EP0442923A1 - Process for producing high-density zeolite-containing granules - Google Patents

Process for producing high-density zeolite-containing granules

Info

Publication number
EP0442923A1
EP0442923A1 EP89912426A EP89912426A EP0442923A1 EP 0442923 A1 EP0442923 A1 EP 0442923A1 EP 89912426 A EP89912426 A EP 89912426A EP 89912426 A EP89912426 A EP 89912426A EP 0442923 A1 EP0442923 A1 EP 0442923A1
Authority
EP
European Patent Office
Prior art keywords
weight
zeolite
water
granules
parts
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.)
Pending
Application number
EP89912426A
Other languages
German (de)
French (fr)
Inventor
Jochen Jacobs
Ulrich Jahnke
Franz-Josef Carduck
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 EP0442923A1 publication Critical patent/EP0442923A1/en
Pending legal-status Critical Current

Links

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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • 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
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • 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 present invention relates to a new production process for zeolite-containing granules with a pronounced adsorption capacity for liquid to waxy active substances.
  • the granules are characterized by a high density, i. H. a bulk density between 750 and 1 000 g / 1 (grams per liter) and are suitable for use in detergents and cleaning agents.
  • DE-A-33 16 513 discloses granules containing fine powdered zeolites and salts of (co) polymeric carboxylic acids produced by spray drying aqueous slurries. They have a bulk density of only 560 - 610 g / 1. A teaching of the content that such granules can be used as carrier material for liquid to waxy detergent components is not to be found in this document.
  • DE-A-34 44 960 describes granules which contain zeolites, salts of (co) polymeric carboxylic acids and additionally small amounts of alkali metal silicates and serve as carrier material for liquid detergent components, in particular nonionics.
  • the bulk density of these granules produced by spray drying is a maximum of 700 g / 1 and is preferably between 500 and 650 g / 1.
  • Document EP-A-149 264 teaches that commercially available spray-dried zeolites or mixtures thereof with inorganic salts, such as sodium sulfate, can be used for the same purpose.
  • the bulk density of this spray pro products is in the range of 400 - 600 g / 1.
  • From EP-A-21 267 agglomerates containing zeolites and alkali metal silicates are known which have a bulk density of 300-700 g / l.
  • a dry premix of zeolite and alkali metal silicate (mixing ratio 1: 1 to 1: 8) is sprayed with water in a granulator and agglomerated, whereupon the excess water to a residual proportion of less than 5% by weight. -% is removed by drying.
  • the granules are also suitable for adsorbing liquid detergent components, in particular from Nonionics.
  • the main disadvantage is their high content of strongly alkaline-reacting alkali silicates, which severely limits their use in neutral to weakly alkaline-reacting detergents suitable for sensitive textiles and furthermore reduces the proportion of zeolite capable of ion exchange.
  • bulk densities of over 700 g / 1 cannot be achieved.
  • the invention relates to a process for the production of granules containing fine crystalline zeolite, sodium or potassium salts of polymeric or copolymeric carboxylic acids and water, characterized in that (a) in a first mixing stage a homogeneous, powdery mixture of zeolite and the salt of the (co) polymeric carboxylic acid, agglomerating this mixture (b) in a second mixing and granulation stage and (c) the agglomerate obtained until a free-flowing mixture is reached Granules with a bulk density of 750-1000 g / 1 after-rocket.
  • the granules which are produced by the process according to the invention generally contain (based on anhydrous substance) 60-80% by weight of zeolite, 2-15% by weight of a sodium salt of (co) polymeric carboxylic acids and 15 25% by weight of water, including the water bound to the zeolite.
  • water-free zeolite is understood to mean a sodium zeolite dewatered at the annealing temperature.
  • Granules with a content of 62-75% by weight, in particular 65-70% by weight of zeolite (calculated as anhydrous) and 4-12% by weight, in particular 5-10% by weight of Na salt (co- ) polymeric carboxylic acids (water content: difference up to 100% by weight) are preferred.
  • the granules For the production of the granules, it is expedient to start from spray-dried, finely powdered zeolite, which generally has a water content of 17-25% by weight, preferably 19-22% by weight.
  • This water includes constitutional water and adhering moisture.
  • 70-95 parts by weight, preferably 75-93 parts by weight and in particular 80-90 parts by weight of this water-containing zeolite are mixed in a mixing device with 2-12 parts by weight, preferably 4-10 parts by weight. parts and in particular 5 - 8 parts by weight of the sodium salt of the polymeric or copoly eric carboxylic acid combined into a homogeneous powder mixture.
  • agglomeration 15-25 parts by weight, preferably 18-23 parts by weight of water are mixed in with constant further mixing.
  • the water is preferably sprayed onto the powder mixture kept in motion by means of nozzles and mechanically processed until granular agglomerates are formed.
  • the still moist but already free-flowing agglomerate is then dried, for example with hot flowing air or with hot combustion gases, the drying being carried out until the water added in the granulation stage to a proportion of less than 5% by weight. divide, preferably less than 3 parts by weight.
  • further water components that were originally introduced with the zeolite or a (co) polymeric salt which is not used anhydrous can be removed during drying.
  • Such "over-dried" granules can have application-technical advantages, for example when added to detergents which contain active ingredients which are sensitive to moisture.
  • the dewatering of the zeolite should preferably not be driven below a water content of 18% by weight in order to avoid a reduction in activity.
  • the water content of the granules is expediently in a range in which the water-binding capacity of the zeolite is largely saturated, ie in which the zeolite has a total water content of 19-22% by weight (including constitutional water).
  • Suitable zeolites are those of the zeolite A type. Mixtures of zeolite NaA and NaX can also be used, the proportion of the zeolite NaX in such mixtures advantageously being less than 30%, in particular less than 20%. Suitable zeolites have no particles larger than 30 ⁇ m and consist of at least 80% of particles smaller than 10 ⁇ m. Their average particle size (volume distribution, measurement method: Coulter Counter) is 1 to 10 ⁇ m. Their calcium binding capacity, which is determined in accordance with DE 24 12 837 and is based on anhydrous substance, is in the range from 100 to 200 mg CaO / g.
  • Examples of the homopolymeric and / or copolymeric carboxylic acids contained in the granules, in the present case as water-soluble salts, of which the sodium salts are preferred, are polyacrylic acid, polymethacrylic acid and polymaleic acid, copolymers of acrylic acid with methacrylic acid or maleic acid with vinyl ethers, such as vinyl methyl ether or vinyl ethyl ether , further with vinyl esters, such as vinyl acetate or vinyl propionate, Acryla id, Methacryla id and with ethylene, propylene or styrene.
  • copolymeric acids in which one of the components has no acid function, the proportion thereof in the interest of sufficient water solubility is not more than 50 mol percent, preferably less than 30 mol percent.
  • Copolymers of acrylic acid or methacrylic acid with maleic acid as described in more detail in EP 25 551 B1, for example, have proven to be particularly suitable. These are copolymers which contain 50 to 90% by weight of acrylic acid or methacrylic acid and 50 to 10% by weight of maleic acid. Copolymers in which 45 to 85% by weight of acrylic acid and 55 to 15% by weight of maleic acid are present are particularly preferred.
  • the molecular weight of the homo- or copolymeric polycarboxylates is generally 2,000 to 150,000, preferably 5,000 to 100,000.
  • salts of (co) polymeric carboxylic acids in powder form often contain 5 to 15% by weight of moisture. This proportion of water is included in the calculation of the water balance, or the amount of water introduced into the pelletizing stage can be reduced by this proportion.
  • the proportion of salts in the preparation of the compositions or in the composition of the finished granules is based on anhydrous salt.
  • the granulation can be carried out batchwise or continuously in conventional mixing and granulating devices.
