EP0357989B1 - 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
EP0357989B1
EP0357989B1 EP89114795A EP89114795A EP0357989B1 EP 0357989 B1 EP0357989 B1 EP 0357989B1 EP 89114795 A EP89114795 A EP 89114795A EP 89114795 A EP89114795 A EP 89114795A EP 0357989 B1 EP0357989 B1 EP 0357989B1
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Prior art keywords
particle size
zeolite
zeolite powder
viscosity
der
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German (de)
French (fr)
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EP0357989A1 (en
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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

Definitions

  • 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 are practical have no particle sizes above 40 »m.
  • CA-PS 1202 857 describes a liquid detergent. which as aluminum silicate zeolite A with a particle size of 0.01 to 5 »m, preferably 0.5 to 1.5» m.
  • the document Kuzel (US Pat. No. 4,405,483) describes liquid detergents which contain aluminosilicate as a builder component.
  • the aluminosilicate can have a particle size of approximately 0.1 »m to approximately 10» m.
  • Amorphous material can be smaller, for example 0.01 »m to 10» m.
  • the particle size can also be 0.2 to 4 »m.
  • the average particle size is determined using a scanning electron microscope.
  • EP-A 0 015 024 describes a detergent which contains zeolite A with a diameter of 3 »m.
  • Document FR-A 2 370 689 describes a zeolite powder of type A with a 50% value of at most 4.9 »m in the particle size distribution, the particle size distribution being measured using a Coulter Counter.
  • the document EP-A 0 013 417 describes a molecular sieve type Na A with an average particle size smaller than 3 »m.
  • the known liquid detergents have the disadvantage that they have too high a viscosity for use in household washing machines.
  • the invention relates to a zeolite powder of the type Na A, characterized by a Particle size distribution of »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 measured with the Cilas 715 granulometer.
  • the zeolite powder of the 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.
  • Another object of the invention is a liquid detergent which contains the zeolite powder of type Na A with the above-mentioned particle size distribution, measured with the Cilas granulometer 715 as a phosphate substitute.
  • the zeolite powder of 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.
  • Zeolite powder of the type Na A with a particle size of 3.2 »m and 8.6» m are produced according to 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 grinding in a colloid mill, drying and grinding 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 Fig. 4 157 12th 3.2 Fig. 3 169 29 1.8 Fig. 2 170 32 1.1 Fig. 1 157 50
  • the particle size distribution is carried out using the Cilas 715 E627 granulometer.
  • 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.
  • samples of 100 ml are stored in closed glass bottles for 1 week and 1 month at 22 ° C and 40 ° C.
  • the filling height is 50 mm.
  • the behavior of the liquid phase is assessed visually.
  • the suspensions are prepared as follows: The starting materials are weighed into a 250 ml glass bottle. The zeolite powder is filled in last.
  • the mixture is dispersed by means of 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.
  • the particle size of the zeolite is 3.2 »m.
  • 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.
  • 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 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 viscosity and particle size on storage stability.
  • the influence of the particle size is obviously 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.
  • the suspension with a zeolite which has a particle size of 1.8 »m, shows the best overall result in terms of flowability and storage stability.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (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)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Detergent Compositions (AREA)

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 »m, insbesondere von 8 bis 0,1 »m, bestehen und praktisch keine Teilchengrößen oberhalb 40 »m 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 »m, in particular 8 to 0.1» m, and are practical have no particle sizes above 40 »m.

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

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.

Das Dokument Kuzel (US-PS 4,405,483) beschreibt Flüssigwaschmittel, die als Builderkomponente Alumosilikat enthalten. Gemäß Spalte 6 kann das Alumosilikat eine Teilchengröße von circa 0,1 »m bis circa 10 »m aufweisen. Amorphes Material kann kleiner, zum Beispiel 0,01 »m bis gegen 10 »m, sein. Die Teilchengröße kann außerdem 0,2 bis 4 »m betragen. Die mittlere Teilchengröße wird gemäß Kuzel durch ein Rasterelektronenmikroskop ermittelt.The document Kuzel (US Pat. No. 4,405,483) describes liquid detergents which contain aluminosilicate as a builder component. According to column 6, the aluminosilicate can have a particle size of approximately 0.1 »m to approximately 10» m. Amorphous material can be smaller, for example 0.01 »m to 10» m. The particle size can also be 0.2 to 4 »m. According to Kuzel, the average particle size is determined using a scanning electron microscope.

