EP0364881A2 - Process for preparing granules containing surface-active agents - Google Patents

Abstract

A process for manufacturing pourable granulates with an apparent density of 650 to 1000 g/l containing non-ionic tensides from the class of polyglycol ether derivatives as well as fine-particle, water-soluble and/or water-insoluble solids and water comprises a first mixing step (A) in which the non-ionic tenside is mixed with water, which may contain a fraction less than 50 wt.% of the total amount of water-soluble or water-insoluble solids in dissolved or dispersed form, to form a viscous gel phase. In a second mixing step (B), the remaining larger fraction of the water-soluble or water-insoluble solids is added in solid powder form and the mixture is processed until granulates are formed and a maximum apparent density is reached. The weight ratio of non-ionic tenside and water in the gel phase to the total solids present referred to the anhydrous substance lies between 25:75 and 65:35. Zeolites and bentonites are particularly suitable as water-insoluble solids.

Description

The invention relates to a process for producing granules which, despite their high content of nonionic surfactants and adsorbed water, are free-flowing, have a high bulk density and a very homogeneous grain spectrum. The granules can be obtained by a comparatively simple mixing process and do not require any subsequent drying. They can be used directly as detergents or cleaning agents or as additional powder components in composite detergents and cleaning agents.

Granules with a content of carrier substances and liquid or paste-like nonionic surfactants adsorbed thereon are known. Methods have been developed for their production in which the liquid or melted nonionic surfactant is sprayed onto a previously spray-dried powder or mixed with a powdery carrier substance under granulating conditions. Loose, in particular spray-dried, water-soluble salts, such as phosphates, silicates, borates or perborates or salt mixtures previously prepared in a certain manner, e.g. B. proposed from sodium triphosphate and sodium silicate or sodium carbonate and sodium bicarbonate as well as water-insoluble compounds, for. B. zeolites, bentonites and silicon dioxide (Aerosil) and mixtures of the substances mentioned. Mixtures of water-soluble and water-insoluble Backing materials were used. DE 32 06 265 describes phosphate-free carrier grains which consist of 25 or 52% sodium carbonate or hydrogen carbonate, 10 to 50% zeolite, 0 to 18% sodium carbonate and 1 to 20% bentonite or 0.05 to 2% polyacrylate . DE 34 44 960-A1 discloses a granular adsorbent which is able to absorb high proportions of liquid to pasty detergent constituents, in particular nonionic surfactants, and (based on anhydrous substance) from 60 to 80% by weight of zeolite, 0.1 to 8% by weight .-% sodium silicate, 3 to 15 wt .-% of homo- or copolymers of acrylic acid, methacrylic acid and / or maleic acid, 8 to 18 wt .-% water and optionally up to 5 wt .-% of nonionic surfactants and by spray drying is available. EP 149 264 teaches that commercially available spray-dried zeolites and their mixtures with inorganic salts, such as sodium sulfate, can be used for the same purpose, the grain size and the bulk density of these spray products being within the usual range.

All of these processes are comparatively complex since first of all an aqueous slurry of the carrier substance is produced and this has to be converted into a granular, porous preliminary product by spray drying, ie with considerable energy expenditure. The second stage of the process, namely the spraying of the carrier grains with the nonionic surfactant, also requires additional equipment and time, especially since the diffusion of the nonionic surfactant takes place with a delay and adsorbates with a high proportion of nonionic surfactants only after a certain treatment and resting time sufficiently adeptly are. If, on the other hand, one starts from powdery precursors, for example finely crystalline zeolites or crystalline, water-soluble carrier salts, and treats them with liquid or melted nonionic surfactants under granulating conditions, ie with the powder particles being glued and cemented into larger granules, usually granules with a very uneven grain spectrum and reduced pouring properties are obtained. In addition, the absorption capacity of such granules for nonionic surfactants is considerably lower than that of sprayed carrier grains.

A known property of nonionic surfactants (NT) of the polyglycol ether derivative type is the formation of highly viscous gels if they are mixed with water in a ratio of NT: water such as 5: 1 to 1: 2. Such gels arise e.g. B. if nonionic surfactants are incorporated into the detergent slurry before spray drying. There they lead to a considerable increase in viscosity and thus put a strain on the spray drying process, since water is first added in order to reduce the viscosity and this has to be evaporated again with increased effort in the subsequent drying process. The gels also form when washing pastes containing high levels of nonionic surfactants are dissolved in the wash liquor. Depending on the composition of the paste, tough chunks of mucus can form, which dissolve only very slowly or, if they sink to the bottom, not at all in the wash liquor. They can also form on the surface of detergent particles with non-ionic surfactants adsorbed thereon, for example on the aforementioned carrier grains, if these carrier grains or their mixtures with other detergents are dissolved in water. The gels deteriorate the detergent behavior of the detergents, ie considerable amounts of detergent can remain undissolved in the dosing chambers of the washing machines. The tendency of the nonionic surfactants to form gels is therefore considered undesirable in specialist circles and efforts are concentrated on preventing their formation in the production of detergents as well as in use as far as possible.