  • B. pelletizers which consist of a horizontally arranged or inclined to the horizontal, cylindrical containers, in the longitudinal axis of which a shaft equipped with mixing tools and conveying blades rotates. The water can be supplied by spray nozzles mounted in the wall or on the hollow shaft.
  • two mixers connected in series can be used, the dry premix being produced in the first mixer and the pelletizing being carried out with the addition of water in the second mixer.
  • Continuous work is also possible in a mixer, the powder streams being combined and homogenized in a first mixing section and the mixture being treated with water and agglomerating in a subsequent mixing section in a subsequent mixing section.
  • the drying can be carried out by introducing hot gases in a third mixing section z.
  • coarse and fine particles are sieved. The coarse fractions are ground and mixed into the product, fine fractions or dust are returned to the granulation.
  • the granules have a bulk density of 750-1000 g / 1, usually that of 800-950 g / 1. Due to their tight packing and their small pore volume, their absorption capacity for liquid or pasty detergent components, especially nonionics, is somewhat reduced compared to specifically lighter carrier grains, but is still 15 to a maximum of 20% by weight without any appreciable impairment of the free-flowing properties. This In view of the high packing density, the surprisingly high adsorption capacity is completely sufficient for the usual fields of application, in particular for use as a mixture component in detergents and cleaning agents.
  • the granules can be impregnated with any liquid or paste-like or fat-like detergent constituents which cannot be incorporated into conventional powdery or granular detergents or cleaning agents in other ways or only with a loss of activity.
  • foam inhibitors in particular paraffin hydrocarbons, silicones, silicone resins and bis-acylalkylenediamines derived from long-chain fatty acids and mixtures thereof.
  • Further adsorbable active ingredients are fatty acid alkylolamides and cationic plasticizers, such as quaternary ammonium salts containing long-chain fatty residues, and also fat-dissolving solvents, such as terpenes.
  • the granules are preferably used as carrier grains for nonionic surfactants. This is another aspect of the invention.
  • Suitable nonionic surfactants are alkoxylation products with 10 to 20 carbon atoms in the hydrophobic radical and 3 to 20 glycol ether groups. These include ethoxylation products of alcohols, vicinal diols, amines, thio alcohols, fatty acid amides and fatty acids. Alkylphenol polyglycol ethers with 5 to 12 carbon atoms in the alkyl radical and 3 to 10 ethylene glycol ether groups are also useful. Block polymers of ethylene oxide and propylene oxide, which are commercially available under the name Pluronics, are also suitable. Furthermore, alkyl glycosides or alkyl polyglycosides as well as their mixtures with the ⁇ thoxylation products mentioned can be used »
  • Preferred nonionics which can be adsorbed on the granulate and together with it are in the form of a free-flowing mixture, are derived from alcohols having 12 to 18 carbon atoms which are saturated or olefinically unsaturated, linear or methyl in 2-position branches (oxo residue) can be.
  • Their reaction products with ethylene oxide (EO) or propylene oxide (PO) are water-soluble or water-dispersible mixtures of compounds with different degrees of alkoxylation, the number of EO or PO groups given below being statistical Corresponds to the mean.
  • ethoxylated fatty alcohols examples include C12-I8 "coconut alcohols with 3 to 12 EO, Ci5_i8 ⁇ tallow alcohol with 4 to 16 EO, oleyl alcohol with 4 to 12 EO as well as ethoxylation products of appropriate chain and EO distribution available from other native fatty alcohol mixtures.
  • Aus In the series of ethoxylated oxo alcohols for example, those with the composition C 2-15 + 5 to 10 EO and C14-C15 + 6 to 12 EO are suitable.
  • Mixtures are characterized by low and high levels of detergency against both greasy and mineral soiling highly ethoxylated alcohols, for example those made from tallow alcohol + 3 to 6 EO and tallow alcohol + 12 to 16 EO or Ci3_i5-0xoalkohol + 5 EO and Ci2-i4-0xoalcohol + 8 to 12 EO.
  • Ethylates which contain EO groups and PO groups are also suitable, for.
  • the liquid, optionally heated, additives, in particular nonionics, can be applied to the granules by admixing, preferably spraying, the carrier material advantageously being kept in motion by suitable mixing devices. Further treatment of the granular adsorbate is not necessary. However, allowing the product to rest for several hours at high contents of the applied liquid material can be expedient since its diffusion into the interior of the grain takes some time. The treatment of the granules with the liquid additives leads to a further increase in the bulk density, which can rise to values of over 1,000 g / l.
  • the grains can optionally also be dusted with finely divided powders or coated on the surface.
  • Suitable powdering agents have a grain size of 0.001 to at most 0.1 mm, preferably less than 0.05 mm and can be in proportions of 0.03 to 3, preferably 0.05 mm to 2% by weight, based on the adsorbent loaded with additive.
  • finely powdered zeolites, silica airgel (Aerosil ( R )), colorless or colored pigments such as titanium dioxide are suitable. in the in general, however, such an aftertreatment is superfluous, especially since it does not improve the solution properties.
  • the detergent additives can be combined and mixed in a known manner with the granular or powdered detergent, for example a tower spray powder and its mixtures with other powder components, such as persalts, enzyme granules, bleach activators or defoamers.
  • a tower spray powder and its mixtures with other powder components, such as persalts, enzyme granules, bleach activators or defoamers.
  • the detergents mixed together generally contain 10 to 40% by weight of the additive according to the invention.
  • the granules according to the invention have a different grain structure than those which are produced by conventional granulation processes. This can also be demonstrated by electron micrographs. If, as is customary in conventional granulation processes, the powdered zeolite is placed in the mixer and a solution of the (co) polymeric salt is sprayed on, granules are formed which do not differ externally from the products according to the invention, except that their bulk density is significantly reduced.
  • the images obtained with the scanning electron microscope show sections through two different granules at a magnification of 1: 2 500 (Figs. 1 and 2) and 1: 5 000 (Figs. 3 and 4). Both grains have the same qualitative and quantitative composition as in Example 1.
  • Figures 1 and 3 show a grain in the production of which the spray-dried zeolite was sprayed in a mixer with a 25% strength by weight aqueous solution of the copolymeric salt, granulated and then dried.
  • Figures 2 and 4 show the grain structure of the spiels 1 manufactured product. The arrangement of the cubic zeolite particles in Figures 1 and 3 is completely random. Large pores alternate with strongly bonded, irregularly structured aggregates. In Figures 2 and 4 the zeolite cubes are packed much more densely and uniformly. Individual parts are reminiscent of a structure comparable to a pavement or masonry. The pore size is also significantly reduced.
  • the granulation was carried out in a mixing granulator, consisting of a horizontally arranged cylindrical mixer with a rotating shaft (Lödige type) rotating in the central axis, equipped with mixing elements, with a capacity of 130 liters and a knife mill connected to it, operated at a speed of 1200 to 1500 rpm .
  • 69.5 parts by weight of a synthetic, finely crystalline, spray-dried NaA r type zeolite containing 20 parts by weight of bound water were mixed with 8.8 parts by weight of powdered sodium salt of an acrylic acid-maleic acid copolymer (moisture content 8 wt .-%) mixed to a homogeneous powder mixture.
  • the copolymer (Sokalan ( R ) CP5 from BASF, Ludwigshafen) had a molecular weight of approximately 70,000. After the mixing, which took about 20 seconds, 21.7 parts by weight of water were sprayed in over 90 seconds by means of nozzles and the mixture was granulated for a further 3 minutes with constant mixing. The granules leaving the mixer were dried in a fluidized bed with hot, flowing dry gases.
  • the final product had the following composition:
  • the bulk density of the granules was 900 g / 1.
  • the granules were sprayed in a spray mixer with a liquid, nonionic surfactant heated to 40 ° C., consisting of a 1: 4 mixture of coconut and tallow alcohol reacted with 5 mol EO. After standing for 1 hour, the Adsorbate the following bulk weights:
  • the granules treated with the nonionic surfactant were free-flowing and had a perfect wash-in capacity, both as unblended powder and mixed with a powdery household detergent in a ratio of 1: 4.

