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WO1994029219A1 - Stabilisation de suspensions de silicates d'aluminium et de metaux alcalins zeolitiques finement divises - Google Patents

Stabilisation de suspensions de silicates d'aluminium et de metaux alcalins zeolitiques finement divises Download PDF

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Publication number
WO1994029219A1
WO1994029219A1 PCT/EP1994/001731 EP9401731W WO9429219A1 WO 1994029219 A1 WO1994029219 A1 WO 1994029219A1 EP 9401731 W EP9401731 W EP 9401731W WO 9429219 A1 WO9429219 A1 WO 9429219A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkali metal
silicate
metal aluminum
suspensions
silicates
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.)
Ceased
Application number
PCT/EP1994/001731
Other languages
German (de)
English (en)
Inventor
Wolfgang Seiter
Johannes Hachgenei
Rainer Scholl
Peter Freidank
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of WO1994029219A1 publication Critical patent/WO1994029219A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C11D3/1286—Stabilised aqueous aluminosilicate suspensions

Definitions

  • the present invention relates to a method for stabilizing pumpable suspensions of very finely divided zeolitic alkali metal aluminum silicates.
  • alkali metal aluminum silicates are used, for example, as builders for detergents, dishwashing detergents and cleaning agents, as molecular sieves, catalysts and sorbents and as an additive to ceramic frits and glazes.
  • the alkali metal aluminum silicates are prepared by hydrothermally reacting sodium silicate with sodium aluminate in the presence of alkali.
  • the raw materials metered within defined concentration ranges form a highly water-containing gel in the precipitation container with an increase in viscosity.
  • the precipitation is carried out in a relatively dilute solution and with vigorous stirring.
  • the conversion into the highly ordered crystalline structure begins when the temperature is raised in the downstream crystallizing containers.
  • the mother liquor is drawn off via suitable separation devices (eg vacuum belt filter), and the approximately 30-50% by weight filter cake is washed. Mother liquor and washing water can partly flow back into the substance mixture directly or after evaporation in an evaporator system.
  • suitable separation devices eg vacuum belt filter
  • the filter cake can be spray-dried or stabilized by additions in the form of a suspension.
  • DE 2527388 A1 discloses pumpable suspensions of the alkali metal aluminum silicates mentioned which are stabilized with at least one dispersant which is selected from: 1. an organic, macromolecular, carboxyl and / or hydroxyl group-containing polymer compound; 2. a phosphonic acid which has at least one further phosphonic acid and / or carboxyl group;
  • the dispersant is preferably used in amounts of 0.5 to 6% by weight, based on the total weight of the suspension.
  • the suspensions contain 20 to 42% by weight of alkali metal aluminum silicates.
  • EP-0 000 130 B1 discloses silicate complexing agents for alkaline earth ions and processes for their production.
  • the object of the present invention is to provide a method for stabilizing pumpable suspensions of very finely divided zeolitic alkali metal aluminum silicates, in which detergent-compatible and, in particular, detergent-active stabilizers are used which have no hot air volatility and which also have current ecological requirements enough detergent ingredients.
  • a first embodiment of the present invention consists in a process for stabilizing pumpable suspensions of very finely divided zeolitic alkali metal aluminum silicates of the general formula (I),
  • Me sodium and / or potassium
  • x is a number in the range from 0.8 to 1.3
  • y is a number in the range from 1.3 to 10
  • z is a number in the range from 0 to 6, with a swellable water-insoluble Layered silicate, the layered silicate having a swelling volume in the range from 30 to 80 ml per 2 g of layered silicate.
  • the swelling volume is determined by pouring 100 ml of fully demineralized water into a measuring cylinder, slowly and in portions adding 2 g of the layered silicate to the surface of the water and reading the volume of the layered silicate deposited after a standing time of 1 hour.
  • DE 25 27 388 describes the use of swellable, water-insoluble sheet silicates for the stabilization of alkali metal aluminum silicates, but the sheet silicates mentioned here are ultimately not suitable for the stabilization, since in the range of today's highly concentrated alkali metal aluminum silicate suspensions from 40 to 60% by weight, the amounts mentioned in DE 2527 388 AI of, for example, 2 to 4% by weight (Example 11) do not stabilize the AI lead potassium metal aluminum silicate suspension. Rather, solid suspensions that are no longer pumpable are obtained.
  • the above general formula (I) comprises a large number of substances which, although their chemical composition often differs only slightly, differ considerably in terms of their structure and properties.
  • the X-ray diffraction diagram is generally used to identify such zeolites.
  • type A and X zeolites but also, for example, P and Y.
  • a further preferred embodiment of the present invention consists in that suspensions are used which contain 40 to 60% by weight, in particular 45 to 55% by weight and, with particular advantage, around 50% by weight of alkali metal aluminum silicates.
  • the pH of such preferred suspensions is usually about 7 to 12.
  • the swellable, water-insoluble sheet silicates which are particularly selected in the context of the present invention and can preferably be used correspond to the general formula (II)
  • Me ' sodium and potassium (the ratio of Na 2 0: K 0 preferably 10 to 100: 1 amounts),
  • EP-0 000 130 B1 describes that such swellable, water-insoluble sheet silicates can be prepared by loading alkali with a material obtained by acid activation of a mineral from the montmorillonite-beidellite series.
  • acid-activated bentonite is used as the starting material.
  • the acid-activated material is loaded with an alkali metal hydroxide, carbonate, phosphate or borate by dry or wet mixing.
  • the loading of the acid-activated material is carried out in aqueous suspension and as a paste at 25 to 100 ° C.
  • the swellable, water-insoluble sheet silicates produced in this way differ from the previously customary, commercially available sheet silicates, on the one hand, as described in EP-0000130 B1 by their particularly high specific surface area of about 200 to 350 m 2 / g. According to the invention, however, it was found that the swellable, water-insoluble sheet silicates used according to the invention have a particularly high swelling volume.
  • a commercial product from Südchemie, which is available under the name Vasagel (R), is advantageously used.
  • Vasagel As is known, water-insoluble layered silicates swell more or less quickly when they sink into water, depending on their swelling capacity, and occupy, for example, a more or less large space at the bottom of a measuring cylinder that corresponds to their swelling capacity.
