EP0154291B1 - Stabilized, aqueous zeolite suspension - Google Patents
Stabilized, aqueous zeolite suspension Download PDFInfo
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- EP0154291B1 EP0154291B1 EP85102149A EP85102149A EP0154291B1 EP 0154291 B1 EP0154291 B1 EP 0154291B1 EP 85102149 A EP85102149 A EP 85102149A EP 85102149 A EP85102149 A EP 85102149A EP 0154291 B1 EP0154291 B1 EP 0154291B1
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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
- C11D3/1286—Stabilised aqueous aluminosilicate suspensions
Definitions
- the invention relates to a stabilized, aqueous suspension of synthetically produced zeolite, in particular of type A, and the use of the suspension for the production of low-phosphate and phosphate-free, optionally active chlorine-containing, powdered detergents and cleaning agents.
- type A synthetic zeolites in particular NaA zeolite
- sodium tripolyphosphate in detergents and cleaning agents has become increasingly important in recent years.
- Numerous zeolite-containing detergents with low-phosphate and phosphate-free formulations have already appeared on the market.
- the use of zeolite A as a novel water-insoluble detergent component on an industrial scale has also led to new developments in detergent and cleaning technology;
- the processing of the zeolite in the form of storage-stable, free-flowing suspensions with the highest possible zeolite content should be emphasized here.
- DE-2 527 388 A 1 describes organic, macromolecular, carboxyl and / or hydroxyl group-containing polymer compounds with molecular weights of above 1500, including those derived from natural products such as the polysaccharides. 0.5 to 6.0 percent by weight of these are required to stabilize aqueous suspensions containing more than 40 percent by weight of zeolite.
- aqueous zeolite suspensions which consist of industrially produced A-type zeolite, water and an organic macromolecular polymer compound containing carboxyl and / or hydroxyl groups and having molecular weights above 1500 as a stabilizer can be substantially improved, when the polysaccharide xanthan gum derived from a natural product is added as a stabilizer.
- the improvement consists in a much lower stabilizer content.
- the amount of the suspension stabilizer in the suspension according to the invention can be in the range from 0.05 to 0.25, preferably in the range from 0.10 to 0.15 or 0.20 percent by weight, based on the total stabilized aqueous zeolite suspension.
- suspension stabilizers for zeolite suspensions are already known from DE-3 016 433 A1, but they are very high polymer synthetically produced polyacrylamides or their copolymers.
- the zeolite content can be up to 60, preferably 40 to 55 percent by weight, based on the total stabilized aqueous zeolite suspension.
- Xanthan gum is based on Römpps Chemie-Lexikon, 7th edition (1973), pages 1355 and 1356 and Kirk-Othmer “Encyclopedia of Chemical Technology” 3rd edition (1980), volume 12, pages 62 to 64 Product understood that is known under the Anglo-Saxon name “Xanthan Gum”.
- Xanthan gum is a high molecular weight polysaccharide, i.e. H. an exocellular heteropolysaccharide with a molecular weight of about 2,000,000 and higher, which is produced by various species of Xanthomonas, for example Xanthomonas campestris. They are hydrophilic colloids. Numerous publications deal with their production by aerobic propagation and cultivation of bacteria of the genus Xanthomonas in aqueous nutrient media. The basic work is described in U.S. Patent No. 3,000,790.
- hydrophilic colloids produced by Xanthomonas campestries are polysaccharides that contain mannose, glucose, glucuronic acid, O-acetyl residues and acetyl-linked pyruvic acid. They arise as an exocellular reaction product of the bacterial species mentioned when they are aerobically grown in aqueous nutrient solutions which, in addition to the usual growth-promoting components, contain in particular water-soluble carbohydrate compounds.
- the zeolite A used according to the invention can by numerous known methods, for. B. by precipitation from solutions of sodium silicate and sodium aluminate and subsequent hydrothermal treatment or by hydrothermal treatment of destructured kaolin and sodium hydroxide.
- a number of processes have become known for the industrial production of zeolite A for detergent purposes, in which the zeolite A crystals are formed with rounded corners and edges and the formation of oversize (grit) is avoided by specific process parameters.
- the zeolite A is generally obtained as a moist filter cake with about 40 to 60% water content. Because of its thixotropic properties, this filter cake can be easily stirred and immediately mixed with the suspension stabilizer.
- the suspension according to the invention is low-viscosity at room temperature and up to 50 ° C. and can be pumped and stirred without problems for up to 7 days of storage. Even after further unlimited storage at room temperature, there is only a slight, soft sediment that can be easily stirred up again.