Abstract

On obtient des granulés de haute densité apparente, qui contiennent de la zéolithe en fins cristaux et des sels d'acides carboxyliques (co)polymères, en particulier des copolymères d'acide maléique-acide acrylique, de la manière suivante: on fabrique tout d'abord un premier mélange sec de zéolithe et de polycarboxylate que l'on transforme ensuite en granulés, en ajoutant de l'eau, avant de le sécher. Lesdits granulés contiennent entre 60 et 80 % en poids de zéolithe (% de la matière sans eau), entre 2 et 15 % en poids de polycarboxylate et entre 14 et 25 % en poids d'eau, y compris l'eau fixée à de la zéolithe.Granules of high bulk density, which contain fine crystal zeolite and salts of (co) polymeric carboxylic acids, in particular maleic acid-acrylic acid copolymers, are obtained as follows: 'first a first dry mixture of zeolite and polycarboxylate which is then transformed into granules, by adding water, before drying it. Said granules contain between 60 and 80% by weight of zeolite (% of the material without water), between 2 and 15% by weight of polycarboxylate and between 14 and 25% by weight of water, including water fixed at zeolite.

Description

"Verfahren zur Herstellung zeolithhaltioer Granulate hoher Dichte" "Process for producing high density zeolite containing granules"
Die vorliegende Erfindung betrifft ein neues Herstellungsverfahren für zeolithhaltige Granulate mit ausgeprägtem Adsorptionsvermögen für flüssige bis wachsartige Wirkstoffe. Die Granulate zeichnen sich durch eine hohe Dichte, d. h. ein Schüttgewicht zwischen 750 und 1 000 g/1 (Gramm pro Liter) aus und eignen sich zum Einsatz in Wasch- und Reinigungsmittel.The present invention relates to a new production process for zeolite-containing granules with a pronounced adsorption capacity for liquid to waxy active substances. The granules are characterized by a high density, i. H. a bulk density between 750 and 1 000 g / 1 (grams per liter) and are suitable for use in detergents and cleaning agents.
Durch Sprühtrocknung von wäßrigen Aufschläm ungen hergestellte, feinpulvrige Zeolithe und Salze von (co-)polymeren Carbonsäuren enthaltende Granulate sind aus der DE-A-33 16 513 bekannt. Sie weisen ein Schüttgewicht von lediglich 560 - 610 g/1 auf. Eine Lehre des Inhalts, daß derartige Granulate als Trägermaterial für flüssige bis wachsartige Waschmittelbestandteile brauchbar sind, ist diesem Dokument nicht zu entnehmen. Granulate, die Zeolithe, Salze (co-)polymere Carbonsäuren und zusätzlich geringe Mengen an Alkalimetallsilikaten enthalten und als Trägermaterial für flüs¬ sige Waschmittelbestandteile, insbesondere Nonionics dienen, sind in der DE-A-34 44 960 beschrieben. Das Schüttgewicht dieser durch Sprühtrocknung hergestellten Granulate beträgt maximal 700 g/1 und liegt vorzugsweise zwischen 500 und 650 g/1. Dokument EP-A-149 264 lehrt, daß man für den gleichen Zweck handelsübliche sprühgetrock¬ nete Zeolithe bzw. deren Gemische mit anorganischen Salzen, wie Natriumsulfat, verwenden kann. Das Schüttgewicht dieser Sprühpro- dukte liegt im Bereich von 400 - 600 g/1. Aus EP-A-21 267 sind Agglo erate mit einem Gehalt an Zeolithen und Alkalisil katen be¬ kannt, die ein Schüttgewicht von 300 - 700 g/1 aufweisen. Zu ihrer Herstellung wird ein trockenes Vorgemisch aus Zeolith und Alkali- metallsilikat (Mischungsverhältnis 1 : 1 bis 1 : 8) in einem Gra- nulator mit Wasser besprüht und agglomeriert, worauf das über¬ schüssige Wasser bis auf einen Restanteil von weniger als 5 Gew.-% durch Trocknung entfernt wird. Die Granulate eignen sich ebenfalls zum Adsorbieren flüssiger Waschmittelbestandteile, insbesondere von Nonionics. Nachteilig ist vor allem ihr hoher Gehalt an stark alkalisch reagierenden Alkalisilikaten, die ihren Einsatz in neu¬ tral bis schwach alkalisch reagierenden, für empfindliche Texti¬ lien geeigneten Waschmitteln stark einschränkt und überdies den Anteil des lonenaustausch-fähigen Zeoliths vermindert. Außerdem lassen sich nach den Lehren dieses Dokumentes keine Schüttgewichte von über 700 g/1 erzielen.DE-A-33 16 513 discloses granules containing fine powdered zeolites and salts of (co) polymeric carboxylic acids produced by spray drying aqueous slurries. They have a bulk density of only 560 - 610 g / 1. A teaching of the content that such granules can be used as carrier material for liquid to waxy detergent components is not to be found in this document. DE-A-34 44 960 describes granules which contain zeolites, salts of (co) polymeric carboxylic acids and additionally small amounts of alkali metal silicates and serve as carrier material for liquid detergent components, in particular nonionics. The bulk density of these granules produced by spray drying is a maximum of 700 g / 1 and is preferably between 500 and 650 g / 1. Document EP-A-149 264 teaches that commercially available spray-dried zeolites or mixtures thereof with inorganic salts, such as sodium sulfate, can be used for the same purpose. The bulk density of this spray pro products is in the range of 400 - 600 g / 1. From EP-A-21 267 agglomerates containing zeolites and alkali metal silicates are known which have a bulk density of 300-700 g / l. To prepare them, a dry premix of zeolite and alkali metal silicate (mixing ratio 1: 1 to 1: 8) is sprayed with water in a granulator and agglomerated, whereupon the excess water to a residual proportion of less than 5% by weight. -% is removed by drying. The granules are also suitable for adsorbing liquid detergent components, in particular from Nonionics. The main disadvantage is their high content of strongly alkaline-reacting alkali silicates, which severely limits their use in neutral to weakly alkaline-reacting detergents suitable for sensitive textiles and furthermore reduces the proportion of zeolite capable of ion exchange. In addition, according to the teachings of this document, bulk densities of over 700 g / 1 cannot be achieved.
Durch die vorliegende Erfindung werden die aufgezeigten Nachteile beseitigt und die Herstellung von Granulaten mit hohem Schüttge¬ wicht und hohem Anteil an ionenaustauschenden Bestandteilen er¬ möglicht.The disadvantages indicated are eliminated by the present invention and the production of granules with a high bulk density and a high proportion of ion-exchanging constituents is made possible.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Granulaten mit einem Gehalt an feinkristallinem Zeolith, Natrium¬ oder Kaliumsalzen polymerer bzw. copolymerer Carbonsäuren und Wasser, dadurch gekennzeichnet, daß man (a) in einer ersten Misch¬ stufe eine homogene, pulvrige Mischung aus Zeolith und dem Salz der (co-)polymeren Carbonsäure herstellt, dieses Gemisch (b) in einer zweiten Misch- und Granulationsstuffe agglomeriert und (c) das erhaltene Agglo erat bis zum Erreichen eines gut rieselfähigen Granulates mit einem Schüttgewicht von 750 - 1 000 g/1 nachtrock¬ net.The invention relates to a process for the production of granules containing fine crystalline zeolite, sodium or potassium salts of polymeric or copolymeric carboxylic acids and water, characterized in that (a) in a first mixing stage a homogeneous, powdery mixture of zeolite and the salt of the (co) polymeric carboxylic acid, agglomerating this mixture (b) in a second mixing and granulation stage and (c) the agglomerate obtained until a free-flowing mixture is reached Granules with a bulk density of 750-1000 g / 1 after-rocket.
