material in a mixer and then spraying the aqueous ammonium polyphosphate solution onto the mixture via a nozzle. The spraying can also be carried out, for example, in a rotary tube or on a granulating plate onto the premixed material. It is important to ensure that no more granulating liquid is sprayed on than is necessary for the complete hydration of the sodium triphosphate contained in the mixture. A granulate produced in this way is not dusty, abrasion-resistant and stable in storage. It meets the requirements for further processing in detergents by dry admixing.

Beispiel 1example 1

In einem Freifallmischer wurden 67,5 kg wasserfreies Pentanatriumtriphosphat mit einem Phase I-Gehalt von 50 % und folgender Korngrößenverteilung: >1,6 mm = 0,7 %, >0,8 mm = 3,8 %,>0,4 mm = 20,5 %,> 0,2 mm = 67,8 % und >0,1 mm = 88,2 % sowie 67,5 kg eines Zeoliths (Zeolith A ) mit einem Glühverlust von 19,8 % und einer Korngrößenverteilung von 99 % <15/um, 96 % <10 µm und 3 % <1 µm, während 20 min gemischt. Danach wurden 9 1 einer 8 gewichts%igen wäßrigen Lösung von Ammoniumpolyphosphat - im folgenden APP genannt - mit einer mittleren Kettenlänge von etwa 400 sowie einem P2O5-Gehalt von 72,4 % im Verlauf von 3,5 Stunden unter ständigem weiteren Mischen aufgesprüht. Es wurde ein Mischgranulat aus Pentanatriumtriphosphat und dem Zeolith erhalten, das folgende Eigenschaften besaß:

Figure imgb0003
67.5 kg of anhydrous pentasodium triphosphate with a phase I content of 50% and the following particle size distribution were placed in a free-fall mixer: > 1.6 mm = 0.7%,> 0.8 mm = 3.8%,> 0.4 mm = 20.5%,> 0.2 mm = 67.8% and> 0.1 mm = 88.2% and 67.5 kg of a zeolite (Zeolite A) with a loss on ignition of 19.8% and a grain size distribution of 99% <15 / um, 96% <10 µm and 3% <1 µm, mixed for 20 min. Thereafter, 9 l of an 8% by weight aqueous solution of ammonium polyphosphate - hereinafter called APP - with an average chain length of about 400 and a P 2 O 5 content of 72.4% over the course of 3.5 hours with constant further mixing sprayed on. A mixed granulate of pentasodium triphosphate and the zeolite was obtained, which had the following properties:
Figure imgb0003

Beispiel 2Example 2

Es wurde analog Beispiel 1 verfahren, wobei jedoch 4 1 APP-Lösung in 30 min aufgesprüht wurden. Das erhaltene Mischgranulat aus Pentanatriumtriphosphat und dem Zeolith besaß folgende Eigenschaften:

Figure imgb0004
The procedure was analogous to Example 1, but 4 1 APP solution were sprayed on in 30 min. The mixed granules obtained from pentasodium triphosphate and the zeolite had the following properties:
Figure imgb0004

Beispiel 3Example 3

Es wurde wie in Beispiel 1 verfahren, wobei jedoch eine 4 %ige wäßrige APP-Lösung verwendet wurde. Das erhaltene Mischgranulat aus Natriumtriphosphat und Zeolith besaß folgende Eigenschaften:

Figure imgb0005
The procedure was as in Example 1, but using a 4% aqueous APP solution. The mixed granules obtained from sodium triphosphate and zeolite had the following properties:
Figure imgb0005

Beispiel 4Example 4

Es wurde wie in Beispiel 1 verfahren, wobei jedoch ein Natriumtriphosphat mit folgenden Eigenschaften als Ausgangsprodukt verwendet wurde: Glühverlust: 1,0 Gew%; Phase I-Gehalt: 26 %; Korngrößenverteilung: >0,4 mm = 0,1;>0,2 mm = 3,8 %;>0,1 mm = 25,0 %;>0,05 mm = 36,8%. Außerdem wurde eine 4 gewichts%ige wäßrige Lösung eines Ammoniumpolyphosphats mit einer mittleren Kettenlänge von 270 und einem P205-Gehalt von 72,4 % eingesetzt. Das erhaltene Mischgranulat aus Natriumtriphosphat und dem Zeolith besaß folgende Eigenschaften:

Figure imgb0006
The procedure was as in Example 1, but using a sodium triphosphate with the following properties as the starting product: loss on ignition: 1.0% by weight; Phase I content: 26%; Grain size distribution:> 0.4 mm = 0.1;> 0.2 mm = 3.8%;> 0.1 mm = 25.0%;> 0.05 mm = 36.8%. In addition, a 4% by weight aqueous solution of an ammonium polyphosphate with an average chain length of 270 and a P 2 0 5 content of 72.4% was used. The resulting mixed granules of sodium triphosphate and the zeolite had the following properties:
Figure imgb0006

Beispiel 5Example 5

Auf einem Granulierteller mit einem Durchmesser von 1 m wurden 20 kg eines Gemisches von 50 Gew% Natriumtriphosphat mit den in Beispiel 4 genannten Eigenschaften und 50 Gew% eines Zeoliths mit einem Glühverlust von 1,0 Gew% mit 4 1 APP-Lösung gemäß Beispiel 1 besprüht. Es wurde ein Mischgranulat aus Natriumtriphosphat und dem Zeolith mit folgenden Eigenschaften erhalten:

Figure imgb0007
20 kg of a mixture of 50% by weight sodium triphosphate with the properties mentioned in Example 4 and 50% by weight of a zeolite with a loss on ignition of 1.0% by weight with 4 l APP solution according to Example 1 were placed on a granulating plate with a diameter of 1 m sprayed. A mixed granulate of sodium triphosphate and the zeolite was obtained with the following properties:
Figure imgb0007

Claims (9)