- the suspension according to the invention also shows excellent rheological properties at elevated temperatures, i.e. H. in the range between 50 and 80 ° C. In some technical processing equipment for zeolite suspensions for the production of powder detergents, the zeolite suspension must be warmed up, i.e. H. at temperatures above 50 ° C.
- the suspension remains stable at this temperature over a longer period of time and does not disintegrate.
- the pH of the aqueous zeolite suspension which is approximately pH 11 to 14, is not significantly changed by the neutralizing stabilizer according to the invention.
- the stabilizer used according to the invention is of course without a negative influence on the calcium binding capacity of the zeolite and although the sensitivity of xanthan gum to strongly oxidizing agents such as hypochlorite is known, no impairments were observed when using the claimed suspensions for the production of dishwasher detergents containing active chlorine.
- the suspensions according to the invention can therefore be prepared by simply mixing the constituents.
- the aqueous suspension of the zeolite which is still moist and undried from its production, is preferably used by converting the moist filter cake obtained after separating the mother liquor and washing with water into a flowable suspension by stirring. A further addition of water is generally not necessary.
- the stabilizer added according to the invention is used in the form of a pale yellow powder.
- the suspensions according to the invention can be prepared with zeolite concentrations of at least 20 percent by weight; however, for economic reasons, i.e. H. For example, to save transport and energy costs, set the water content in the suspensions as low as possible.
- the suspensions according to the invention are generally prepared at elevated temperatures, ie. H. at approx. 60 'C, which speeds up the mixing process.
- Dried zeolite powder can be used if the zeolite filter cake that is still moist from the production is not available.
- the stabilized zeolite suspensions are used as liquid raw materials according to the usual manufacturing processes for such agents. It should also be noted that the addition of the suspensions has no negative influence on the foaming behavior of the washing and cleaning agents.
- the stabilized zeolite suspensions can also be directly by conventional drying measures, for. B. by spray drying, into a powder that can be easily redispersed in water. In the production of powdered cleaning agents using the suspensions according to the invention, in particular using the spray drying method, very low-dust products are obtained which are readily wettable.
- the suspensions according to the invention are also suitable for the production of powdered dishwashing detergents.
- the suspension was assessed empirically, i.e. it is not based on precisely measurable quantities and can therefore only be made in a direct comparison within a series of tests.
- test results are shown in the following table. They show that the suspensions according to the invention were stable even at elevated temperature and could be processed without problems after storage.
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Description
Die Erfindung betrifft eine stabilisierte, wäßrige Suspension von synthetisch hergestelltem Zeolith, insbesondere des Typs A, und die Verwendung der Suspension zur Herstellung von phosphatarmen und phosphatfreien, gegebenenfalls aktivchlorhaltigen, pulverförmigen Wasch- und Reinigungsmitteln.The invention relates to a stabilized, aqueous suspension of synthetically produced zeolite, in particular of type A, and the use of the suspension for the production of low-phosphate and phosphate-free, optionally active chlorine-containing, powdered detergents and cleaning agents.
Die Verwendung der synthetischen Zeolithe des Typs A, insbesondere des Zeoliths NaA, als Waschmittel-Builder und damit als Austauschstoff für Natriumtripolyphosphat in Wasch- und Reinigungsmitteln hat in den vergangenen Jahren ständig an Bedeutung gewonnen. So sind bereits zahlreiche zeolithhaltige Waschmittel mit phosphatarmen und phosphatfreien Formulierungen auf dem Markt erschienen. Der Einsatz von Zeolith A als neuartiger wasserunlöslicher Waschmittelbestandteil in großtechnischem Maßstab hat aber auch zu Neuentwicklungen in der Wasch- und Reinigungsmitteltechnologie geführt; hervorzuheben ist hier die Verarbeitung des Zeoliths in Form von lagerstabilen, gut fließfähigen Suspensionen mit einem möglichst hohen Zeolith-Gehalt. (Zur Herstellung zeolithhaltiger Waschmittel, insbesondere unter Verwendung von stabilisierten Zeolith-Suspensionen, s. o. Koch, Seifen-Öle-Fett-Wachse, 106 (1980), Seiten 321 bis 324.)The use of type A synthetic zeolites, in particular NaA zeolite, as a detergent builder and thus as a substitute for sodium tripolyphosphate in detergents and cleaning agents has become increasingly important in recent years. Numerous zeolite-containing detergents with low-phosphate and phosphate-free formulations have already appeared on the market. The use of zeolite A as a novel water-insoluble detergent component on an industrial scale has also led to new developments in detergent and cleaning technology; The processing of the zeolite in the form of storage-stable, free-flowing suspensions with the highest possible zeolite content should be emphasized here. (For the production of detergents containing zeolite, in particular using stabilized zeolite suspensions, see above Koch, Seifen-Öle-Fett-Wwachs, 106 (1980), pages 321 to 324.)