Die Granulate, die nach dem erfindungsgemäßen Verfahren herge¬ stellt werden, enthalten im allgemeinen (bezogen auf wasserfreie Substanz) 60 - 80 Gew.-% Zeolith, 2 - 15 Gew.-% eines Natrium¬ salzes (co-)polymerer Carbonsäuren und 15 - 25 Gew.-% Wasser ein¬ schließlich des an den Zeolith gebundenen Wassers. Als wasser¬ freier Zeolith wird in diesem Falle ein bei Glühtemperatur ent¬ wässerter Na-Zeolith verstanden. Granulate mit einem Gehalt an 62 - 75 Gew.-%, insbesondere 65 - 70 Gew.-% an Zeolith (wasserfrei gerechnet) und 4 - 12 Gew.-%, insbesondere 5 - 10 Gew.-% Na-Salz (co-)polymerer Carbonsäuren (Wassergehalt: Differenz bis 100 Gew.-%) sind bevorzugt.The granules which are produced by the process according to the invention generally contain (based on anhydrous substance) 60-80% by weight of zeolite, 2-15% by weight of a sodium salt of (co) polymeric carboxylic acids and 15 25% by weight of water, including the water bound to the zeolite. In this case, water-free zeolite is understood to mean a sodium zeolite dewatered at the annealing temperature. Granules with a content of 62-75% by weight, in particular 65-70% by weight of zeolite (calculated as anhydrous) and 4-12% by weight, in particular 5-10% by weight of Na salt (co- ) polymeric carboxylic acids (water content: difference up to 100% by weight) are preferred.
Zwecks Herstellung der Granulate geht man zweckmäßigerweise von sprühgetrocknetem, feinpulvrigem Zeolith aus, der im allgemeinen einen Wassergehalt von 17 - 25 Gew.-%, vorzugsweise 19 - 22 Gew.-% aufweist. Dieses Wasser schließt Konstitutionswasser und anhaf¬ tende Feuchtigkeit ein. 70 - 95 Gew.-teile, vorzugsweise 75 - 93 Gew.-teile und insbesondere 80 - 90 Gew.-teile dieses wasserhal¬ tigen Zeoliths werden in einer Mischvorrichtung mit 2 - 12 Gew.- teilen, vorzugsweise 4 - 10 Gew.-teilen und insbesondere 5 - 8 Gew.-teilen des Natriumsalzes der polymeren bzw. copoly eren Car¬ bonsäure zu einem homogenen Pulvergemisch vereinigt. Zwecks Agglomerierung werden unter ständigem weiteren Mischen 15 - 25 Gew.-teile, vorzugsweise 18 - 23 Gew.-teile Wasser zugemischt. Vorzugsweise wird das Wasser mittels Düsen auf das in Bewegung gehaltene Pulvergemisch aufgesprüht und dieses bis zur Ausbildung körniger Agglo erate mechanisch weiterbearbeitet. Das noch feuchte aber bereits rieselfähige Agglomerat wird an¬ schließend getrocknet, beispielsweise mit heißer strömender Luft bzw. mit heißen Verbrennungsgasen, wobei die Trocknung so weit geführt wird, bis das in der Granulationsstufe zugesetzte Wasser bis auf einen Anteil von weniger als 5 Gew.-teilen, vorzugsweise weniger als 3 Gew.-teilen entfernt ist. Zusätzlich können bei der Trocknung noch weitere Wasseranteile, die ursprünglich mit dem Zeolith bzw. einem nicht wasserfrei eingesetzten (co-)polymeren Salz eingebracht wurden, entfernt werden. Derartige "übertrockne¬ te" Granulate können anwendungstechnische Vorteile aufweisen, beispielsweise beim Zusatz zu Waschmitteln, die feuchtigkeits¬ empfindliche Wirkstoffe enthalten. Vorzugsweise sollte jedoch die Entwässerung des Zeoliths nicht unter einen Wassergehalt von 18 Gew.-% getrieben werden, um eine Aktivitätsverminderung zu ver¬ meiden. Zweckmäßigerweise liegt der Wassergehalt der Granulate in einem Bereich, bei dem das Wasserbindungsvermögen des Zeoliths weitgehend abgesättigt ist, d. h. bei dem der Zeolith einen Wassergehalt von insgesamt 19 - 22 Gew.-% (einschließlich Kon¬ stitutionswasser) besitzt.For the production of the granules, it is expedient to start from spray-dried, finely powdered zeolite, which generally has a water content of 17-25% by weight, preferably 19-22% by weight. This water includes constitutional water and adhering moisture. 70-95 parts by weight, preferably 75-93 parts by weight and in particular 80-90 parts by weight of this water-containing zeolite are mixed in a mixing device with 2-12 parts by weight, preferably 4-10 parts by weight. parts and in particular 5 - 8 parts by weight of the sodium salt of the polymeric or copoly eric carboxylic acid combined into a homogeneous powder mixture. For agglomeration, 15-25 parts by weight, preferably 18-23 parts by weight of water are mixed in with constant further mixing. The water is preferably sprayed onto the powder mixture kept in motion by means of nozzles and mechanically processed until granular agglomerates are formed. The still moist but already free-flowing agglomerate is then dried, for example with hot flowing air or with hot combustion gases, the drying being carried out until the water added in the granulation stage to a proportion of less than 5% by weight. divide, preferably less than 3 parts by weight. In addition, further water components that were originally introduced with the zeolite or a (co) polymeric salt which is not used anhydrous can be removed during drying. Such "over-dried" granules can have application-technical advantages, for example when added to detergents which contain active ingredients which are sensitive to moisture. However, the dewatering of the zeolite should preferably not be driven below a water content of 18% by weight in order to avoid a reduction in activity. The water content of the granules is expediently in a range in which the water-binding capacity of the zeolite is largely saturated, ie in which the zeolite has a total water content of 19-22% by weight (including constitutional water).
Geeignete Zeolithe sind solche vom Zeolith A-Typ. Brauchbar sind ferner Gemische aus Zeolith NaA und NaX, wobei der Anteil des Zeoliths NaX in derartigen Gemischen zweckmäßigerweise unter 30 %, insbesondere unter 20 % liegt. Geeignete Zeolithe weisen keine Teilchen mit einer Größe über 30 μ auf und bestehen zu wenigstens 80 % aus Teilchen einer Größe von weniger als 10 μm. Ihre mittlere Teilchengröße (Volumenverteilung, Meßmethode: Coulter Counter) beträgt 1 bis 10 μm. Ihr Calciumbindevermögen, das nach den An¬ gaben der DE 24 12 837 bestimmt und auf wasserfreie Substanz be¬ zogen wird, liegt im Bereich von 100 bis 200 mg CaO/g. Beispiele für die in den Granulaten enthaltenen homopolymeren und/oder copolymeren Carbonsäuren, vorliegend als wasserlösliche Salze, von denen die Natriumsalze bevorzugt werden, sind Poly- acrylsäure, Polymethacrylsäure und Polymaleinsäure, Copolymere der Acrylsäure mit Methacrylsäure oder Maleinsäure mit Vinylethern, wie Vinylmethylether bzw. Vinylethylether, ferner mit Vinylestern, wie Vinylacetat oder Vinylpropionat, Acryla id, Methacryla id sowie mit Ethylen, Propylen oder Styrol. In solchen copolymeren Säuren, in denen eine der Komponenten keine Säurefunktion auf¬ weist, beträgt deren Anteil im Interesse einer ausreichenden Wasserlöslichkeit nicht mehr als 50 Molprozent, vorzugsweise weniger als 30 Molprozent. Als besonders geeignet haben sich Co¬ polymere der Acrylsäure bzw. Methacrylsäure mit Maleinsäure er¬ wiesen, wie sie beispielsweise in EP 25 551 Bl näher charakte¬ risiert sind. Es handelt sich dabei um Copolymerisate, die 50 bis 90 Gew.-% Acrylsäure bzw. Methacrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Besonders bevorzugt sind solche Copolymere, in denen 45 bis 85 Gew.-% Acrylsäure und 55 bis 15 Gew.-% Malein¬ säure anwesend sind. Das Molekulargewicht der homo- bzw. copoly¬ meren Polycarboxylate beträgt im allgemeinen 2 000 bis 150 000, vorzugsweise 5000 bis 100000.Suitable zeolites are those of the zeolite A type. Mixtures of zeolite NaA and NaX can also be used, the proportion of the zeolite NaX in such mixtures advantageously being less than 30%, in particular less than 20%. Suitable zeolites have no particles larger than 30 μm and consist of at least 80% of particles smaller than 10 μm. Their average particle size (volume distribution, measurement method: Coulter Counter) is 1 to 10 μm. Their calcium binding capacity, which is determined in accordance with DE 24 12 837 and is based on anhydrous substance, is in the range from 100 to 200 mg CaO / g. Examples of the homopolymeric and / or copolymeric carboxylic acids contained in the granules, in the present case as water-soluble salts, of which the sodium salts are preferred, are polyacrylic acid, polymethacrylic acid and polymaleic acid, copolymers of acrylic acid with methacrylic acid or maleic acid with vinyl ethers, such as vinyl methyl ether or vinyl ethyl ether , further with vinyl esters, such as vinyl acetate or vinyl propionate, Acryla id, Methacryla id and with ethylene, propylene or styrene. In such copolymeric acids in which one of the components has no acid function, the proportion thereof in the interest of sufficient water solubility is not more than 50 mol percent, preferably less than 30 mol percent. Copolymers of acrylic acid or methacrylic acid with maleic acid, as described in more detail in EP 25 551 B1, for example, have proven to be particularly suitable. These are copolymers which contain 50 to 90% by weight of acrylic acid or methacrylic acid and 50 to 10% by weight of maleic acid. Copolymers in which 45 to 85% by weight of acrylic acid and 55 to 15% by weight of maleic acid are present are particularly preferred. The molecular weight of the homo- or copolymeric polycarboxylates is generally 2,000 to 150,000, preferably 5,000 to 100,000.
