EP0357989A1 - Na A-type zeolite powder for use in liquid detergents - Google Patents

Na A-type zeolite powder for use in liquid detergents Download PDF

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Publication number
EP0357989A1
EP0357989A1 EP89114795A EP89114795A EP0357989A1 EP 0357989 A1 EP0357989 A1 EP 0357989A1 EP 89114795 A EP89114795 A EP 89114795A EP 89114795 A EP89114795 A EP 89114795A EP 0357989 A1 EP0357989 A1 EP 0357989A1
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Prior art keywords
particle size
zeolite
zeolite powder
viscosity
liquid detergents
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EP89114795A
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German (de)
French (fr)
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EP0357989B1 (en
Inventor
Beata - M. Dr. Sax
Wolfgang Dr. Leonhardt
Akos Dr. Kiss
Wolfgang Dr. Lortz
Wolfgang Dr. Roebke
Claus Dietrich
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Evonik Operations GmbH
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Degussa GmbH
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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
    • C11D3/12—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

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  • the invention relates to a zeolite powder of the type Na A and its use in liquid detergents.
  • Liquid detergents are becoming increasingly popular when used in household washing machines.
  • AT-PS 335 033, CA-PS 1202 857 It is known to at least partially replace the proportion of phosphates in liquid detergents with synthetic alkali aluminum silicates (AT-PS 335 033, CA-PS 1202 857).
  • AT-PS 335 03 describes a liquid detergent which contains aluminum silicates as phosphate substitute, which consist of at least 80% by weight of particles with a size of 10 to 0.01 ⁇ m, in particular 8 to 0.1 ⁇ m, and practically no particle sizes have above 40 ⁇ m.
  • CA-PS 1202 857 describes a liquid detergent which, as aluminum silicate, contains zeolite A with a particle size of 0.01 to 5 ⁇ m, preferably 0.5 to 1.5 ⁇ m.
  • the known liquid detergents have the disadvantage that they have too high a viscosity for use in household washing machines.
  • the zeolite powder of type Na A can preferably have an average particle size of 1.7 to 2.5 ⁇ m
  • the average particle size can be 1.7 to 2.0 ⁇ m.
  • the zeolite powder of the type Na A according to the invention has the advantage that the liquid detergents produced therewith have the viscosity which is favorable for the application.
  • the zeolite powder of the type Na has the following particle size distribution: ⁇ m % ⁇ 0.5 3 - 0 ⁇ 1.0 30-0 ⁇ 1.5 98-2 ⁇ 2.0 99 - 20 ⁇ 3.0 100 - 82 ⁇ 4.0 100-95 ⁇ 5.0 100-98 ⁇ 6.0 100-99 ⁇ 10.0 100-100
  • the Na type zeolite powder has the following particle size distribution: ⁇ m % ⁇ 0.5 0 - 0 ⁇ 1.0 4 - 0 ⁇ 1.5 30-10 ⁇ 2.0 85-50 ⁇ 3.0 100-95 ⁇ 4.0 100-99 ⁇ 6.0 100-100 ⁇ 10.0 100-100
  • Zeolite powder of the type Na A with a particle size of 3.2 ⁇ m and 8.6 ⁇ m are produced in accordance with DE-PS 2517 218 and DE-PS 2660 726, respectively.
  • a zeolite powder is obtained by grinding with an air jet mill, which has a particle size of 1.8 ⁇ m.
  • the particle size of 1.1 ⁇ m is obtained by wet milling in a colloid mill, drying and milling in a pin mill.
  • the calcium and magnesium binding capacity is determined by complexometric titration of the remaining hardness of Ca and Mg ions after a contact time of 15 minutes. These values are listed in Table 1: Table 1 Particle size CaBV [mg CaO / g] MgBV [mg CaO / g] 8.6 157 12 3.2 169 29 1.8 170 32 1.1 157 50 The particle size distribution is carried out with the Cilas granulometer 715 E627.
  • the determined particle size distribution curves are shown in FIGS. 1, 2, 3 and 4.
  • HÜLS Sodium alkylbenzenesulphonate
  • BASF Defoamer Wacker S 132 (Wacker Chemie) in an amount of 0.1%.
  • the viscosity is carried out using a Brookfield RVT viscometer at 5 and 50 revolutions per minute and the spindle 4.
  • the suspension is poured into a 100 ml beaker in which the spindle is immersed up to the appropriate mark. The reading is taken every 3 minutes.
  • Flow time is determined by determining the time it takes 100 ml of suspension to flow through a 6 m nozzle without applying pressure.