  • the method for determining the swelling volume is carried out as follows: A commercially available, graduated measuring cylinder for 100 ml without spout
  • Rubber or ground glass stopper is filled with 100 ml of fully demineralized water. 2 g of the substance to be measured (swellable, water-insoluble layer silicate) is slowly and in portions, about 0.1 to 0.2 g each, added to the surface of the water with the spatula. You now wait for a portion to drop before adding the next portion.
  • the amount of the swollen substance which it takes up in the measuring cylinder is read off in ml per 2 g after one hour.
  • Layered silicates included. Adequate stabilization of the suspension of alkali metal aluminum silicates over a long period (a few days to weeks) is possible within this range. If the specified amount is undershot, the stabilization effect is of course limited, while on the other hand, if the amount of stabilizer (layered silicate) is exceeded, it does not result in improved stabilization, but rather an increased viscosity, which occurs in particular in the case of highly concentrated alkali metal aluminum silicate suspensions. For the purposes of the present invention, therefore, particular preference is given to the stabilization of suspensions which contain 0.2 to 1% by weight of the layered silicates mentioned.
  • the suspensions can be prepared by simply mixing their constituents, the alkali metal aluminum silicates, for example as such or, if appropriate, from the preparation — already moist or in aqueous suspension — being used. It is particularly advantageous, also within the meaning of the present invention, to enter the alkali metal aluminum silicates which are still moist, for example as filter cakes, in a dispersion of the swellable, water-insoluble layer silicates. The dispersion of the layered silicates is preferably warmed somewhat, for example to 50-70 ° C.
  • alkali metal aluminum silicates which have already been dried, ie which have been freed from adhering water and which may still have bound water.
  • the layered silicate will in particular be incorporated directly into the suspension.
  • a particularly good incorporation of a dry powder or an aqueous suspension is possible. If, for example, the layered silicate is pre-swollen in water, corresponding to a weight ratio of layered silicate to water of 1:10, a softer, more flowable batch is obtained. It was also found that the tolerance to higher alkalinity is greater. Through the use of swollen layered silicate, however, water is introduced into the filter cake, so that the concentration of alkali metal aluminum silicate drops. Therefore, if pre-swollen layered silicates are used, highly concentrated aqueous suspensions are preferred.
  • the suspensions obtainable with the aid of the present invention are notable for particularly high stability. They can be pumped over a longer period of time (days to weeks), so that they make it easy to handle moist alkali metal aluminum silicates. Even after long interruptions in the pumping process, the suspensions can be pumped around again without any problems. Due to the high stability, the alkali metal aluminum silicate suspensions can also be transported sedimentation-stable in conventional tank tank wagons for several days without fear of the formation of useless or disruptive residues. There are also no phase separations. The highly concentrated alkali metal aluminum silicate suspensions are therefore in accordance with the present invention excellent as a delivery form of alkali metal aluminum silicates and for
  • the alkali metal aluminum silicate suspensions can be stored at room temperature or at a higher temperature, pumped through pipelines or transported in some other way.
  • the suspensions are usually handled at temperatures between room temperature and about 60 ° C.
  • the highly concentrated alkali metal aluminum silicate suspensions according to the invention are particularly suitable for further processing to appear dry, pourable or free-flowing products, for example for the production of powdered water softening agents and in particular washing and cleaning agents.
  • the swellable, water-insoluble sheet silicates to be used according to the invention have a binding capacity for calcium ions between about 700 and 1,000 meq / 100 g in a pH value range from about 9 to 11, according to EP-0 000 130 B1, when using these substances a detergent-active component is added, since the binding capacity of the layered silicates to be used here is about a power of 10 greater than the ion exchange capacity of natural bentonites, which is about 70 to 100 meq / 100 g.
  • the layer silicates 1 (according to the invention) and 2 (comparison) were used.
  • a further stabilizing agent a tallow fatty alcohol with 5 moles of ethylene oxide per mole of tallow fatty alcohol was used.
  • the chemical composition and important properties of the layered likate 1 and 2 are listed below:
  • Example 1 1.1 kg of the filter cake mentioned in Example 1 were analogously mixed with the layered silicate 1 in an amount of 1% by weight, based on the filter cake.
  • the data obtained analogously to Example 1 are shown in Tables 1 and 2.
  • Comparative Example 3 0.997 kg of the filter cake according to Comparative Example 1 were treated with the layered silicate 2 in an amount of 1% by weight, based on the filter cake, analogously to Comparative Example 1 and stored. The data obtained are shown in Tables 1 and 2. Comparative Example 3:
  • Comparative examples 3 and 4 which each contain the same type and amount of stabilizer (not according to the invention) with a different content of alkali metal aluminum silicate, made it clear that an increase in the concentration of alkali metal aluminum silicate involves difficulties in stabilizing the filter cake.
  • the separation of the water from the solid was checked.
  • the substance is poured into a 100 ml standing cylinder and closed with a stopper, if necessary filled up to the 100 ml calibration mark. Difficulties sometimes arise when filling the cylinders with the viscous substances (air bubbles in the vessel, inaccurate calibration mark due to smearing on the edges).
  • the suspension obtained in this way was stored for 2 weeks at room temperature and then the concentration of silicate was determined to be 49.8% by weight. In addition, it was found that the calcium binding capacity remains unchanged at 161 mg CaO / g atro.
  • Example 3 Analogously to Example 3, the filter cake mentioned in this example was produced with the layered silicate 1 in the form of a dilute suspension, the amount of layered silicate 1 being set such that it corresponded to that of Example 3.
  • the layered silicate can be introduced in the form of an aqueous suspension in a technically simple manner. However, in this procedure additional water was introduced into the system, which ultimately reduced the concentration of alkali metal aluminum silicate.