Handelsübliche Salze (co-)polymerer Carbonsäuren in pulvriger Form enthalten vielfach Feuchtigkeitsanteile von 5 - 15 Gew.-%. Dieser Wasseranteil wird in die Berechnung der Wasserbilanz eingebracht, bzw. die in die Granulierstufe eingebrachte Wassermenge kann um diesen Anteil reduziert werden. Rechnerisch ist der Anteil der Salze bei der Herstellung der Mittel bzw. bei der Zusammensetzung der fertigen Granulate auf wasserfreies Salz zu beziehen. Die Granulierung kann in üblichen Misch- und Granuliervorrich¬ tungen diskontinuierlich oder kontinuierlich durchgeführt werden. Geeignet sind z. B. Granuliervorrichtungen, die aus einem hori¬ zontal angeordneten oder gegen die Horizontale geneigten, zylin¬ drischen Behältern bestehen, in deren Längsachse eine mit Misch¬ werkzeugen und Förderschaufeln ausgerüstete Welle rotiert. Die Zuführung des Wassers kann durch in der Wandung oder an der hohlen Welle angebrachte Sprühdüsen erfolgen. Sofern kontinuierlich ge¬ arbeitet wird, können zwei hintereinander geschaltete Mischer ver¬ wendet werden, wobei im ersten Mischer die Herstellung des trock¬ nen Vorgemisches und im zweiten Mischer die Granulierung unter Wasserzusatz erfolgt. Ein kontinuierliches Arbeiten ist auch in einem Mischer möglich, wobei in einer ersten Mischstrecke die Pulverströme vereinigt und homogenisiert werden und das Gemisch nach dem Weitertransport in einer nachfolgenden Mischstrecke mit Wasser behandelt und agglomeriert wird. Das Nachtrocknen kann durch Einleiten heißer Gase in einer dritten Mischstrecke z. B. einer Wirbelschicht, oder auch nach dem Austragen der Granulate aus dem Mischer beispielsweise in einer Rüttelstrecke, einem Frei- falltrockner oder auch in dünner Schicht auf einem Transportband erfolgen. Abschließend werden Grob- und Feinanteile abgesiebt. Die Grobanteile werden gemahlen und dem Produkt zugemischt, Feinan¬ teile bzw. Staub in die Granulation zurückgeführt.Commercially available salts of (co) polymeric carboxylic acids in powder form often contain 5 to 15% by weight of moisture. This proportion of water is included in the calculation of the water balance, or the amount of water introduced into the pelletizing stage can be reduced by this proportion. In mathematical terms, the proportion of salts in the preparation of the compositions or in the composition of the finished granules is based on anhydrous salt. The granulation can be carried out batchwise or continuously in conventional mixing and granulating devices. Are suitable for. B. pelletizers, which consist of a horizontally arranged or inclined to the horizontal, cylindrical containers, in the longitudinal axis of which a shaft equipped with mixing tools and conveying blades rotates. The water can be supplied by spray nozzles mounted in the wall or on the hollow shaft. If work is carried out continuously, two mixers connected in series can be used, the dry premix being produced in the first mixer and the pelletizing being carried out with the addition of water in the second mixer. Continuous work is also possible in a mixer, the powder streams being combined and homogenized in a first mixing section and the mixture being treated with water and agglomerating in a subsequent mixing section in a subsequent mixing section. The drying can be carried out by introducing hot gases in a third mixing section z. B. a fluidized bed, or after discharging the granules from the mixer, for example in a vibrating section, a free-fall dryer or in a thin layer on a conveyor belt. Finally coarse and fine particles are sieved. The coarse fractions are ground and mixed into the product, fine fractions or dust are returned to the granulation.
Die Granulate weisen ein Schüttgewicht von 750 - 1 000 g/1, meist ein solches von 800 - 950 g/1 auf. Auf Grund ihrer dichten Packung und ihres geringen Porenvolumens ist ihr Aufnahmevermögen für flüssige bzw. pastenförmige Waschmittelbestandteile, insbesondere Nonionics, gegenüber spezifisch leichteren Trägerkörnern etwas vermindert, beträgt jedoch immer noch 15 bis maximal 20 Gew.-% ohne nennenswerte Beeinträchtigung der Rieselfähigkeit. Dieses angesichts der hohen Packungsdichte immer noch überraschende hohe Adsorptionsvermögen reicht für die üblichen Anwendungsgebiete, insbesondere für einen Einsatz als Mischungskomponente in Wasch- und Reinigungsmitteln, vollkommen aus.The granules have a bulk density of 750-1000 g / 1, usually that of 800-950 g / 1. Due to their tight packing and their small pore volume, their absorption capacity for liquid or pasty detergent components, especially nonionics, is somewhat reduced compared to specifically lighter carrier grains, but is still 15 to a maximum of 20% by weight without any appreciable impairment of the free-flowing properties. This In view of the high packing density, the surprisingly high adsorption capacity is completely sufficient for the usual fields of application, in particular for use as a mixture component in detergents and cleaning agents.
Überraschend ist ferner, daß die Granulate ungeachtet ihrer hohen Packungsdichte und ihres hohen Gehaltes an wasserunlöslichen Be¬ standteilen in kaltem Wasser schnell und vollständig zerfallen und in den Einspülvorrichtungen von Waschautomaten keine Rückstände hinterlassen, d. h. sie besitzen ein sehr gutes Einspülvermögen. Diese vorteilhafte Eigenschaft macht sich auch nach dem Impräg¬ nieren mit Nonionics sowie im Gemisch mit anderen pulverför igen Waschmittelkomponenten bemerkbar.It is also surprising that, regardless of their high packing density and their high content of water-insoluble constituents, the granules disintegrate quickly and completely in cold water and do not leave any residues in the washing-up devices of washing machines, ie. H. they have a very good induction ability. This advantageous property is also noticeable after impregnation with nonionics and in a mixture with other powder detergent components.
Die Granulate können mit beliebigen flüssigen oder pastenförmigen bzw. fettartigen Waschmittelbestandteilen imprägniert werden, die auf anderen Wegen nicht oder nur unter Wirkungsverlust in übliche pulverför ige bzw. granuläre Wasch- oder Reinigungsmittel einge¬ arbeitet werden können. Hierzu zählen Schauminhibitoren, insbe¬ sondere Paraffinkohlenwasserstoffe, Silikone, Silikonharze und von langkettigen Fettsäuren abgeleitete Bis-acyl-alkylendia ine sowie deren Gemische. Weitere adsorbierbare Wirkstoffe sind Fettsäure- alkylolamide und kationische Weichmacher, wie langkettige Fett¬ reste aufweisende quartäre Ammoniumsalze, ferner fettlösende Lösungsmittel, wie Terpene. Bevorzugt werden die Granulate als Trägerkörner für nichtionische Tenside eingesetzt. Dies ist ein weiterer Aspekt der Erfindung.The granules can be impregnated with any liquid or paste-like or fat-like detergent constituents which cannot be incorporated into conventional powdery or granular detergents or cleaning agents in other ways or only with a loss of activity. These include foam inhibitors, in particular paraffin hydrocarbons, silicones, silicone resins and bis-acylalkylenediamines derived from long-chain fatty acids and mixtures thereof. Further adsorbable active ingredients are fatty acid alkylolamides and cationic plasticizers, such as quaternary ammonium salts containing long-chain fatty residues, and also fat-dissolving solvents, such as terpenes. The granules are preferably used as carrier grains for nonionic surfactants. This is another aspect of the invention.