Das Dokument EP-A 0 015 024 beschreibt ein Waschmittel, welches Zeolith A mit einem Durchmesser von 3 »m enthält.The document EP-A 0 015 024 describes a detergent which contains zeolite A with a diameter of 3 »m.

Das Dokument FR-A 2 370 689 beschreibt ein Zeolithpulver des Typs A mit einem 50-%-Wert von maximal 4,9 »m bei der Teilchengrößenverteilung, wobei die Teilchengrößenverteilung mittels Coulter Counter gemessen wurde.Document FR-A 2 370 689 describes a zeolite powder of type A with a 50% value of at most 4.9 »m in the particle size distribution, the particle size distribution being measured using a Coulter Counter.

Das Dokument EP-A 0 013 417 beschreibt ein Molekularsieb-Typ Na A mit einer mittleren Teilchengröße kleiner als 3 »m.The document EP-A 0 013 417 describes a molecular sieve type Na A with an average particle size smaller than 3 »m.

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 Teilchengrößenverteilung 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 Teilchengrößenverteilung von »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
gemessen mit dem Cilas-Granulometer 715.The invention relates to a zeolite powder of the type Na A, characterized by a Particle size distribution of »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
measured with the Cilas 715 granulometer.

Vorzugsweise kann das Zeolithpulver des Typs Na A eine mittlere Teilchengröße von 1,7 bis 2,5 »m aufweisen.The zeolite powder of the 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 »m betragen.In particular, the average particle size can be 1.7 to 2.0 »m.

Ein weiterer Gegenstand der Erfindung ist ein Flüssigwaschmittel, welches das Zeolithpulver des Typs Na A mit der oben genannten Teilchengrößenverteilung, 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 type Na A with the above-mentioned particle size distribution, measured with the Cilas granulometer 715 as a phosphate substitute.

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 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.

Das Zeolithpulver gemäß Figur 2 weist die folgende Teilchengrößenverteilung auf: Mikrometer »m % 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 »m The zeolite powder according to FIG. 2 has the following particle size distribution: Micrometer »M % 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 »m

BeispieleExamples

Zeolithpulver des Typs Na A mit einer Teilchengröße von 3,2 »m und 8,6 »m 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 »m and 8.6» m are produced according to DE-PS 2517 218 and DE-PS 2660 726, respectively.

Ausgehend von einer Teilchengröße von 3,2 »m wird durch Mahlen mit einer Luftstrahlmühle ein Zeolithpulver erhalten, welches eine Teilchengröße von 1,8 »m aufweist. Die Teilchengröße von 1,1 »m wird durch Naßmahlen in einer Kolloidmühle, Trocknen und Mahlen in einer Stiftmühle erhalten.Starting from a particle size of 3.2 »m, 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 grinding in a colloid mill, drying and grinding 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 Fig.4 157 12 3,2 Fig.3 169 29 1,8 Fig.2 170 32 1,1 Fig.1 157 50 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 Fig. 4 157 12th 3.2 Fig. 3 169 29 1.8 Fig. 2 170 32 1.1 Fig. 1 157 50

Die Teilchengrößenverteilung wird mit dem Cilas-Granulometer 715 E627 durchgeführt.The particle size distribution is carried out using the Cilas 715 E627 granulometer.

Dabei werden die folgenden Bedingungen eingehalten:
Die ermittelten Teilchengrößenverteilungskurven sind in den Figuren 1, 2, 3, und 4 dargestellt.The following conditions are met:
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 22°C und 40°C 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 ° C and 40 ° 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 prepared 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 by means of 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. Die Teilchengröße des Zeolithes beträgt 3,2 »m.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. The particle size of the zeolite is 3.2 »m.

Die Ergebnisse dieser Tests sind in den Figuren 5, 6 und 7 graphisch dargestellt.

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 »m. 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%.
The results of these tests are shown graphically in FIGS. 5, 6 and 7.
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 »m. 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.