1) Granulat mit einer Teilchengröße von im wesentlichen etwa 0,2 - 2 mm, bestehend aus a) etwa 2 - 95 Gew% eines teilweise oder vollkommen hydratisierten Pentanatriumtriphosphates, b) weniger als 3 Gew% eines Ammoniumpolyphosphates der allgemeinen Formel (I)
Figure imgb0008
in welcher n einen ganzzahligen Durchschnittswert von 100 bis 1000, m eine ganze Zahl bis maximal n+2 bedeutet und m/n einen Wert von etwa 1 darstellt und dem Rest c) in Form eines wasserunlöslichen Aluminiumsilikationenaustauschmaterials der allgemeinen Formel (II)
Figure imgb0009
in welcher Kat ein mit Calcium austauschbares Kation der Wertigkeit n, x eine Zahl von 0,7 - 1,5, Me gleich Bor oder Aluminium, y eine Zahl von 0,8 - 6 und z eine Zahl von 1,8 - 13,5 ist. 1) Granules with a particle size of substantially about 0.2-2 mm, consisting of a) about 2-95% by weight of a partially or fully hydrated pentasodium triphosphate, b) less than 3% by weight of an ammonium polyphosphate of the general formula (I)
Figure imgb0008
 in which n is an integer average value from 100 to 1000, m is an integer up to a maximum of n + 2 and m / n is a value of approximately 1 and the rest c) in the form of a water-insoluble aluminum silicate exchange material of the general formula (II)
Figure imgb0009
 in which cat a cation exchangeable with calcium of the valence n, x a number from 0.7 to 1.5, Me is boron or aluminum, y a number from 0.8 to 6 and z a number from 1.8 to 13, 5 is. 2) Granulat nach Anspruch 1, dadurch gekennzeichnet, daß der Anteil des teilweise oder vollkommen hydratisierten Pentanatriumtriphosphates 30 - 70 Gew% beträgt.2) Granules according to claim 1, characterized in that the proportion of the partially or fully hydrated pentasodium triphosphate is 30-70% by weight. 3) Granulat nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Anteil des Ammoniumpolyphosphates 0,03 bis 1,6 Gew% beträgt.3) Granules according to claim 1 or 2, characterized in that the proportion of ammonium polyphosphate is 0.03 to 1.6% by weight. 4) Granulat nach Anspruch 1 - 3, dadurch gekennzeichnet, daß mindestens 10 Gew% des Pentanatriumtriphosphates als Hexahydrat und mindestens 30 Gew% des Aluminiumsilikates als Hydrat mit höchstens 13,5 Mol Wasser pro Mol Aluminiumsilikat vorliegen.4) Granules according to claims 1-3, characterized in that at least 10% by weight of the pentasodium triphosphate is present as hexahydrate and at least 30% by weight of the aluminum silicate is present as a hydrate with at most 13.5 moles of water per mole of aluminum silicate. 5) Verfahren zur Herstellung von Granulaten nach einem der Ansprüche 1 - 4, dadurch gekennzeichnet, daß man auf ein inniges pulverförmiges Gemisch aus etwa 1 bis 99 Gew% eines wasserfreien oder gegebenenfalls höchstens 5 Gew% Wasser enthaltenden Natriumtripolyphosphates und etwa 99 bis 1 Gew% eines pulverförmigen, wasserfreien oder gegebenenfalls gebundenes Wasser enthaltenden Alumosilicationenaustauschmaterials der allgemeinen Formel (Kat2/nO)x.Me2O3.(SiO2)y, in welcher Kat, Me, x, n und y die genannte Bedeutung haben, unter intensivem Durchmischen eine wäßrige, 0,5 - 20 gew%ige Lösung eines Ammoniumpolyphosphates der allgemeinen Formel I in einem feinen Nebel aufsprüht und das Gemisch unter teilweise oder vollkommener Hydratisierung des Pentanatriumtriphosphates bzw. des Alumosilicationaustauschmaterials granuliert.5) Process for the preparation of granules according to one of claims 1-4, characterized in that an intimate powdery mixture of about 1 to 99% by weight of an anhydrous or optionally containing at most 5% by weight of water sodium tripolyphosphate and about 99 to 1% by weight a powdery, anhydrous or optionally bound water-containing aluminosilicon ion exchange material of the general formula (Kat 2 / n O) x.Me 2 O 3. (SiO 2 ) y , in which Kat, Me, x, n and y have the meaning given below intensive mixing, spraying an aqueous 0.5-20% strength by weight solution of an ammonium polyphosphate of the general formula I in a fine mist and granulating the mixture with partial or complete hydration of the pentasodium triphosphate or the alumosilication exchange material. 6) Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß das pulverförmige Gemisch aus 30 bis 70 Gew% des Natriumtripolyphosphates und 70 bis 30 Gew% des Alumosilicates besteht.6) Method according to claim 5, characterized in that the powdery mixture consists of 30 to 70% by weight of the sodium tripolyphosphate and 70 to 30% by weight of the aluminosilicate. 7) Verfahren nach Anspruch 5 oder 6, dadurch gekennzeichnet, daß das Alumosilicationenaustauschmaterial Zeolithe der Formel Na2O.Al2O3·(SiO2)2· 4,5 H20 sind.7) Method according to claim 5 or 6, characterized in that the aluminosilicate ion exchange material are zeolites of the formula Na 2 O.Al 2 O 3 · (SiO 2 ) 2 · 4.5 H 2 0. 8) Verfahren nach Anspruch 5 - 7, dadurch gekennzeichnet, daß man die zur Granulierung erforderliche Wassermenge derart bemißt, daß im fertigen Granulat mindestens 10 Gew% des Pentanatriumtriphosphates als Hexahydrat und mindestens 30 Gew% des Alumosilikates als Hydrat mit höchstens 13,5 Mol Wasser pro Mol Alumosilikat vorliegen.8) Process according to claim 5-7, characterized in that the amount of water required for granulation is measured such that in the finished granulate at least 10% by weight of pentasodium triphosphate as hexahydrate and at least 30% by weight of the aluminosilicate as hydrate with a maximum of 13.5 mol water are present per mole of aluminosilicate. 9) Verfahren nach Anspruch 5 - 8, dadurch gekennzeichnet, daß man das Gemisch mit einer wäßrigen 1 - 10 gew%igen Lösung von Ammoniumpolyphosphat besprüht.9) Method according to claim 5-8, characterized in that the mixture is sprayed with an aqueous 1-10% by weight solution of ammonium polyphosphate.
EP82101655A 1981-03-21 1982-03-04 Granule of alkali metal aluminium silicate and pentasodium tripolyphosphate, and process for its preparation Expired EP0061599B2 (en)