  • the behavior of the liquid phase is assessed visually.
  • the suspensions are made as follows: The starting materials are weighed into a 250 ml glass bottle. The zeolite powder is filled in last.
  • the mixture is dispersed using an Ultra Turrax (9 m / sec) under a water jet vacuum for 15 minutes.
  • Simple systems consisting of detergent, zeolite and water are used to investigate the influence of the detergents and the mixture of the detergents on the viscosity and the storage stability.
  • a zeolite content of 15, 25 and 35% is used together with a content of 20% detergent. Either the detergents are used alone or in a mixing ratio of 1: 2, 1: 1 and 2: 1.
  • Figure 5 shows the viscosity at 5 and 50 revolutions per minute as a function of the zeolite content and the detergent mixture.
  • the zeolite has a particle size of 3.2 microns. It is found that the pure anionic detergent and mixtures with a high proportion of anionic detergent lead to a high viscosity. This effect is particularly evident with a zeolite content of 25 and 35%.
  • FIG. 7 shows the thixotropy index TI of the suspensions according to FIG. 5.
  • TI ⁇ (5 revolutions per minute) to ⁇ (50 revolutions per minute).
  • the thixotropy index is the quotient of two values for the viscosity, which are determined at different shear rates.
  • the thixotropy index characterizes the structural viscosity of the system. The higher the thixotropy index, the more structured the system and the better the storage stability. The most favorable result shows - as can be seen in FIG. 7 - the mixture which contains 13% anionic and 7% non-ionic detergent.
  • the mixture which contains 13% anionic and 7% non-ionic detergent, is used to investigate the storage stability and the flow behavior depending on the particle size distribution of the zeolite A.
  • FIG. 8 shows the viscosity of the suspensions as a function of the zeolite A particle size distribution and the zeolite A content, measured at 5 revolutions per minute.
  • FIG. 9 shows the viscosity of the suspensions as a function A particle size distribution and the zeolite A content, measured at 50 revolutions per minute.
  • the zeolite powder with a particle size of 1.1 ⁇ m shows a pronounced thickening effect in the viscosity behavior.
  • the suspension with a content of 25% and in particular the suspension with a content of 35% zeolite show a paste-like consistency.
  • the other zeolite powders each result in a liquid suspension, the zeolite with the particle size of 1.8 ⁇ m showing the least thickening effect with increasing concentration.
  • the low viscosity is an advantage for the application because these suspensions can be poured easily.
  • FIG. 10 shows the flow behavior of the suspensions as a function of the zeolite content and the particle size. It becomes clear that the suspension with the zeolite powder having a particle size of 1.8 ⁇ m has a constant flow rate for the concentrations of this zeolite of 25 and 35%. This independence of the flow behavior from the concentration is confirmed by the thixotropy index.
  • FIG. 11 shows the thixotropy index as a function of the particle size and the concentration of the zeolite powder.
  • the zeolite with a particle size of 1.8 ⁇ m gives values from 1.2 to 1.3.
  • the zeolite with the particle size of 1.1 ⁇ m gives a value of 3 to 4.
  • the storage test is carried out with the same suspensions as were used in the tests according to FIGS. 8 to 11.
  • the degree of separation is determined from the ratio of the clear phase to the level of the filling and expressed in percent.
  • the storage test shows the influence of both the viscosity and the particle size on the storage stability, the influence of the particle size obviously being greater.
  • the most favorable values, from the point of view of viscosity, are achieved with a particle size of 3.2 ⁇ m.
  • the shelf life of this suspension is significantly lower than the suspension which has a zeolite powder with a particle size of 1.8 ⁇ m. This becomes particularly clear when comparing the suspension with a zeolite content of 25%.
  • the suspension with the zeolite with a particle size of 1.1 ⁇ m has too high a viscosity, which makes it unusable for the application.

