EP0357989A1 - 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
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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EP
European Patent Office
Prior art keywords
particle size
zeolite
zeolite powder
viscosity
liquid detergents
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.)
Granted
Application number
EP89114795A
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German (de)
English (en)
Other versions
EP0357989B1 (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
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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
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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 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.

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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)
  • Detergent Compositions (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
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 true EP0357989A1 (fr) 1990-03-14
EP0357989B1 EP0357989B1 (fr) 1995-02-08

Family

ID=25871033

Family Applications (1)

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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)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993004155A1 (fr) * 1991-08-27 1993-03-04 Henkel Kommanditgesellschaft Auf Aktien Produit liquide de lavage contenant des zeolithes
WO1994000545A1 (fr) * 1992-06-25 1994-01-06 Unilever N.V. Composition pour le lavage en machine de la vaisselle
WO1996034828A1 (fr) * 1995-05-01 1996-11-07 Crosfield Limited Zeolite de type p a particules de petite taille
WO2000053710A1 (fr) * 1999-03-09 2000-09-14 The Procter & Gamble Company Compositions de detergents
WO2000053709A1 (fr) * 1999-03-09 2000-09-14 The Procter & Gamble Company Compositions de detergents
WO2001000528A1 (fr) * 1999-06-25 2001-01-04 Albemarle Corporation Zéolites haute densité et leur 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 (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2370689A1 (fr) * 1976-11-11 1978-06-09 Degussa Poudre de zeolite cristalline de type a
EP0015024A1 (fr) * 1979-02-16 1980-09-03 THE PROCTER & 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

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2856278A1 (de) * 1978-12-27 1980-07-10 Degussa Verfahren zur herstellung feinstteiliger natriumaluminiumsilikate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2370689A1 (fr) * 1976-11-11 1978-06-09 Degussa Poudre de zeolite cristalline de type a
EP0015024A1 (fr) * 1979-02-16 1980-09-03 THE PROCTER & 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

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993004155A1 (fr) * 1991-08-27 1993-03-04 Henkel Kommanditgesellschaft Auf Aktien Produit liquide de lavage contenant des zeolithes
WO1994000545A1 (fr) * 1992-06-25 1994-01-06 Unilever N.V. Composition pour le lavage en machine de la vaisselle
WO1996034828A1 (fr) * 1995-05-01 1996-11-07 Crosfield Limited Zeolite de type p a particules de petite taille
CN1092603C (zh) * 1995-05-01 2002-10-16 克罗斯菲尔德有限公司 小粒度p型沸石,其生产方法和含有该沸石的液体洗涤剂配方
WO2000053710A1 (fr) * 1999-03-09 2000-09-14 The Procter & Gamble Company Compositions de detergents
WO2000053709A1 (fr) * 1999-03-09 2000-09-14 The Procter & Gamble Company Compositions de detergents
WO2001000528A1 (fr) * 1999-06-25 2001-01-04 Albemarle Corporation Zéolites haute densité et leur 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

Also Published As

Publication number Publication date
EP0357989B1 (fr) 1995-02-08
ATE118243T1 (de) 1995-02-15

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