Für die Stabilisierung von wäßrigen Zeolith-Suspensionen, die auch nach Lagerung und Transport noch fließfähig sind, und die gerührt und durch Leitungen gepumpt werden können, sind bereits eine größere Zahl von Stabilisatoren vorgeschlagen worden. Als Stabilisatoren werden beispielsweise in der DE-2 527 388 A 1 organische, makromolekulare, Carboxyl- und/oder Hydroxylgruppen aufweisende Polymerverbindungen mit Molgewichten von oberhalb 1500, darunter solche, die von Naturprodukten wie den Polysacchariden abgeleitet werden, beschrieben. Man benötigt davon 0,5 bis 6,0 Gewichtsprozent zum Stabilisieren von mehr als 40 Gewichtsprozent Zeolith enthaltenden wäßrigen Suspensionen.A large number of stabilizers have already been proposed for the stabilization of aqueous zeolite suspensions which are still flowable even after storage and transport and which can be stirred and pumped through lines. As stabilizers, for example, DE-2 527 388 A 1 describes organic, macromolecular, carboxyl and / or hydroxyl group-containing polymer compounds with molecular weights of above 1500, including those derived from natural products such as the polysaccharides. 0.5 to 6.0 percent by weight of these are required to stabilize aqueous suspensions containing more than 40 percent by weight of zeolite.
Es wurde nun gefunden, daß sich stabilisierte wäßrige Zeolith-Suspensionen, die aus großtechnisch hergestelltem Zeolith vom A-Typ, Wasser und einer organischen makromolekularen, Carboxyl- und/oder Hydroxylgruppen aufweisenden Polymerverbindung mit Molgewichten von oberhalb 1500 als Stabilisator bestehen, wesentlich verbessern lassen, wenn als Stabilisator das von einem Naturprodukt abgeleitete Polysaccharid Xanthangummi zugesetzt wird. Die Verbesserung besteht in einem wesentlich geringeren Stabilisatorgehalt.It has now been found that stabilized aqueous zeolite suspensions which consist of industrially produced A-type zeolite, water and an organic macromolecular polymer compound containing carboxyl and / or hydroxyl groups and having molecular weights above 1500 as a stabilizer can be substantially improved, when the polysaccharide xanthan gum derived from a natural product is added as a stabilizer. The improvement consists in a much lower stabilizer content.
Die Menge des Suspensionsstabilisators kann in der erfindungsgemäßen Suspension im Bereich von 0,05 bis 0,25, vorzugsweise im Bereich von 0,10 bis 0,15 oder 0,20 Gewichtsprozent, bezogen auf die gesamte stabilisierte wäßrige Zeolith-Suspension liegen.The amount of the suspension stabilizer in the suspension according to the invention can be in the range from 0.05 to 0.25, preferably in the range from 0.10 to 0.15 or 0.20 percent by weight, based on the total stabilized aqueous zeolite suspension.
Derartig geringe Mengen an Suspensionsstabilisatoren für Zeolith-Suspensionen sind zwar schon aus der DE-3 016 433 A 1 bekannt, jedoch handelt es sich dort um sehr hochpolymere synthetisch hergestellte Polyacrylamide oder deren Copolymere.Such small amounts of suspension stabilizers for zeolite suspensions are already known from DE-3 016 433 A1, but they are very high polymer synthetically produced polyacrylamides or their copolymers.
Der Zeolithgehalt kann bis zu 60, vorzugsweise 40 bis 55 Gewichtsprozent, bezogen auf die gesamte stabilisierte wäßrige Zeolith-Suspension betragen.The zeolite content can be up to 60, preferably 40 to 55 percent by weight, based on the total stabilized aqueous zeolite suspension.
Unter "Xanthangummi" wird hier in Anlehnung an Römpps Chemie-Lexikon, 7. Auflage (1973), Seiten 1355 und 1356 und Kirk-Othmer "Encyclopedia of Chemical Technology" 3. Auflage (1980), Band 12, Seiten 62 bis 64 ein Produkt verstanden, das unter der angelsächsischen Bezeichnung "Xanthan Gum" bekannt ist. Xanthangummi ist ein hochmolekulares Polysaccharid, d. h. ein exozellulares Heteropolysaccharid mit einem Molgewicht von etwa 2 000 000 und höher, das von verschiedenen Xanthomonasarten, zum Beispiel Xanthomonas campestris, produziert wird. Es sind hydrophile Kolloide. Zahlreiche Veröffentlichungen befassen sich mit ihrer Herstellung durch die aerobe Vermehrung und Züchtung von Bakterien der Gattung Xanthomonas in wäßrigen Nährmedien. Die grundlegenden Arbeiten sind in der US-PS-3 000 790 beschrieben."Xanthan gum" is based on Römpps Chemie-Lexikon, 7th edition (1973), pages 1355 and 1356 and Kirk-Othmer "Encyclopedia of Chemical Technology" 3rd edition (1980), volume 12, pages 62 to 64 Product understood that is known under the Anglo-Saxon name "Xanthan Gum". Xanthan gum is a high molecular weight polysaccharide, i.e. H. an exocellular heteropolysaccharide with a molecular weight of about 2,000,000 and higher, which is produced by various species of Xanthomonas, for example Xanthomonas campestris. They are hydrophilic colloids. Numerous publications deal with their production by aerobic propagation and cultivation of bacteria of the genus Xanthomonas in aqueous nutrient media. The basic work is described in U.S. Patent No. 3,000,790.
