EP0357989B1 - Zéolite Na A en poudre pour l'utilisation dans les produits détergents liquides - Google Patents

Zéolite Na A en poudre pour l'utilisation dans les produits détergents liquides 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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EP
European Patent Office
Prior art keywords
particle size
zeolite
zeolite powder
viscosity
der
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP89114795A
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German (de)
English (en)
Other versions
EP0357989A1 (fr
Inventor
Beata - M. Dr. Sax
Wolfgang Dr. Leonhardt
Akos Dr. Kiss
Wolfgang Dr. Lortz
Wolfgang Dr. Roebke
Claus Dietrich
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from EP89109796A external-priority patent/EP0356625A1/fr
Application filed by Degussa GmbH filed Critical Degussa GmbH
Publication of EP0357989A1 publication Critical patent/EP0357989A1/fr
Application granted granted Critical
Publication of EP0357989B1 publication Critical patent/EP0357989B1/fr
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Classifications

    • 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.

Landscapes

  • 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)

Claims (2)

  1. Zéolite en poudre du type Na A, caractérisée par une répartition de tailles de particules de : »m % < 0,5 0 - 0 < 1 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
    mesurée avec un granulomètre CILAS 715.
  2. Agent détergent liquide qui renferme la zéolite en poudre du type Na A conformément à la revendication 1.
EP89114795A 1988-08-12 1989-08-10 Zéolite Na A en poudre pour l'utilisation dans les produits détergents liquides Expired - Lifetime EP0357989B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE3827360 1988-08-12
DE3827360 1988-08-12
EP89109796A EP0356625A1 (fr) 1988-08-12 1989-05-31 Zéolite Na A en poudre pour l'utilisation dans les produits détergents liquides
EP89109796 1989-05-31

Publications (2)

Publication Number Publication Date
EP0357989A1 EP0357989A1 (fr) 1990-03-14
EP0357989B1 true EP0357989B1 (fr) 1995-02-08

Family

ID=25871033

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89114795A Expired - Lifetime EP0357989B1 (fr) 1988-08-12 1989-08-10 Zéolite Na A en poudre pour l'utilisation dans les produits détergents liquides

Country Status (2)

Country Link
EP (1) EP0357989B1 (fr)
AT (1) ATE118243T1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4128426A1 (de) * 1991-08-27 1993-03-04 Henkel Kgaa Zeolithhaltiges fluessigwaschmittel
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 (fr) * 1999-03-09 2001-12-05 The Procter & Gamble Company Compositions de detergents
EP1159383A1 (fr) * 1999-03-09 2001-12-05 The Procter & Gamble Company Compositions de detergents
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)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0013417A1 (fr) * 1978-12-27 1980-07-23 Henkel Kommanditgesellschaft auf Aktien Procédé pour la production d'alumino-silicates de sodium finement divisés, cristallin et insoluble dans l'eau

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2651419A1 (de) * 1976-11-11 1978-05-18 Degussa Kristallines zeolithpulver des typs a iv
EP0015024A1 (fr) * 1979-02-16 1980-09-03 THE PROCTER &amp; GAMBLE COMPANY Compositions détergentes contenant un système d'adjuvant binaire
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 (fr) * 1978-12-27 1980-07-23 Henkel Kommanditgesellschaft auf Aktien Procédé pour la production d'alumino-silicates de sodium finement divisés, cristallin et insoluble dans l'eau

Also Published As

Publication number Publication date
ATE118243T1 (de) 1995-02-15
EP0357989A1 (fr) 1990-03-14

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