Abstract

Na A-type zeolite powder characterised by a median particle size (= 50% point) of 1.6 to 3.2 mu m measured with a Cilas 715 granulometer. This zeolite powder is employed as phosphate substitute in liquid detergents.

Description

Die Erfindung betrifft ein Zeolithpulver des Typs Na A sowie dessen Verwendung in Flüssigwaschmitteln.The invention relates to a zeolite powder of the type Na A and its use in liquid detergents.

Flüssigwaschmittel finden ein zunehmendes Interesse bei der Verwendung in Haushaltswaschmaschinen.Liquid detergents are becoming increasingly popular when used in household washing machines.

Es ist bekannt, in Flüssigwaschmitteln den Anteil an Phosphaten zumindest teilweise durch synthetische Alkalialuminiumsilikate zu ersetzen (AT-PS 335 033, CA-PS 1202 857). Die AT-PS 335 03 beschreibt ein Flüssigwaschmittel, welches als Phosphatersatzstoff Aluminiumsilikate enthält, die zu wenigstens 80 Gew.-% aus Teilchen einer Größe von 10 bis 0,01 µm, insbeson­dere von 8 bis 0,1 µm, bestehen und praktisch keine Teilchengrößen oberhalb 40 µm aufweisen.It is known to at least partially replace the proportion of phosphates in liquid detergents with synthetic alkali aluminum silicates (AT-PS 335 033, CA-PS 1202 857). AT-PS 335 03 describes a liquid detergent which contains aluminum silicates as phosphate substitute, which consist of at least 80% by weight of particles with a size of 10 to 0.01 µm, in particular 8 to 0.1 µm, and practically no particle sizes have above 40 µm.

Die CA-PS 1202 857 beschreibt ein Flüssigwaschmittel, welches als Aluminiumsilikat Zeolith A mit einer Teilchengröße von 0,01 bis 5 µm, vorzugsweise 0,5 bis 1,5 µm.CA-PS 1202 857 describes a liquid detergent which, as aluminum silicate, contains zeolite A with a particle size of 0.01 to 5 μm, preferably 0.5 to 1.5 μm.

Die Herstellung dieses Zeolith A wird, wie die CA-PS 1202 857 angibt, in den US-Patentschriften 4096 081 und 4180 485 beschrieben.The production of this zeolite A, as specified in CA-PS 1202 857, is described in US Pat. Nos. 4,096,081 and 4,180,485.

Die bekannten Flüssigwaschmittel haben den Nachteil, daß sie eine für die Anwendung in Haushaltswaschma­schinen zu hohe Viskosität aufweisen.The known liquid detergents have the disadvantage that they have too high a viscosity for use in household washing machines.

Es wurde nun gefunden, daß die Viskosität der Flüssig­waschmittel, die Zeolith A als Phosphatersatzstoff enthalten, in hohem Maße von der Teillchengrößenvertei­lung des Zeolithpulver des Typ A abhängt.It has now been found that the viscosity of the liquid detergents which contain zeolite A as a phosphate substitute depends to a large extent on the particle size distribution of the type A zeolite powder.

Gegenstand der Erfindung ist ein Zeolithpulver des Typs Na A, gekennzeichnet durch eine mittlere Teilchengröße (= 50%-Punkt der Verteilungskurve) von 1,6 bis 3,2 µm, gemessen mit dem Cilas-Granulometer 715.The invention relates to a zeolite powder of the type Na A, characterized by an average particle size (= 50% point of the distribution curve) of 1.6 to 3.2 μm, measured with the Cilas 715 granulometer.

Vorzugsweise kann das Zeolithpulver des Typs Na A eine mittlere Teilchengröße von 1,7 bis 2,5 µm aufweisenThe zeolite powder of type Na A can preferably have an average particle size of 1.7 to 2.5 μm

Insbesondere kann die mittlere Teilchengröße 1,7 bis 2,0 µm betragen.In particular, the average particle size can be 1.7 to 2.0 μm.

Ein weiterer Gegenstand der Erfindung ist ein Flüssig­waschmittel, welches das Zeolithpulver des Typs Na A mit einer mittleren Teilchengröße (= 50%-Punkt der Verteilungskurve) von 1,6 bis 3,2 µm, gemessen mit dem Cilas-Granulometer 715 als Phosphat-Substitut enthält.Another object of the invention is a liquid detergent which contains the zeolite powder of the type Na A with an average particle size (= 50% point of the distribution curve) of 1.6 to 3.2 μm, measured with the Cilas 715 granulometer as a phosphate substitute contains.

Das erfindungsgemäße Zeolithpulver des Typs Na A weist den Vorteil auf, daß die damit hergestellten Flüssig­waschmittel, die für die Anwendung günstige Viskosität haben.The zeolite powder of the type Na A according to the invention has the advantage that the liquid detergents produced therewith have the viscosity which is favorable for the application.

In einer bevorzugten Form der Erfindung weist das Zeolithpulver des Typs Na die folgende Teilchengrößenverteilung auf: µm % < 0,5 3 - 0 < 1,0 30 - 0 < 1,5 98 - 2 < 2,0 99 - 20 < 3,0 100 - 82 < 4,0 100 - 95 < 5,0 100 - 98 < 6,0 100 - 99 < 10,0 100 - 100 In a preferred form of the invention, the zeolite powder of the type Na has the following particle size distribution: µm % <0.5 3 - 0 <1.0 30-0 <1.5 98-2 <2.0 99 - 20 <3.0 100 - 82 <4.0 100-95 <5.0 100-98 <6.0 100-99 <10.0 100-100