Die von Xanthomonas campestries produzierten hydrophilen Kolloide sind Polysaccharide, die Mannose, Glucose, Glucuronsäure, O-Acetyl-Reste und acetyl-verknüpfte Brenztraubensäure enthalten. Sie entstehen als exozelluläres Reaktionsprodukt der genannten Bakterienarten bei deren aerober Züchtung in wäßrigen Nährlösungen, die neben den üblichen wachstumsfördernden Komponenten insbesondere wasserlösliche Kohlenhydratverbindungen enthalten.The hydrophilic colloids produced by Xanthomonas campestries are polysaccharides that contain mannose, glucose, glucuronic acid, O-acetyl residues and acetyl-linked pyruvic acid. They arise as an exocellular reaction product of the bacterial species mentioned when they are aerobically grown in aqueous nutrient solutions which, in addition to the usual growth-promoting components, contain in particular water-soluble carbohydrate compounds.
Derartige Produkte sind handelsüblich und werden beispielsweise von der Firma Kelco Comp. Oklahoma /USA unter dem Namen Kelzan• vertrieben. Dafür wird folgende Formel angegeben:
Der erfindungsgemäß verwendete Zeolith A kann nach zahlreichen bekannten Verfahren, z. B. durch Fällung aus Lösungen von Natriumsilikat und Natriumaluminat und anschließender hydrothermaler Behandlung bzw. durch hydrothermale Behandlung von destrukturiertem Kaolin und Natriumhydroxid hergestellt werden. Für die großtechnische Herstellung von Zeolith A für Waschmittelzwecke sind eine Reihe von Verfahren bekannt geworden, bei denen die Zeolith-A-Kristalle mit abgerundeten Ecken und Kanten anfallen und die Bildung von Uberkorn (Grit) durch spezifische Verfahrensparameter vermieden wird. Derartige Verfahren werden beispielsweise in den deutschen Offenlegungsschriften 2 447 021, 2 517 218, 2 533 614, 2651 419, 2 651 420, 2 651 436, 2 651 445, 2 651 485, 2 704 310, 2 734 296, 2 941 636, 3 011 834, 3 021 370 beschrieben.The zeolite A used according to the invention can by numerous known methods, for. B. by precipitation from solutions of sodium silicate and sodium aluminate and subsequent hydrothermal treatment or by hydrothermal treatment of destructured kaolin and sodium hydroxide. A number of processes have become known for the industrial production of zeolite A for detergent purposes, in which the zeolite A crystals are formed with rounded corners and edges and the formation of oversize (grit) is avoided by specific process parameters. Such methods are described, for example, in German Offenlegungsschriften 2,447,021, 2,517,218, 2,533,614, 2,651,419, 2,651,420, 2,651,436, 2,651,445, 2,651,485, 2,704,310, 2,734,296, 2,941,636 , 3,011,834, 3,021,370.
Bei der Synthese fällt der Zeolith A im allgemeinen als feuchter Filterkuchen mit etwa 40 bis 60 % Wassergehalt an. Wegen seiner thixotropen Eigenschaften läßt sich dieser Filterkuchen leicht verrühren und dabei unmittelbar mit dem Suspensionsstabilisator versetzen.In the synthesis, the zeolite A is generally obtained as a moist filter cake with about 40 to 60% water content. Because of its thixotropic properties, this filter cake can be easily stirred and immediately mixed with the suspension stabilizer.