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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)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

Des suspensions de silicates d'aluminium et de métaux alcalins zéolitiques finement divisés, susceptibles d'être pompées et hautement concentrées, peuvent être stabilisées au moyen de silicates stratifiés sélectionnés insolubles dans l'eau et aptes au gonflement, et présentant un volume de gonflement particulièrement élevé.
PCT/EP1994/001731 1993-06-04 1994-05-27 Stabilisation de suspensions de silicates d'aluminium et de metaux alcalins zeolitiques finement divises Ceased WO1994029219A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19934318573 DE4318573A1 (de) 1993-06-04 1993-06-04 Stabilisierung von Suspensionen feinstteiliger zeolithischer Alkalimetallaluminiumsilikate
DEP4318573.8 1993-06-04

Publications (1)

Publication Number Publication Date
WO1994029219A1 true WO1994029219A1 (fr) 1994-12-22

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Family Applications (1)

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PCT/EP1994/001731 Ceased WO1994029219A1 (fr) 1993-06-04 1994-05-27 Stabilisation de suspensions de silicates d'aluminium et de metaux alcalins zeolitiques finement divises

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DE (1) DE4318573A1 (fr)
WO (1) WO1994029219A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2527388A1 (de) * 1974-10-10 1976-04-22 Henkel & Cie Gmbh Stabile suspensionen wasserunloeslicher, zum binden von calciumionen befaehigter silikate und deren verwendung zur herstellung von wasch- und reinigungsmitteln
DE2615698A1 (de) * 1976-04-09 1977-10-20 Henkel & Cie Gmbh Stabile suspensionen wasserunloeslicher, zum binden von calciumionen befaehigter silikate und deren verwendung zur herstellung von wasch- und reinigungsmitteln
JPS59203722A (ja) * 1983-05-04 1984-11-17 Nippon Chem Ind Co Ltd:The 懸濁安定性のよい濃厚ゼオライトスラリ−

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2527388A1 (de) * 1974-10-10 1976-04-22 Henkel & Cie Gmbh Stabile suspensionen wasserunloeslicher, zum binden von calciumionen befaehigter silikate und deren verwendung zur herstellung von wasch- und reinigungsmitteln
FR2287504A1 (fr) * 1974-10-10 1976-05-07 Henkel & Cie Gmbh Suspensions stables de silicates insolubles dans l'eau et capables de fixer les ions calcium, et leur utilisation dans la preparation de produits de lavage et de nettoyage
DE2615698A1 (de) * 1976-04-09 1977-10-20 Henkel & Cie Gmbh Stabile suspensionen wasserunloeslicher, zum binden von calciumionen befaehigter silikate und deren verwendung zur herstellung von wasch- und reinigungsmitteln
JPS59203722A (ja) * 1983-05-04 1984-11-17 Nippon Chem Ind Co Ltd:The 懸濁安定性のよい濃厚ゼオライトスラリ−

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 102, no. 12, 25 March 1985, Columbus, Ohio, US; abstract no. 97719b, page 111; *

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