In einer besonderen Form der Erfindung weist das Zeolithpulver des Typs Na die folgende Teilchengrößenverteilung auf: µm % < 0,5 0 - 0 < 1,0 4 - 0 < 1,5 30 - 10 < 2,0 85 - 50 < 3,0 100 - 95 < 4,0 100 - 99 < 6,0 100 - 100 < 10,0 100 - 100 In a particular form of the invention, the Na type zeolite powder has the following particle size distribution: µm % <0.5 0 - 0 <1.0 4 - 0 <1.5 30-10 <2.0 85-50 <3.0 100-95 <4.0 100-99 <6.0 100-100 <10.0 100-100

Das Zeolithpulver gemäß Figur 2 weist die folgende Teilchengrößenverteilung auf: Mikrometer µm % 1,0 2,2 1,5 16,6 2,0 65,7 3,0 99,4 4,0 100,0 6,0 100,0 8,0 100,0 12,0 100,0 16,0 100,0 24,0 100,0 32,0 100,0 48,0 100,0 64,0 100,0 96,0 100,0 128,0 100,0 192,0 100,0 D (50,0 %) = 1,8 µm The zeolite powder according to FIG. 2 has the following particle size distribution: Micrometer µm % 1.0 2.2 1.5 16.6 2.0 65.7 3.0 99.4 4.0 100.0 6.0 100.0 8.0 100.0 12.0 100.0 16.0 100.0 24.0 100.0 32.0 100.0 48.0 100.0 64.0 100.0 96.0 100.0 128.0 100.0 192.0 100.0 D (50.0%) = 1.8 µm

BeispieleExamples

Zeolithpulver des Typs Na A mit einer Teilchengröße von 3,2 µm und 8,6 µm werden gemäß DE-ps 2517 218 beziehungsweise gemäß DE-PS 2660 726 hergestellt.Zeolite powder of the type Na A with a particle size of 3.2 μm and 8.6 μm are produced in accordance with DE-PS 2517 218 and DE-PS 2660 726, respectively.

Ausgehend von einer Teilchengröße von 3,2 µm wird durch Mahlen mit einer Luftstrahlmühle ein Zeolithpulver erhalten, welches eine Teilchengröße von 1,8 µm aufweist. Die Teilchengröße von 1,1 µm wird durch Naßmahlen in einer Kolloidmühle, Trocknen und Mahlen in einer Stiftmühle erhalten.Starting from a particle size of 3.2 µm, a zeolite powder is obtained by grinding with an air jet mill, which has a particle size of 1.8 µm. The particle size of 1.1 μm is obtained by wet milling in a colloid mill, drying and milling in a pin mill.

Die Kalzium- und Magnesiumbindekapazität wird durch komplexometrische Titration der bleibenden Härte an Ca- und Mg-Ionen nach einer Kontaktzeit von 15 Minuten bestimmt. Diese Werte sind in Tabelle 1 aufgeführt: Tabelle 1 Teilchengröße CaBV [mg CaO/g] MgBV [mg CaO/g] 8,6 157 12 3,2 169 29 1,8 170 32 1,1 157 50 Die Teilchengrößenverteilung wird mit dem Cilas-Granulometer 715 E627 durchgeführt. The calcium and magnesium binding capacity is determined by complexometric titration of the remaining hardness of Ca and Mg ions after a contact time of 15 minutes. These values are listed in Table 1: Table 1 Particle size CaBV [mg CaO / g] MgBV [mg CaO / g] 8.6 157 12 3.2 169 29 1.8 170 32 1.1 157 50 The particle size distribution is carried out with the Cilas granulometer 715 E627.

Dabei werden die folgenden Bedingungen eingehalten:The following conditions are met:

Die ermittelten Teilchengrößenverteilungskurven sind in den Figuren 1, 2, 3, und 4 dargestellt.The determined particle size distribution curves are shown in FIGS. 1, 2, 3 and 4.

Als Detergentien werden eingesetzt:
Natriumalkylbenzolsulphonate (HÜLS)
C₁₃-C₁₅-Oxoalkohol mit 7 EO (BASF)
Entschäumer Wacker S 132 (Wacker Chemie) in einer Menge von 0,1 %.The following are used as detergents:
Sodium alkylbenzenesulphonate (HÜLS)
C₁₃-C₁₅ oxo alcohol with 7 EO (BASF)
Defoamer Wacker S 132 (Wacker Chemie) in an amount of 0.1%.

Die Viskosität wird mittels eines Brookfield Viskosimeters RVT bei 5 und 50 Umdrehungen pro Minute und der Spindel 4 durchgeführt. Die Suspension wird dabei in einen 100 ml Becher eingefüllt, in welchen die Spindel bis zur entsprechenden Markierung eingetaucht wird. Die Ablesung erfolgt nach jeweils 3 Minuten.The viscosity is carried out using a Brookfield RVT viscometer at 5 and 50 revolutions per minute and the spindle 4. The suspension is poured into a 100 ml beaker in which the spindle is immersed up to the appropriate mark. The reading is taken every 3 minutes.