Geeignete nichtionische Tenside sind Alkoxylierungsprodukte mit 10 bis 20 Kohlenstoffatomen im hydrophoben Rest und 3 bis 20 Glykol- ethergruppen. Hierzu zählen Ethoxylierungsprodukte von Alkoholen, vicinalen Diolen, A inen, Thioalkoholen, Fettsäureamiden und Fett¬ säuren. Weiterhin sind Alkylphenolpolyglykolether mit 5 bis 12 C-Atomen im Alkylrest und 3 bis 10 Ethylenglykolethergruppen brauchbar. Ebenso kommen auch Blockpolymere aus Ethylenoxid und Propylenoxid, die unter der Bezeichnung Pluronics handelsüblich sind, in Betracht. Weiterhin können Alkylglycoside bzw. Alkyl- polyglykoside sowie deren Gemische mit den genannten Εthoxylie- rungsprodukteπ verwendet werden»Suitable nonionic surfactants are alkoxylation products with 10 to 20 carbon atoms in the hydrophobic radical and 3 to 20 glycol ether groups. These include ethoxylation products of alcohols, vicinal diols, amines, thio alcohols, fatty acid amides and fatty acids. Alkylphenol polyglycol ethers with 5 to 12 carbon atoms in the alkyl radical and 3 to 10 ethylene glycol ether groups are also useful. Block polymers of ethylene oxide and propylene oxide, which are commercially available under the name Pluronics, are also suitable. Furthermore, alkyl glycosides or alkyl polyglycosides as well as their mixtures with the Εthoxylation products mentioned can be used »
Bevorzugte Nonionics, die an dem Granulat adsorbiert sein können und mit diesem zusammen als rieselfähiges Gemisch vorliegen, lei¬ ten sich von Alkoholen mit 12 bis 18 C-Atomen ab, die gesättigt oder olefinisch ungesättigt, linear oder in 2-Ste lung methyl er¬ zweigt (Oxo-Rest) sein können. Ihre Umsetzungsprodukte mit Ethy¬ lenoxid (EO) bzw. Propylenoxid (PO) sind wasserlösliche bzw. in Wasser dispergierbare Gemische von Verbindungen mit unterschied¬ lichem Alkoxyl erungsgrad, wobei die im folgenden angegebene An¬ zahl der EO- bzw. PO-Gruppen einem statistischen Mittelwert ent¬ spricht.Preferred nonionics, which can be adsorbed on the granulate and together with it are in the form of a free-flowing mixture, are derived from alcohols having 12 to 18 carbon atoms which are saturated or olefinically unsaturated, linear or methyl in 2-position branches (oxo residue) can be. Their reaction products with ethylene oxide (EO) or propylene oxide (PO) are water-soluble or water-dispersible mixtures of compounds with different degrees of alkoxylation, the number of EO or PO groups given below being statistical Corresponds to the mean.
Beispiele für bevorzugte ethoxylierte Fettalkohole sind C12-I8" Cocosalkohole mit 3 bis 12 EO, Ci5_i8~Talgalkohol mit 4 bis 16 EO, Oleylalkohol mit 4 bis 12 EO sowie aus anderen nativen Fettalko¬ holgemischen erhältliche Ethoxylierungsprodukte entsprechender Ketten- und EO-Verteilung. Aus der Reihe der ethoxylierten Oxo- alkohole sind beispielsweise solche der Zusammensetzung C 2-15 + 5 bis 10 EO und C14-C15 + 6 bis 12 EO geeignet. Durch eine erhöhte Waschkraft sowohl gegenüber fettartigen und mineralischen An¬ schmutzungen zeichnen sich Gemische aus niedrig und hoch ethoxy¬ lierten Alkoholen aus, beispielsweise solche aus Talgalkohol + 3 bis 6 EO und Talgalkohol + 12 bis 16 EO oder Ci3_i5-0xoalkohol + 5 EO und Ci2-i4-0xoalkohol + 8 bis 12 EO. Weiterhin sind auch Eth- oxylate geeignet, die EO-Gruppen und PO-Gruppen enthalten, z. B. C12_i8-Alkohole der Formel R-(PO)a-(EO)b bzw. R-(EO)b~(PO)c, worin a Zahlen von 1 bis 3, b solche von 5 bis 20 und c solche von 1 bis 10 (b größer als c) bedeuten.Examples of preferred ethoxylated fatty alcohols are C12-I8 "coconut alcohols with 3 to 12 EO, Ci5_i8 ~ tallow alcohol with 4 to 16 EO, oleyl alcohol with 4 to 12 EO as well as ethoxylation products of appropriate chain and EO distribution available from other native fatty alcohol mixtures. Aus In the series of ethoxylated oxo alcohols, for example, those with the composition C 2-15 + 5 to 10 EO and C14-C15 + 6 to 12 EO are suitable. Mixtures are characterized by low and high levels of detergency against both greasy and mineral soiling highly ethoxylated alcohols, for example those made from tallow alcohol + 3 to 6 EO and tallow alcohol + 12 to 16 EO or Ci3_i5-0xoalkohol + 5 EO and Ci2-i4-0xoalcohol + 8 to 12 EO. Ethylates which contain EO groups and PO groups are also suitable, for. B. C 12 _i8 alcohols of the formula R- (PO) a - (EO) b or R- (EO) b ~ (PO) c , in which a numbers from 1 to 3, b such from 5 to 20 and c mean those from 1 to 10 (b greater than c).
Das Aufbringen der flüssigen, ggf. erwärmten Zusatzstoffe, insbe¬ sondere Nonionics auf das Granulat kann durch Zumischen, vorzugs¬ weise Aufsprühen erfolgen, wobei das Trägermaterial zweckmäßiger¬ weise durch geeignete Mischvorrichtungen in Bewegung gehalten wird. Eine weitere Nachbehandlung des körnigen Adsorbates ist nicht erforderlich. Allerdings kann ein mehrstündiges Ruhenlassen des Produktes bei hohen Gehalten an aufgebrachtem flüssigen Mate¬ rial zweckmäßig sein, da dessen Diffusion in das Korninnere einige Zeit in Anspruch nimmt. Die Behandlung der Granulate mit den flüssigen Zusatzstoffen führt zu einem weiteren Anstieg des Schüttgewichtes, das bis auf Werte von über 1 000 g/1 ansteigen kann.The liquid, optionally heated, additives, in particular nonionics, can be applied to the granules by admixing, preferably spraying, the carrier material advantageously being kept in motion by suitable mixing devices. Further treatment of the granular adsorbate is not necessary. However, allowing the product to rest for several hours at high contents of the applied liquid material can be expedient since its diffusion into the interior of the grain takes some time. The treatment of the granules with the liquid additives leads to a further increase in the bulk density, which can rise to values of over 1,000 g / l.
Nach dem Aufbringen des flüssigen Zusatzstoffes können die Körner egebenenfalls noch mit feinteiligen Pulvern bestäubt bzw. ober¬ flächlich beschichtet werden. Hierdurch kann die bei hohen, 15 % übersteigenden Gehalten an Nonionics die Rieselfähigkeit verbes¬ sert und das Schüttgewicht geringfügig erhöht werden. Geeignete Puderungsmittel weisen eine Körngröße von 0,001 bis höchstens 0,1 mm, vorzugsweise von weniger als 0,05 mm auf und können in Antei¬ len von 0,03 bis 3, vorzugsweise 0,05 mm bis 2 Gew.-%, bezogen auf das mit Zusatzstoff beladene Adsorptionsmittel, angewendet werden. In Frage kommen z. b. feinpulvrige Zeolithe, Kieselsäureaerogel (Aerosil(R)), farblose oder farbige Pigmente, wie Titandioxid. Im allgemeinen ist eine solche Nachbehandlung jedoch überflüssig, zumal durch sie die Lösungseigenschaften nicht verbessert werden.After the liquid additive has been applied, the grains can optionally also be dusted with finely divided powders or coated on the surface. In this way, the free-flowing properties can be improved and the bulk density slightly increased, if the nonionics content exceeds 15%. Suitable powdering agents have a grain size of 0.001 to at most 0.1 mm, preferably less than 0.05 mm and can be in proportions of 0.03 to 3, preferably 0.05 mm to 2% by weight, based on the adsorbent loaded with additive. For example, finely powdered zeolites, silica airgel (Aerosil ( R )), colorless or colored pigments such as titanium dioxide are suitable. in the in general, however, such an aftertreatment is superfluous, especially since it does not improve the solution properties.