Die erfindungsgemäße Suspension ist bei Raumtemperatur und bis zu 50°C niedrig-viskos und kann ohne Probleme bis zu 7 Tagen Lagerung gepumpt und gerührt werden. Auch nach weiterer unbegrenzter Lagerung bei Raumtemperatur entsteht nur ein geringer weicher Bodensatz, der ohne weiteres wieder aufgerührt werden kann. Zusätzlich zu den guten Stabilitätseigenschaften bei Raumtemperatur zeigt die erfindungsgemäße Suspension aber auch ausgezeichnete rheologische Eigenschaften bei erhöhten Temperaturen, d. h. im Bereich zwischen 50 und 80°C. Bei manchen technischen Verarbeitungseinrichtungen für Zeolith-Suspensionen zur Herstellung von pulverförmigen Reinigungsmitteln muß die Zeolith-Suspension im angewärmten Zustand, d. h. bei Temperaturen über 50° C, verwendet werden. Entscheidend für die Brauchbarkeit ist es dann, daß die Suspension bei dieser Temperatur über einen längeren Zeitraum stabil bleibt und nicht zerfällt. Durch den erfindungsgemäßen neutral reagierenden Stabilisator wird außerdem der pH-Wert der wäßrigen Zeolith-Suspension, der bei ungefähr pH 11 bis 14 liegt, nicht wesentlich verändert. Der erfindungsgemäß eingesetzte Stabilisator ist selbstverständlich ohne negativen Einfluß auf das Calciumbindevermögen des Zeoliths und obgleich die Empfindlichkeit von Xanthangummi gegen stark oxydierende Mittel wie Hypochlorite bekannt ist, konnten beim Einsatz der beanspruchten Suspensionen zur Herstellung von aktivchlorhaltigen Geschirrspülmitteln keinerlei Beeinträchtigungen beobachtet werden.The suspension according to the invention is low-viscosity at room temperature and up to 50 ° C. and can be pumped and stirred without problems for up to 7 days of storage. Even after further unlimited storage at room temperature, there is only a slight, soft sediment that can be easily stirred up again. In addition to the good stability properties at room temperature, the suspension according to the invention also shows excellent rheological properties at elevated temperatures, i.e. H. in the range between 50 and 80 ° C. In some technical processing equipment for zeolite suspensions for the production of powder detergents, the zeolite suspension must be warmed up, i.e. H. at temperatures above 50 ° C. It is then decisive for the usability that the suspension remains stable at this temperature over a longer period of time and does not disintegrate. In addition, the pH of the aqueous zeolite suspension, which is approximately pH 11 to 14, is not significantly changed by the neutralizing stabilizer according to the invention. The stabilizer used according to the invention is of course without a negative influence on the calcium binding capacity of the zeolite and although the sensitivity of xanthan gum to strongly oxidizing agents such as hypochlorite is known, no impairments were observed when using the claimed suspensions for the production of dishwasher detergents containing active chlorine.
Die erfindungsgemäßen Suspensionen lassen sich also durch einfaches Vermischen der Bestandteile herstellen. In der Praxis benutzt man vorzugsweise die wäßrige Suspension des von seiner Herstellung noch feuchten und ungetrockneten Zeoliths, indem man den nach dem Abtrennen der Mutterlauge und Waschen mit Wasser erhaltenen feuchten Filterkuchen durch Verrühren in eine fließfähige Suspension verwandelt. Dabei ist ein weiterer Wasserzusatz im allgemeinen nicht erforderlich. Der erfindungsgemäß zugesetzte Stabilisator wird in Form eines schwach gelben Pulvers eingesetzt. Die erfindungsgemäßen Suspensionen lassen sich mit Zeolith-Konzentrationen von wenigstens 20 Gewichtsprozent herstellen; allerdings wird man aus ökonomischen Gründen, d. h. um zum Beispiel Transport- und Energiekosten einzusparen, den Wassergehalt in den Suspensionen möglichst gering einstellen. So wird man bestrebt sein, den Zeolith-Gehalt auf Werte über 40 Gewichtsprozent, ja möglichst auf Werte über 50 Gewichtsprozent einzustellen. Bei der Herstellung der erfindungsgemäßen Suspensionen arbeitet man im allgemeinen bei erhöhten Temperaturen, d. h. bei ca. 60' C, wodurch der Mischungsvorgang beschleunigt wird.The suspensions according to the invention can therefore be prepared by simply mixing the constituents. In practice, the aqueous suspension of the zeolite, which is still moist and undried from its production, is preferably used by converting the moist filter cake obtained after separating the mother liquor and washing with water into a flowable suspension by stirring. A further addition of water is generally not necessary. The stabilizer added according to the invention is used in the form of a pale yellow powder. The suspensions according to the invention can be prepared with zeolite concentrations of at least 20 percent by weight; however, for economic reasons, i.e. H. For example, to save transport and energy costs, set the water content in the suspensions as low as possible. So one will endeavor to set the zeolite content to values above 40 percent by weight, if possible to values above 50 percent by weight. The suspensions according to the invention are generally prepared at elevated temperatures, ie. H. at approx. 60 'C, which speeds up the mixing process.