Die Fließzeit wird bestimmt, indem man die Zeit bestimmt, die 100 ml Suspension benötigt, um durch eine 6 m Düse ohne Anwendung von Druck zu fließen.Flow time is determined by determining the time it takes 100 ml of suspension to flow through a 6 m nozzle without applying pressure.

Zur Bestimmung der Lagerstabilität werden Proben von 100 ml in geschlossenen Glasflaschen für 1 Woche und 1 Monat bei 22oC und 40oC gelagert. Die Füllhöhe ist 50 mm.To determine the storage stability, samples of 100 ml are stored in closed glass bottles for 1 week and 1 month at 22 o C and 40 o C. The filling height is 50 mm.

Das Verhalten der flüssigen Phase wird visuell beurteilt.The behavior of the liquid phase is assessed visually.

Die Suspensionen werden folgendermaßen hergestellt:
In einer 250 ml Glasflasche werden die Ausgangsma­terialien eingewogen. Das Zeolithpulver wird zuletzt eingefüllt.The suspensions are made as follows:
The starting materials are weighed into a 250 ml glass bottle. The zeolite powder is filled in last.

Die Mischung wird mittels eines Ultra Turrax (9 m/sec) unter Wasserstrahlvakuum für 15 Minuten dispergiert.The mixture is dispersed using an Ultra Turrax (9 m / sec) under a water jet vacuum for 15 minutes.

Einfache Systeme, bestehend aus Detergens, Zeolith und Wasser, werden verwendet, um den Einfluß der Detergentien und der Mischung der Detergentien auf die Viskosität und die Lagerstabilität zu untersuchen.Simple systems consisting of detergent, zeolite and water are used to investigate the influence of the detergents and the mixture of the detergents on the viscosity and the storage stability.

Ein Zeolith-Gehalt von 15, 25 und 35% wird zusammen mit einem Gehalt von 20% Detergens eingesetzt. Es werden entweder die Detergentien allein oder im Mischungsverhältnis 1:2, 1:1 und 2:1 eingesetzt.A zeolite content of 15, 25 and 35% is used together with a content of 20% detergent. Either the detergents are used alone or in a mixing ratio of 1: 2, 1: 1 and 2: 1.

Die Ergebnisse dieser Tests sind in den Figuren 5, 6 und 7 graphisch dargestellt.The results of these tests are shown graphically in FIGS. 5, 6 and 7.

Figur 5 zeigt die Viskosität bei 5 und 50 Umdrehungen pro Minute als eine Funktion des Zeolith-Gehalts und der Detergens-Mischung.
Der Zeolith hat eine Teilchengröße von 3,2 µm.
Es wird festgestellt, daß das reine anionische Detergens sowie Mischungen mit einem hohen Anteil an anionischem Detergens zu einer hohen Viskosität führen. Dieser Effekt wird beson­ders deutlich bei einem Zeolith-Gehalt von 25 und 35%.Figure 5 shows the viscosity at 5 and 50 revolutions per minute as a function of the zeolite content and the detergent mixture.
The zeolite has a particle size of 3.2 microns.
It is found that the pure anionic detergent and mixtures with a high proportion of anionic detergent lead to a high viscosity. This effect is particularly evident with a zeolite content of 25 and 35%.

Obwohl hohe Viskositäten zu einer Verbesserung der Lagerstabilität führen, werden Anwendungseigenschaften wie Fließen und Benetzen negativ beeinflußt. Die ermittelten Fließzeiten sind in der Figur 6 graphisch dargestellt. Gute Fließzeiten gemeinsam mit einer brauchbaren Viskosität werden bei Mischungen der beiden Detergentien im Verhältnis anionisch zu nicht­ionisch 2:1 und 1:1 ermittelt.Although high viscosities lead to an improvement in storage stability, application properties such as flow and wetting are adversely affected. The flow times determined are shown graphically in FIG. Good flow times together with a usable viscosity are determined for mixtures of the two detergents in the ratio anionic to nonionic 2: 1 and 1: 1.

Figur 7 zeigt den Thixotropie-Index TI der Suspensionen gemäß Figur 5. TI = η (5 Umdre­hungen pro Minute) zu η (50 Umdrehungen pro Minute).FIG. 7 shows the thixotropy index TI of the suspensions according to FIG. 5. TI = η (5 revolutions per minute) to η (50 revolutions per minute).