Die Waschmitteladditive können mit dem körnigen bzw. pulverför- migen Waschmittel, beispielsweise einem Turmsprühpulver sowie dessen Gemischen mit weiteren Pulverkomponenten, wie Persalze, Enzymgranulate, Bleichaktivatoren bzw. Entschäumer enthaltenden Granulaten, in bekannter Weise vereinigt und vermischt werden. Das hohe Schüttgewicht und das günstige Einspülverhalten der erfin¬ dungsgemäßen Additive überträgt sich auf diese komplexen Gemische. In der Praxis enthalten die zusammengemischten Waschmittel im allgemeinen 10 bis 40 Gew.-% des erfindungsgemäßen Additivs.The detergent additives can be combined and mixed in a known manner with the granular or powdered detergent, for example a tower spray powder and its mixtures with other powder components, such as persalts, enzyme granules, bleach activators or defoamers. The high bulk density and the favorable flushing behavior of the additives according to the invention are transferred to these complex mixtures. In practice, the detergents mixed together generally contain 10 to 40% by weight of the additive according to the invention.
Die erf ndungsgemäßen Granulate weisen einen anderen Kornaufbau auf als solche, die nach konventionellen Granulierverfahren her¬ gestellt werden. Dies läßt sich auch durch elektronenmikroskopi¬ sche Aufnahmen nachweisen. Wird, wie bei konventionellen Granu¬ lierverfahren üblich, der pulverförmige Zeolith im Mischer vor¬ gelegt und eine Lösung des (co-)polymeren Salzes aufgesprüht, so entstehen Granulate, die sich äußerlich nicht von den erfindungs¬ gemäßen Produkten unterscheiden, außer das ihr Schüttgewicht deut¬ lich verringert ist. Die mit dem Rasterelektronenmikroskop erhal¬ tenen Abbildungen zeigen Schnitte durch zwei verschiedene Granu¬ latkörner im Vergrößerungsmaßstab 1 : 2 500 (Abb. 1 und 2) bzw. 1 : 5 000 (Abb. 3 und 4). Beide Körner weisen die identische qua¬ litative und quantitative Zusammensetzung entsprechend den Angaben des Beispiels 1 auf. Die Abbildungen 1 und 3 zeigen ein Korn, bei dessen Herstellung der sprühgetrocknete Zeolith im Mischer mit einer 25 Gew.-%igen wäßrigen Lösung des copolymeren Salzes be¬ sprüht, granuliert und anschließend getrocknet wurde. Die Abbil¬ dungen 2 und 4 zeigen den Kornaufbau des nach den Angaben des Bei- spiels 1 hergestellten Produktes. Die Anordnung der kubischen Zeo- lithteilchen in Abbildung 1 und 3 ist völlig regellos. Große Poren wechseln mit stark verklebten, unregelmäßig aufgebauten Aggrega¬ ten. In Abbildung 2 und 4 sind die Zeolithwürfel wesentlich dichter und gleichförmiger gepackt. Einzelne Partien erinnern an einen Aufbau vergleichbar einem Straßenpflaster bzw. einem Mauer¬ werk. Auch die Porengröße ist deutlich verringert. The granules according to the invention have a different grain structure than those which are produced by conventional granulation processes. This can also be demonstrated by electron micrographs. If, as is customary in conventional granulation processes, the powdered zeolite is placed in the mixer and a solution of the (co) polymeric salt is sprayed on, granules are formed which do not differ externally from the products according to the invention, except that their bulk density is significantly reduced. The images obtained with the scanning electron microscope show sections through two different granules at a magnification of 1: 2 500 (Figs. 1 and 2) and 1: 5 000 (Figs. 3 and 4). Both grains have the same qualitative and quantitative composition as in Example 1. Figures 1 and 3 show a grain in the production of which the spray-dried zeolite was sprayed in a mixer with a 25% strength by weight aqueous solution of the copolymeric salt, granulated and then dried. Figures 2 and 4 show the grain structure of the spiels 1 manufactured product. The arrangement of the cubic zeolite particles in Figures 1 and 3 is completely random. Large pores alternate with strongly bonded, irregularly structured aggregates. In Figures 2 and 4 the zeolite cubes are packed much more densely and uniformly. Individual parts are reminiscent of a structure comparable to a pavement or masonry. The pore size is also significantly reduced.
Beispiel 1example 1
Die Granulierung erfolgte in einem Mischgranulator, bestehend aus einem horizontal angeordneten zylindrischen Mischer mit einer in der Mittelachse rotierenden, mit Mischorganen bestückten Drehwelle (Bauart Lödige) mit einem Fassungsvermögen von 130 Litern und einer daran angeschlossenen, mit einer Drehzahl von 1200 bis 1500 Upm betriebenen Messermühle. In dem Mischgranulator wurden 69,5 Gew.-teile eines synthetischen, feinkristallinen, sprühge¬ trockneten Zeoliths vom Typ NaAr enthaltend 20 Gew.- gebundenes Wasser, mit 8,8 Gew.-teilen pulverförmigem Natriumsalz eines Acrylsäure-maleinsäure-copolymers (Feuchtigkeitsgehalt 8 Gew.-%) zu einem homogenen Pulvergemisch vermischt. Das Copolymer (Soka- lan(R) CP5 der Firma BASF, Ludwigshafen) wies ein Molekulargewicht von ca. 70 000 auf. Nach dem Mischen, das ca. 20 sec in Anspruch nahm, wurden mittels Düsen 21,7 Gew.-teile Wasser im Verlauf von 90 sec eingesprüht und das Gemisch unter ständigem Mischen noch weitere 3 Minuten granuliert. Das den Mischer verlassende Granulat wurde in einer Wirbelschicht mit heißen, strömenden Trockengasen getrocknet. Das Endprodukt wies die folgende Zusammensetzung auf:The granulation was carried out in a mixing granulator, consisting of a horizontally arranged cylindrical mixer with a rotating shaft (Lödige type) rotating in the central axis, equipped with mixing elements, with a capacity of 130 liters and a knife mill connected to it, operated at a speed of 1200 to 1500 rpm . 69.5 parts by weight of a synthetic, finely crystalline, spray-dried NaA r type zeolite containing 20 parts by weight of bound water were mixed with 8.8 parts by weight of powdered sodium salt of an acrylic acid-maleic acid copolymer (moisture content 8 wt .-%) mixed to a homogeneous powder mixture. The copolymer (Sokalan ( R ) CP5 from BASF, Ludwigshafen) had a molecular weight of approximately 70,000. After the mixing, which took about 20 seconds, 21.7 parts by weight of water were sprayed in over 90 seconds by means of nozzles and the mixture was granulated for a further 3 minutes with constant mixing. The granules leaving the mixer were dried in a fluidized bed with hot, flowing dry gases. The final product had the following composition:
72,9 Gew.-% Zeolith (wasserfrei gerechnet) 9,3 Gew.-% Polymersalz (wasserfrei gerechnet) 17,8 Gew.-% Wasser72.9% by weight of zeolite (calculated as anhydrous) 9.3% by weight of polymer salt (calculated as anhydrous) 17.8% by weight of water
Das Wasser war praktisch vollständig an dem Zeolith gebunden, wo¬ raus sich ein Wassergehalt des Zeoliths von 19,7 Gew.-% errechnet. Nach Absieben von ca. 15 % Grobkorn ergab eine Siebanalyse die folgende Kornverteilung (angegeben ist die auf den Sieben verblei¬ bende Menge in Gew.-%): The water was practically completely bound to the zeolite, from which a water content of the zeolite of 19.7% by weight was calculated. After screening about 15% coarse grain, a sieve analysis showed the following grain distribution (the amount remaining on the sieves is given in% by weight):
Das Schüttgewicht des Granulates betrug 900 g/1.The bulk density of the granules was 900 g / 1.
Das Granulat wurde in einem Sprühmischer mit einem auf 40 °C er¬ wärmten, flüssigen, nichtionischen Tensid besprüht, bestehend aus einem mit 5 Mol EO umgesetzten Gemisch von Cocos- und Talgalkohol im Verhältnis 1 : 4. Nach einer Standzeit von 1 Stunde wiesen die Adsorbate die folgenden Schüttgewichte auf:The granules were sprayed in a spray mixer with a liquid, nonionic surfactant heated to 40 ° C., consisting of a 1: 4 mixture of coconut and tallow alcohol reacted with 5 mol EO. After standing for 1 hour, the Adsorbate the following bulk weights:
Die mit dem nichtionischen Tensid behandelten Granulate waren gut rieselfähig und wiesen ein einwandfreies Einspülvermögen auf und zwar sowohl als unverschnittenes Pulver wie auch vermischt mit einem pulverförmigen Haushaltsmittel im Verhältnis 1 : 4. The granules treated with the nonionic surfactant were free-flowing and had a perfect wash-in capacity, both as unblended powder and mixed with a powdery household detergent in a ratio of 1: 4.