Selbstverständlich kann für die Herstellung der erfindungsgemäßen Suspensionen auch ein bereits getrocknetes Zeolith-Pulver verwendet werden, wenn der von der Herstellung noch feuchte Zeolith-Filterkuchen nicht zur Verfügung steht.Of course, one can already be used to prepare the suspensions according to the invention Dried zeolite powder can be used if the zeolite filter cake that is still moist from the production is not available.
Für die Weiterverarbeitung zu Wasch- und Reinigungsmitteln werden die stabilisierten Zeolith-Suspensionen als flüssiger Rohstoff nach den üblichen Herstellungsverfahren für derartige Mittel eingesetzt. Zu bemerken ist noch, daß der Zusatz der Suspensionen das Schaumverhalten der Wasch- und Reinigungsmittel in keiner Weise negativ beeinflußt. Die stabilisierten Zeolith-Suspensionen können aber auch direkt durch übliche Trocknungsmaßnahmen, z. B. durch Sprühtrocknung, in ein Pulver, das leicht wieder in Wasser dispergiert werden kann, übergeführt werden. Bei der Herstellung von pulverförmigen Reinigungsmitteln unter Verwendung der erfindungsgemäßen Suspensionen, insbesondere nach der Methode der Zerstäubungstrocknung, werden sehr staubarme Produkte erhalten, die gut benetzbar sind. Die erfindungsgemäßen Suspensionen sind auch zur Herstellung von pulverförmigen Geschirr-Reinigungsmitteln geeignet.For further processing into detergents and cleaning agents, the stabilized zeolite suspensions are used as liquid raw materials according to the usual manufacturing processes for such agents. It should also be noted that the addition of the suspensions has no negative influence on the foaming behavior of the washing and cleaning agents. The stabilized zeolite suspensions can also be directly by conventional drying measures, for. B. by spray drying, into a powder that can be easily redispersed in water. In the production of powdered cleaning agents using the suspensions according to the invention, in particular using the spray drying method, very low-dust products are obtained which are readily wettable. The suspensions according to the invention are also suitable for the production of powdered dishwashing detergents.
Zur Herstellung der stabilisierten Suspensionen wurde ein feuchter Filterkuchen von Zeolith NaA mit den folgenden Eigenschaften verwendet:
- Gehalt an Zeolith NaA, bezogen auf die wasserfreie Substanz (Glührückstand nach einstündigem Erhitzen auf 800° C): 47,0 %;
- Calciumbindevermögen: 155 bis 157 mg CaO/g wasserfreier Substanz (bestimmt nach der unten angegebenen Methode); Teilchengrößenbestimmung (Coulter Counter, Volumenverteilung): 100 % kleiner als 15 µm; 98,1 % kleiner als 10 µm; 79 % kleiner als 5 µm; 36,5 kleiner als 3 µm; mittlerer Teilchendurchmesser 3,9 µm;
- Alkaligehalt: 0,35 Gew.-%.
- Zeolite NaA content, based on the anhydrous substance (residue on ignition after heating at 800 ° C. for one hour): 47.0%;
- Calcium binding capacity: 155 to 157 mg CaO / g anhydrous substance (determined according to the method given below); Particle size determination (Coulter Counter, volume distribution): 100% smaller than 15 µm; 98.1% smaller than 10 µm; 79% smaller than 5 µm; 36.5 less than 3 µm; average particle diameter 3.9 µm;
- Alkali content: 0.35% by weight.
Es wurde 1 I einer wäßrigen, 0,594 CaCI2 (entsprechend 300 mg CaO/1 = 30 °d) enthaltenden Lösung mit verdünnter Natronlauge auf einen pH-Wert von 10 eingestellt und unter Rühren mit 2,13 g des Filterkuchens ( - 1,00 g wasserfreier Zeolith A) versetzt. Die Suspension wurde anschließend 10 Minuten lang bei einer Raumtemperatur von 22 ± 2°C gerührt. Nach dem Abfiltrieren des Zeoliths wurde die Resthärte X im Filtrat durch komplexometrische Titration mit Ethylendiamintetraessigsäure bestimmt; das Calciumbindevermögen in mg CaO/g errechnet sich dann nach der Formel: (30 - X) - 10.1 l of an aqueous solution containing 0.594 CaCl 2 (corresponding to 300 mg CaO / 1 = 30 ° d) was adjusted to a pH of 10 using dilute sodium hydroxide solution and, with stirring, 2.13 g of the filter cake (- 1.00 g of anhydrous zeolite A). The suspension was then stirred for 10 minutes at a room temperature of 22 ± 2 ° C. After the zeolite had been filtered off, the residual hardness X in the filtrate was determined by complexometric titration with ethylenediaminetetraacetic acid; the calcium binding capacity in mg CaO / g is then calculated using the formula: (30 - X) - 10.