Der Thixotropie-Index ist der Quotient aus zwei Werten für die Viskosität, die bei verschiedenen Schergefällen ermittelt werden. Der Thixotropie-Index kennzeichnet die Strukturviskosität des Systems. Je höher der Thixotropie-Index ausfällt, umso strukturierter ist das System, und umso besser ist die Lagerstabilität. Das günstigste Ergebnis zeigt - wie der Figur 7 entnommen werden kann - die Mischung, die 13 % anionisches und 7 % nicht-ionisches Detergens enthält.The thixotropy index is the quotient of two values for the viscosity, which are determined at different shear rates. The thixotropy index characterizes the structural viscosity of the system. The higher the thixotropy index, the more structured the system and the better the storage stability. The most favorable result shows - as can be seen in FIG. 7 - the mixture which contains 13% anionic and 7% non-ionic detergent.

Die Mischung, die 13 % anionisches und 7 % nicht-ioni­sches Detergens enthält, wird verwendet, um die Lagerstabilität und das Fließverhalten in Abhängigkeit von der Teilchengrößenverteilung des Zeolith A zu untersuchen.The mixture, which contains 13% anionic and 7% non-ionic detergent, is used to investigate the storage stability and the flow behavior depending on the particle size distribution of the zeolite A.

Die Ergebnisse sind in den Figuren 8 und 9 graphisch dargestellt.The results are shown graphically in FIGS. 8 and 9.

Figur 8 zeigt die Viskosität der Suspensionen als eine Funktion der Zeolith A-Teilchengrößenvertei­lung und des Zeolith A-Gehaltes, gemessen bei 5 Umdrehungen pro Minute.FIG. 8 shows the viscosity of the suspensions as a function of the zeolite A particle size distribution and the zeolite A content, measured at 5 revolutions per minute.

Figur 9 zeigt die Viskosität der Suspensionen als eine Funktion A-Teilchengrößenverteilung und des Zeolith A-Gehaltes, gemessen bei 50 Umdrehun­gen pro Minute.FIG. 9 shows the viscosity of the suspensions as a function A particle size distribution and the zeolite A content, measured at 50 revolutions per minute.

Es wird festgestellt, daß besonders das Zeolithpulver mit einer Teilchengröße von 1,1 µm einen ausgeprägten Verdickungseffekt in dem Viskositätsverhalten zeigt. Die Suspension mit einem Gehalt von 25 % und insbeson­ders die Suspension mit einem Gehalt von 35 % Zeolith zeigen eine pastenartige Konsistenz.It is found that especially the zeolite powder with a particle size of 1.1 μm shows a pronounced thickening effect in the viscosity behavior. The suspension with a content of 25% and in particular the suspension with a content of 35% zeolite show a paste-like consistency.

Die anderen Zeolithpulver ergeben jeweils eine flüssige Suspension, wobei der Zeolith mit der Teilchengröße von 1,8 µm den geringsten Verdickungs­effekt mit zunehmender Konzentration zeigt.The other zeolite powders each result in a liquid suspension, the zeolite with the particle size of 1.8 μm showing the least thickening effect with increasing concentration.

Die niedrige Viskosität ist ein Vorteil für die Anwendung, weil diese Suspensionen leicht gegossen werden können.The low viscosity is an advantage for the application because these suspensions can be poured easily.

Figur 10 zeigt das Fließverhalten der Suspensionen in Abhängigkeit von dem Zeolith-Gehalt und der Teilchengröße. Dabei wird deutlich, daß die Suspension mit dem Zeolithpulver der Teil­chengröße 1,8 µm für die Konzentrationen an diesem Zeolith von 25 und 35 % eine konstante Fließgeschwindigkeit aufweist. Diese Unab­hängigkeit des Fließverhaltens von der Konzentration wird durch den Thixotropie-­Index bestätigt.FIG. 10 shows the flow behavior of the suspensions as a function of the zeolite content and the particle size. It becomes clear that the suspension with the zeolite powder having a particle size of 1.8 μm has a constant flow rate for the concentrations of this zeolite of 25 and 35%. This independence of the flow behavior from the concentration is confirmed by the thixotropy index.

Figur 11 zeigt den Thixotropie-Index in Abhängigkeit von der Teilchengröße und der Konzentration des Zeolithpulvers.
So ergibt der Zeolith mit der Teilchengröße von 1,8 µm Werte von 1,2 bis 1,3.
Der Zeolith mit der Teilchengröße von 1,1 µm ergibt einen Wert von 3 bis 4.FIG. 11 shows the thixotropy index as a function of the particle size and the concentration of the zeolite powder.
The zeolite with a particle size of 1.8 µm gives values from 1.2 to 1.3.
The zeolite with the particle size of 1.1 µm gives a value of 3 to 4.