Claims

Patentansprüche Claims
1. Verfahren zur Herstellung von Granulaten mit einem Gehalt an feinkristallinem Zeolith, Natrium- oder Kaliumsalzen polymerer bzw. copoly erer Carbonsäuren und Wasser, dadurch gekennzeich¬ net, daß man (a) in einer ersten Mischstufe eine homogene, pulv¬ rige Mischung aus Zeolith und dem Salz der (co-)polymeren Car¬ bonsäure herstellt, dieses Gemisch (b) in einer zweiten Misch- und Granulationsstuffe agglomeriert und (c) das erhaltene Ag- glomerat bis zum Erreichen eines gut rieselfähigen Granulates mit einem Schüttgewicht von 750 - 1000 g/1 nachtrocknet.1. A process for the preparation of granules containing fine crystalline zeolite, sodium or potassium salts of polymeric or copolyeric carboxylic acids and water, characterized in that (a) in a first mixing stage a homogeneous, powdery mixture of zeolite and the salt of the (co) polymeric carboxylic acid, this mixture (b) agglomerates in a second mixing and granulation stage and (c) the agglomerate obtained until a free-flowing granulate with a bulk density of 750-1000 is reached g / 1 dried.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man ein Granulat herstellt, das (auf wasserfreie Substanz bezogen) 60 - 80 Gew.-% Zeolith, 2 - 15 Gew.-% des Natriumsalzes der (co-)- polymeren Carbonsäure und 14 - 25 Gew.-% Wasser einschließlich des an Zeolith gebundenen Wassers enthält.2. The method according to claim 1, characterized in that one produces granules which (based on anhydrous substance) 60-80 wt .-% zeolite, 2-15 wt .-% of the sodium salt of the (co) polymeric carboxylic acid and Contains 14-25% by weight of water including water bound to zeolite.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man ein Granulat herstellt, das (auf wasserfreie Substanz bezogen) 62 - 75 Gew.- , insbesondere 65 - 70 Gew.-% Zeolith und 4 - 123. The method according to claim 1, characterized in that one produces a granulate which (based on anhydrous substance) 62-75 wt .-%, in particular 65-70 wt .-% zeolite and 4-12
Gew.-%, insbesondere 5 - 10 Gew.-% Natriumsalz (co-)polymerer Carbonsäuren enthält.% By weight, in particular 5-10% by weight, of sodium salt of (co) polymeric carboxylic acids.
4. Verfahren nach Anspruch 1 sowie einem der Ansprüche 2 oder 3, dadurch gekennzeichnet, daß man 70 - 95 Gew.-teile eines sprüh¬ getrockneten, feinpulvrigen Zeoliths, der 15 - 25, vorzugsweise 18 - 22 Gew.-% gebundenes Wasser einschließlich Konstitutions¬ wasser enthält, mit 3 - 12 Gew.-teilen eines Natriumsalzes (co-)polymerer Säuren, homogen miteinander vermischt, diese Mischung unter Zusatz von 15 - 25 Gew.-teilen Wasser agglome¬ riert und durch anschließende Trocknung das in der Granula¬ tionsstufe (b) zugeführte Wasser durch Trocknung auf einen An¬ te l von weniger als 5 Gew.-teilen, vorzugsweise weniger als 3 Gew.-teilen entfernt.4. The method according to claim 1 and one of claims 2 or 3, characterized in that 70-95 parts by weight of a spray-dried, finely powdered zeolite, including 15-25, preferably 18-22% by weight of bound water Constitution water contains, with 3 - 12 parts by weight of a sodium salt (Co) polymeric acids, homogeneously mixed with one another, this mixture is agglomerated with the addition of 15-25 parts by weight of water and the water supplied in the granulation stage (b) is subsequently dried by drying to a proportion less than 5 parts by weight, preferably less than 3 parts by weight.
5. Nach einem oder mehreren der Ansprüche 1 bis 4 hergestelltes Granulat, imprägniert mit bis zu 20 Gew.-% (bezogen auf Adsor- bat) mindestens eines flüssigen, pastenförmigen oder fettar¬ tigen Waschmittelbestandteils.5. Granules produced according to one or more of claims 1 to 4, impregnated with up to 20% by weight (based on adsorbent) of at least one liquid, pasty or fat-like detergent component.
6. Mittel nach Anspruch 5, dadurch gekennzeichnet, daß das Impräg¬ nierungsmittel aus nichtionischen Tensiden besteht.6. Composition according to claim 5, characterized in that the impregnating agent consists of nonionic surfactants.
7. Verwendung eines Mittels, hergestellt gemäß einem oder mehreren der Ansprüche 1 bis 4, 5 oder 6 als Pulverkomponente in Wasch- und Reinigungsmitteln. 7. Use of an agent prepared according to one or more of claims 1 to 4, 5 or 6 as a powder component in detergents and cleaning agents.
EP89912426A 1988-11-10 1989-11-02 Process for producing high-density zeolite-containing granules Pending EP0442923A1 (en)

Applications Claiming Priority (2)

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DE3838086A DE3838086A1 (en) 1988-11-10 1988-11-10 METHOD FOR PRODUCING HIGH DENSITY GRANULES CONTAINING ZEOLITE
DE3838086 1988-11-10

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JP (1) JPH04501730A (en)
KR (1) KR900701992A (en)
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PT (1) PT92223B (en)
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DK86891D0 (en) 1991-05-08
DK86891A (en) 1991-07-08
TR24018A (en) 1991-02-01
EP0368137B1 (en) 1994-01-05
EP0368137A1 (en) 1990-05-16
DE3838086A1 (en) 1990-05-17
ES2047091T3 (en) 1994-02-16
DE58906639D1 (en) 1994-02-17

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