Figur 7
zeigt den Thixotropie-Index TI der Suspensionen gemäß Figur 5. TI = η (5 Umdrehungen pro Minute) zu η (50 Umdrehungen pro Minute)
Figure imgb0001
Figure imgb0002
 .
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.
Figure 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)
Figure imgb0001
Figure imgb0002
 .

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.

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.
Figur 9
zeigt die Viskosität der Suspensionen als eine Funktion A-Teilchengrößenverteilung und des Zeolith A-Gehaltes, gemessen bei 50 Umdrehungen pro Minute.
The results are shown graphically in FIGS. 8 and 9.
Figure 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.
Figure 9
shows the viscosity of the suspensions as a function of 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 »m 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 »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.

Die anderen Zeolithpulver ergeben jeweils eine flüssige Suspension, wobei der Zeolith mit der Teilchengröße von 1,8 »m 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 »m showing the least thickening effect with increasing concentration.

Die niedrige Viskosität ist ein Vorteil für die Anwendung, weil diese Suspensionen leicht gegossen werden können.

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 »m 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.
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 »m Werte von 1,2 bis 1,3.
Der Zeolith mit der Teilchengröße von 1,1 »m ergibt einen Wert von 3 bis 4, Während der Zeolith mit der Teilchengröße 3,2 »m beziehungsweise 8,6 »m jeweils einen Wert zwischen 1,3 und 2,0 ergeben.
The low viscosity is an advantage for the application because these suspensions can be poured easily.
Figure 10
shows the flow behavior of the suspensions depending on the zeolite content and the particle size. It becomes clear that the suspension with the zeolite powder of particle size 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.
Figure 11
shows the thixotropy index depending on 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, While the zeolite with the particle size 3.2 »m or 8.6» m 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 »m 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 % betragt, 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 »m 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 »m erzielt. Die Lagerfähigkeit dieser Suspension ist jedoch deutlich unter der Suspension, die ein Zeolithpulver mit einer Teilchengröße von 1,8 »m 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 »m eine zu hohe Viskosität auf, die sie für die Anwendung unbrauchbar macht.The storage test shows the influence of both viscosity and particle size on storage stability. the influence of the particle size is obviously greater. The most favorable values, from the point of view of viscosity, are achieved with a particle size of 3.2 »m. 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 »m. 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 »m has too high a viscosity, which makes it unusable for the application.

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

Die Suspension mit einem Zeolith, der eine Teilchengröße von 1,8 »m 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 »m, shows the best overall result in terms of flowability and storage stability.

Claims (2)

  1. Na A-type zeolite powder, characterised by a particle-size distribution of »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
    measured using a Cilas granulometer 715.
  2. Liquid detergent which contains the Na A-type zeolite powder 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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DE3827360 1988-08-12
DE3827360 1988-08-12
EP89109796 1989-05-31
EP89109796A EP0356625A1 (en) 1988-08-12 1989-05-31 Na A-type zeolite powder for use in liquid detergents

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Publication number Priority date Publication date Assignee Title
DE4128426A1 (en) * 1991-08-27 1993-03-04 Henkel Kgaa LIQUID DETERGENT WITH ZEOLITE
AU4326193A (en) * 1992-06-25 1994-01-24 Unilever Plc Machine dishwashing composition
GB9508821D0 (en) * 1995-05-01 1995-06-21 Unilever Plc Small particle size p-type zeolite
EP1159384A1 (en) * 1999-03-09 2001-12-05 The Procter & Gamble Company Detergent compositions
EP1159383A1 (en) * 1999-03-09 2001-12-05 The Procter & Gamble Company Detergent compositions
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

Citations (1)

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Publication number Priority date Publication date Assignee Title
EP0013417A1 (en) * 1978-12-27 1980-07-23 Henkel Kommanditgesellschaft auf Aktien Process for producing finely devided crystalline water insoluble sodium aluminium silicates

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DE2651419A1 (en) * 1976-11-11 1978-05-18 Degussa TYPE A IV 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

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0013417A1 (en) * 1978-12-27 1980-07-23 Henkel Kommanditgesellschaft auf Aktien Process for producing finely devided crystalline water insoluble sodium aluminium silicates

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