Während der Zeolith mit der Teilchengröße 3,2 µm beziehungsweise 8,6 µm jeweils einen Wert zwischen 1,3 und 2,0 ergeben.While the zeolite with a particle size of 3.2 µm or 8.6 µm gives a value between 1.3 and 2.0.

Der Lagertest wird mit denselben Suspensionen durch­geführt, wie sie bei den Versuchen gemäß den Figuren 8 bis 11 eingesetzt wurden.The storage test is carried out with the same suspensions as were used in the tests according to FIGS. 8 to 11.

Die Ergebnisse des Lagertestes sind in der Tabelle 2 aufgeführt. Tabelle 2 Teilchengröße µm Gehalt an Zeolith % Separation % a 20°C 40°C 1,1 15 0 0 1,1 25 b - - 1,1 35 b - - 1,8 15 36 / - 22 / - 1,8 25 14 / - 10 / - 1,8 35 2 / 6 1 / 2 3,2 15 50 / - 55 / - 3,2 25 50 / - 50 / - 3,2 35 3 / 6 3 / 8 8,6 15 60 / - 68 / - 8,6 25 30 / - 40 / - 8,6 35 12 / - 20 / - a = 1. Zahl ist die Separation nach 7 Tagen 2. Zahl ist die Separation nach 28 Tagen Wenn die Separation nach 7 Tagen mehr als 10 % beträgt, wird die Separation nach 28 Tagen nicht mehr gemessen. b = Der Lagertest wird hier nicht durchgeführt, weil die Suspension eine pastenförmige Konsistenz aufweist. The results of the storage test are listed in Table 2. Table 2 Particle size µm Zeolite content% Separation% a 20 ° C 40 ° C 1.1 15 0 0 1.1 25 b - - 1.1 35 b - - 1.8 15 36 / - 22 / - 1.8 25th 14 / - 10 / - 1.8 35 2/6 1/2 3.2 15 50 / - 55 / - 3.2 25th 50 / - 50 / - 3.2 35 3/6 3/8 8.6 15 60 / - 68 / - 8.6 25th 30 / - 40 / - 8.6 35 12 / - 20 / - a = 1st number is the separation after 7 days 2nd number is the separation after 28 days If the separation after 7 days is more than 10%, the separation is no longer measured after 28 days. b = The storage test is not carried out here because the suspension has a pasty consistency.

Der Grad der Separation wird bestimmt aus dem Verhältnis der klaren Phase zu der Höhe der Füllung und ausgedrückt in Prozent.The degree of separation is determined from the ratio of the clear phase to the level of the filling and expressed in percent.

Der Lagertest zeigt den Einfluß sowohl der Viskosität als auch der Teilchengröße auf die Lagerstabilität, wobei offensichtlich der Einfluß der Teilchengröße größer ist. Die günstigsten Werte, vom Standpunkt der Viskosität aus gesehen, werden mit einer Teilchengröße von 3,2 µm erzielt. Die Lagerfähigkeit dieser Suspension ist jedoch deutlich unter der Suspension, die ein Zeolithpulver mit einer Teilchengröße von 1,8 µm aufweist. Dies wird besonders deutlich, wenn man die Suspension mit einem Gehalt an Zeolith von 25 % vergleicht. Jedoch weist die Suspension mit dem Zeolith einer Teilchengröße von 1,1 µm eine zu hohe Viskosität auf, die sie für die Anwendung unbrauchbar macht.The storage test shows the influence of both the viscosity and the particle size on the storage stability, the influence of the particle size obviously being greater. The most favorable values, from the point of view of viscosity, are achieved with a particle size of 3.2 µm. However, the shelf life of this suspension is significantly lower than the suspension which has a zeolite powder with a particle size of 1.8 μm. This becomes particularly clear when comparing the suspension with a zeolite content of 25%. However, the suspension with the zeolite with a particle size of 1.1 µm has too high a viscosity, which makes it unusable for the application.

Bei einer Teilchengröße von 8,6 µm tritt innerhalb weniger Tage eine totale Separation ein.With a particle size of 8.6 µm, total separation occurs within a few days.

Die Suspension mit einem Zeolith, der eine Teilchen­größe von 1,8 µm aufweist, zeigt das in der Summe beste Ergebnis in Bezug auf Fließfähigkeit und Lager­fähigkeit.The suspension with a zeolite, which has a particle size of 1.8 µm, shows the best overall result in terms of flowability and storage stability.