Es wurden jeweils Ansätze von 2 kg des feuchten Zeolith-A-Filterkuchens (ca. 50 Gew.-% Wasser) bei 60: C gerührt. Die Rührintensität eines MIG-Rührers betrug 500 Umdrehungen pro Minute. Unter diesen Bedingungen wurde der Filterkuchen zu einer gut rührbaren Suspension. In diese Suspension wurde der Stabilisator langsam eingetragen. Nach etwa 10 Minuten wurden homogene stabilisatorhaltige Suspensionen erhalten, ohne daß Klumpenbildung auftrat. Anschließend wurden mittels eines Brookfield-Viskosimeters mit 20 Spindelumdrehungen pro Minute die Viskositäten m Pa.s bei 20 und bei 50°C bestimmt. Außerdem wurden die Suspensionen nach den Sedimentationskriterien Bodensatzbildung und Bodensatzkonsistenz beurteilt.Batches of 2 kg of the moist zeolite A filter cake (approx. 50% by weight of water) were stirred at 60 : C. The stirring intensity of a MIG stirrer was 500 revolutions per minute. Under these conditions the filter cake became an easily stirrable suspension. The stabilizer was slowly introduced into this suspension. After about 10 minutes, homogeneous suspensions containing stabilizer were obtained without the formation of lumps. The viscosities m Pa.s at 20 and at 50 ° C. were then determined using a Brookfield viscometer with 20 spindle revolutions per minute. In addition, the suspensions were assessed according to the sedimentation criteria of sediment formation and consistency.
Die Beurteilung der Suspension erfolgte empirisch, beruht also nicht auf exakt meßbaren Größen und kann daher jeweils nur im direkten Vergleich innerhalb einer Versuchsreihe vorgenommen werden.The suspension was assessed empirically, i.e. it is not based on precisely measurable quantities and can therefore only be made in a direct comparison within a series of tests.
Verwendete man übrigens zur Herstellung der Suspensionen anstelle von Zeolith A Gemische aus Zeolith A und Hydrosodalith, z. B. im Verhältnis 10 : 1 bis 1 : 1, oder Gemische aus Zeolith A und Zeolith X, dann wurden vergleichbare Stabilisitätseigenschaften beobachtet.Incidentally, was used to prepare the suspensions instead of zeolite A mixtures of zeolite A and hydrosodalite, eg. B. in a ratio of 10: 1 to 1: 1, or mixtures of zeolite A and zeolite X, then comparable stability properties were observed.
Als Behälter für den Lagerversuch wurden 250 ml-Schraubdeckelgläser verwendet. Die Füllhöhe der frisch eingefüllten Suspension wurde gleich 100 % gesetzt. Nach der Lagerzeit wurde die Höhe der klaren Flüssigkeitszone über der Suspension gemessen und das Sedimentationsverhalten in "% Suspension" ausgedrückt. Dementsprechend bedeuten "100 % Suspension", daß sich keine klare Flüssigkeitsphase gebildet hat.250 ml screw-top jars were used as containers for the storage test. The filling level of the freshly filled suspension was set to 100%. After the storage period, the height of the clear liquid zone above the suspension was measured and the sedimentation behavior was expressed in "% suspension". Accordingly, "100% suspension" means that no clear liquid phase has formed.
In den gleichen Gefäßen wurde außerdem die Konsistenz des Bodensatzes, der sich nach der Lagerung gebildet hatte, durch Abtasten mit einem Glasstab geprüft. Bei der Beurteilung des Bodensatzes kommt es nicht nur darauf an, ob und in welchem Ausmaß sich ein Bodensatz gebildet hat, sondern auch ob sich dieser Bodensatz leicht oder schwer oder gar nicht wieder aufrühren läßt. Es wurden deshalb die folgenden Benotungen gewählt:
- BF = kein Bodensatz in der Suspension;
- Bw = Bodensatzbildung mit weicher Konsistenz, leicht aufrührbar;
- BM = Bodensatzbildung mit mittlerer Konsistenz, schwer aufrührbar;
- BH = Bodensatzbildung mit harter Konsistenz, nicht aufrührbar.
- B F = no sediment in the suspension;
- B w = sediment formation with a soft consistency, easy to stir;
- B M = sediment formation with medium consistency, difficult to stir;
- W H = sediment formation with hard consistency, cannot be stirred.
Die Versuchsergebnisse werden in der folgenden Tabelle wiedergegeben. Sie zeigen, daß die erfindungsgemäßen Suspensionen auch bei erhöhter Temperatur stabil waren und nach Lagerung einwandfrei weiterverarbeitet werden konnten.The test results are shown in the following table. They show that the suspensions according to the invention were stable even at elevated temperature and could be processed without problems after storage.