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AT82101655T ATE11792T1 (en) 1981-03-21 1982-03-04 ALKALI AUMOSILICATE AND PENTANATRIUM TRIPHOSPHATE GRANULES AND PROCESS FOR PRODUCTION THEREOF.

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DE3111236 1981-03-21
DE3111236A DE3111236A1 (en) 1981-03-21 1981-03-21 GRANULATE FROM ALKALIALUMINUM SILICATE AND PENTANATRIUM TRIPHOSPHATE AND METHOD FOR THE PRODUCTION THEREOF

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Cited By (2)

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EP0088267A1 (en) * 1982-03-06 1983-09-14 Hoechst Aktiengesellschaft Cogranulate from alkali silicate and alkali phosphate, and process for the preparation of the granulate
DE4009082A1 (en) * 1990-03-21 1991-09-26 Aquamot Ag METHOD FOR CLEANING INDUSTRIAL, AGRICULTURAL, OR PRIVATE WASTEWATER FROM YOUR AMMONIUM COMPOUNDS

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US4655782A (en) * 1985-12-06 1987-04-07 Lever Brothers Company Bleach composition of detergent base powder and agglomerated manganese-alluminosilicate catalyst having phosphate salt distributed therebetween
US4711748A (en) * 1985-12-06 1987-12-08 Lever Brothers Company Preparation of bleach catalyst aggregates of manganese cation impregnated aluminosilicates by high velocity granulation

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US4014806A (en) * 1973-12-07 1977-03-29 David Connor Novel organopolyphosphates in aqueous cleaning compositions
US4248911A (en) * 1976-12-02 1981-02-03 Colgate-Palmolive Company Concentrated heavy duty particulate laundry detergent
DE2714604C3 (en) * 1977-04-01 1985-04-25 Joh. A. Benckiser Gmbh, 6700 Ludwigshafen Granulate based on polymer phosphate and ion-exchanging alkali aluminosilicate
DE2744773C3 (en) * 1977-10-05 1986-08-21 Joh. A. Benckiser Gmbh, 6700 Ludwigshafen Granulate based on polymer phosphate and ion-exchanging alkali aluminosilicate
DE2751354A1 (en) * 1977-11-17 1979-05-23 Hoechst Ag PROCESS FOR THE PREPARATION OF MIXTURES FROM CRYSTALLINE ZEOLITE AND SODIUM TRIPHOSPHATE
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0088267A1 (en) * 1982-03-06 1983-09-14 Hoechst Aktiengesellschaft Cogranulate from alkali silicate and alkali phosphate, and process for the preparation of the granulate
DE4009082A1 (en) * 1990-03-21 1991-09-26 Aquamot Ag METHOD FOR CLEANING INDUSTRIAL, AGRICULTURAL, OR PRIVATE WASTEWATER FROM YOUR AMMONIUM COMPOUNDS

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US4386024A (en) 1983-05-31
DE3111236A1 (en) 1982-09-30
DE3262256D1 (en) 1985-03-28
EP0061599B1 (en) 1985-02-13
ATE11792T1 (en) 1985-02-15
CA1161416A (en) 1984-01-31
EP0061599B2 (en) 1988-07-06

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