Claims (2)

1. Zeolithpulver des Typs Na A, gekennzeichnet durch eine mittlere Teilchengröße (= 50%-Punkt) von 1,6 bis 3,2 µm, gemessen mit dem Cilas Granulometer 7151. Zeolite powder of the type Na A, characterized by an average particle size (= 50% point) of 1.6 to 3.2 μm, measured with the Cilas 715 granulometer 2. Flüssigwaschmittel, welches das Zeolithpulver des Typs Na A gemäß des Anspruch 1 enthält.2. Liquid detergent which contains the zeolite powder of the type Na A according to claim 1.
EP89114795A 1988-08-12 1989-08-10 Na A-type zeolite powder for use in liquid detergents Expired - Lifetime EP0357989B1 (en)

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EP89109796A EP0356625A1 (en) 1988-08-12 1989-05-31 Na A-type zeolite powder for use in liquid detergents
EP89109796 1989-05-31

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993004155A1 (en) * 1991-08-27 1993-03-04 Henkel Kommanditgesellschaft Auf Aktien Zeolite-containing liquid washing agent
WO1994000545A1 (en) * 1992-06-25 1994-01-06 Unilever N.V. Machine dishwashing composition
WO1996034828A1 (en) * 1995-05-01 1996-11-07 Crosfield Limited Small particle size p-type zeolite
WO2000053709A1 (en) * 1999-03-09 2000-09-14 The Procter & Gamble Company Detergent compositions
WO2000053710A1 (en) * 1999-03-09 2000-09-14 The Procter & Gamble Company Detergent compositions
WO2001000528A1 (en) * 1999-06-25 2001-01-04 Albemarle Corporation High density zeolites and their production
US6357678B1 (en) 1999-10-29 2002-03-19 Albermarle Corporation Process for producing ultra finely-divided zeolite powder
US6432380B1 (en) 2000-09-08 2002-08-13 Albemarle Corporation Synthesis of aluminosilicates via cofeeding an alkali metal aluminate and sodium silicate and cofeeding apparatus therefor
US7037352B2 (en) 2000-12-12 2006-05-02 Showa Denko Kabushiki Kaisha Polishing particle and method for producing polishing particle

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FR2370689A1 (en) * 1976-11-11 1978-06-09 Degussa TYPE A CRYSTALLINE ZEOLITE POWDER
EP0015024A1 (en) * 1979-02-16 1980-09-03 THE PROCTER &amp; GAMBLE COMPANY Detergent compositions containing binary builder system
US4405483A (en) * 1982-04-27 1983-09-20 The Procter & Gamble Company Stable liquid detergents containing aluminosilicate ion exchange material
US4560492A (en) * 1984-11-02 1985-12-24 The Procter & Gamble Company Laundry detergent composition with enhanced stain removal

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DE2856278A1 (en) * 1978-12-27 1980-07-10 Degussa METHOD FOR PRODUCING FINE-PARTICLE SODIUM ALUMINUM SILICATES

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Publication number Priority date Publication date Assignee Title
FR2370689A1 (en) * 1976-11-11 1978-06-09 Degussa TYPE A CRYSTALLINE ZEOLITE POWDER
EP0015024A1 (en) * 1979-02-16 1980-09-03 THE PROCTER &amp; GAMBLE COMPANY Detergent compositions containing binary builder system
US4405483A (en) * 1982-04-27 1983-09-20 The Procter & Gamble Company Stable liquid detergents containing aluminosilicate ion exchange material
US4560492A (en) * 1984-11-02 1985-12-24 The Procter & Gamble Company Laundry detergent composition with enhanced stain removal

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993004155A1 (en) * 1991-08-27 1993-03-04 Henkel Kommanditgesellschaft Auf Aktien Zeolite-containing liquid washing agent
WO1994000545A1 (en) * 1992-06-25 1994-01-06 Unilever N.V. Machine dishwashing composition
WO1996034828A1 (en) * 1995-05-01 1996-11-07 Crosfield Limited Small particle size p-type zeolite
CN1092603C (en) * 1995-05-01 2002-10-16 克罗斯菲尔德有限公司 Small particle size p-type zeolite
WO2000053709A1 (en) * 1999-03-09 2000-09-14 The Procter & Gamble Company Detergent compositions
WO2000053710A1 (en) * 1999-03-09 2000-09-14 The Procter & Gamble Company Detergent compositions
WO2001000528A1 (en) * 1999-06-25 2001-01-04 Albemarle Corporation High density zeolites and their production
US6221835B1 (en) 1999-06-25 2001-04-24 Albemarle Corporation High density zeolites and their production
US6357678B1 (en) 1999-10-29 2002-03-19 Albermarle Corporation Process for producing ultra finely-divided zeolite powder
US6432380B1 (en) 2000-09-08 2002-08-13 Albemarle Corporation Synthesis of aluminosilicates via cofeeding an alkali metal aluminate and sodium silicate and cofeeding apparatus therefor
US7037352B2 (en) 2000-12-12 2006-05-02 Showa Denko Kabushiki Kaisha Polishing particle and method for producing polishing particle

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