Claims (4)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19843408040 DE3408040A1 (en) | 1984-03-05 | 1984-03-05 | STABILIZED, AQUEOUS ZEOLITE SUSPENSION |
| DE3408040 | 1984-03-05 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0154291A2 EP0154291A2 (en) | 1985-09-11 |
| EP0154291A3 EP0154291A3 (en) | 1988-02-03 |
| EP0154291B1 true EP0154291B1 (en) | 1989-08-23 |
Family
ID=6229609
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP85102149A Expired EP0154291B1 (en) | 1984-03-05 | 1985-02-27 | Stabilized, aqueous zeolite suspension |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0154291B1 (en) |
| JP (1) | JPS60204615A (en) |
| DE (2) | DE3408040A1 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0217440A1 (en) * | 1985-09-27 | 1987-04-08 | The Procter & Gamble Company | Stable aqueous pharmaceutical suspensions |
| JPS62167216A (en) * | 1986-01-17 | 1987-07-23 | Lion Corp | Aqueous zeolite suspension |
| DE3607673A1 (en) * | 1986-03-08 | 1987-09-10 | Henkel Kgaa | POWDERED, ACTIVE CHLORINE, MACHINE APPLICABLE DISHWASHER |
| GB2200900A (en) * | 1987-02-16 | 1988-08-17 | Ecc Int Ltd | Aqueous suspensions of gypsum |
| FR2628341B1 (en) * | 1988-03-09 | 1991-06-14 | Rhone Poulenc Chimie | STABLE AQUEOUS SUSPENSION OF SILICO-ALUMINATES |
| EP0352358A1 (en) * | 1988-07-29 | 1990-01-31 | AUSIDET S.p.A. | Stable aqueous suspensions of inorganic silica-based materials insoluble in water |
| FR2652818B1 (en) * | 1989-10-09 | 1994-04-01 | Rhone Poulenc Chimie | ZEOLITE SUSPENSION COMPRISING A SILICONE RESIN. |
| US5476610A (en) * | 1991-07-22 | 1995-12-19 | Henkel Kommanditgesellschaft Auf Aktien | Process for stabilizing aqueous zeolite suspensions |
| DE4203789A1 (en) * | 1992-02-10 | 1993-08-12 | Henkel Kgaa | METHOD FOR STABILIZING AQUEOUS ZEOLITE SUSPENSIONS |
| US5800603A (en) * | 1996-03-25 | 1998-09-01 | Eka Chemicals Ab | Zeolite dispersion |
| DE10056362A1 (en) * | 2000-11-14 | 2002-05-29 | Thomas Bein | Synthesis and stabilization of nanoscale zeolite particles |
| DE10116210A1 (en) * | 2001-03-31 | 2002-09-05 | Henkel Kgaa | Particulate zeolite composition useful in detergent manufacture has high zeolite content and defined particle size |
| CN112408728A (en) * | 2019-08-20 | 2021-02-26 | 广西金桂浆纸业有限公司 | Treatment method of alkali recovery green mud and in-furnace desulfurization method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT335035B (en) * | 1974-10-10 | 1977-02-25 | Henkel & Cie Gmbh | STABLE SUSPENSIONS OF WATER-INSOLUBLE, SILICATES CAPABLE OF BINDING CALCIUMIONS AND THEIR USE FOR THE MANUFACTURE OF DETERGENTS AND DETERGENTS |
| CA1132357A (en) * | 1977-03-18 | 1982-09-28 | Gianfranco Mecatti | Suspension medium |
| DE3210480C2 (en) * | 1982-03-22 | 1994-07-14 | Mizusawa Industrial Chem | Process for the preparation of zeolite slurries with good static and dynamic stability |
| DE3301577A1 (en) * | 1983-01-19 | 1984-07-19 | Henkel KGaA, 4000 Düsseldorf | DETERGENT AND CLEANING AGENT |
-
1984
- 1984-03-05 DE DE19843408040 patent/DE3408040A1/en not_active Ceased
-
1985
- 1985-02-27 DE DE8585102149T patent/DE3572509D1/en not_active Expired
- 1985-02-27 EP EP85102149A patent/EP0154291B1/en not_active Expired
- 1985-03-04 JP JP60041382A patent/JPS60204615A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE3408040A1 (en) | 1985-09-12 |
| EP0154291A3 (en) | 1988-02-03 |
| DE3572509D1 (en) | 1989-09-28 |
| EP0154291A2 (en) | 1985-09-11 |
| JPH0429604B2 (en) | 1992-05-19 |
| JPS60204615A (en) | 1985-10-16 |
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