It was therefore highly surprising that the formation of such gels can be used to advantage to produce detergent granules with a number of outstanding properties in a particularly simple manner.

The invention relates to a process for the production of free-flowing granules with a high bulk density, containing nonionic surfactants from the class of polyglycol ether derivatives, finely divided, water-soluble and / or water-insoluble solids and water, characterized in that (A) the nonionic surfactant is mixed with water may contain a portion, but less than 50% by weight of the total amount of water-soluble or water-insoluble solids in dissolved or dispersed form, mixed until a viscous gel phase is formed, whereupon (B) the remaining majority of the water-soluble or water-insoluble solids are added in powder form and mechanically processed until granules are formed, the weight ratio of nonionic surfactant and water in the gel phase to total solids present (calculated as anhydrous substance) being 25:75 to 65:35.

The weight ratio of nonionic surfactant and water in the gel phase to total solids present (calculated as anhydrous substance) is 30:70 to 60:40. In general, 0 to 40% by weight, preferably 0 to 30% by weight and in particular 5 to 25% by weight of the total solids used as an aqueous solution and / or aqueous dispersion in the formation of the gel phase (A) and the remaining main amount is added as a dry powder in the granulation phase (B) and granulated.

Suitable nonionic surfactants (part of gel phase A) according to the definition of the invention 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, thioalcohols, fatty acid amides and fatty acids. Alkylphenol polyglycol ethers with 5 to 12 carbon atoms in the alkyl radical and 3 to 15 ethylene glycol ether groups can also be used. The ethoxylates mentioned can also contain glycol ether groups derived from propylene oxide, for example as block groups or in statistical distribution. Finally, block polymers of ethylene oxide and propylene oxide, which are commercially available under the name Pluronics, are also suitable.

Preferred are liquid to pasty nonionic surfactants derived from alcohols with 12 to 18 ° C atoms. These alcohols can be saturated or olefinically unsaturated, linear or methyl-branched in the 2-position (oxo radical). Examples of these are C₁₂₋₁₈ coconut alcohol with 3 to 12 EO, C₁₆₋₁₈ tallow alcohol with 4 to 16 EO, oleyl alcohol with 4 to 12 EO and ethoxylation products of corresponding chain and EO distribution available from other native fatty alcohol mixtures. From the series of ethoxylated oxo alcohols, for example, those of the composition c₁₂₋₁₅ with 3 to 10 EO and C₁₄ - C₁₅ with 5 to 12 EO are suitable. Mixtures of low and highly ethoxylated alcohols are distinguished by increased detergency against both greasy and mineral stains, for example those made from tallow alcohol with 3 to 6 EO and tallow alcohol with 12 to 16 EO or C₁₃₋₁₅ oxo alcohol with 3 to 5 EO and C₁₂ ₋₁₄-oxo alcohol with 8 to 12 EO. Ethoxylates which contain EO groups and PO groups are also suitable hold, e.g. B. c₁₂₋₁₈ 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 3 to 20 and c those from 1 to 10 (b greater than a or c) mean.

Preferred solids are water-insoluble compounds and mixtures thereof with water-soluble salts. In a further preferred version, at least 50% by weight of the solids consist of finely divided water-insoluble solids.

Silica and silicates, preferably zeolites and layered silicates (bentonites) and mixtures thereof are suitable as finely divided, water-insoluble solids (component of the granulation phase B and optionally the gel phase A). Their grain size is preferably less than 100 μm, in particular less than 50 μm.

Suitable zeolites are those of the zeolite A type. Mixtures of zeolite NaA and NaX can also be used, the proportion of the zeolite Nah in such mixtures advantageously being below 30%, in particular below 20%. Suitable zeolites have no particles larger than 30 µm and consist of at least 80% 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 according to the information in DE 24 12 837, is in the range from 100 to 200 mg CaO / g.

Suitable layered silicates are of natural and synthetic origin, such as those used for. B. from DE 23 34 899 B2, EP 26 529 A1 and DE 35 26 405 A1 are known. Their usability as a carrier material is not limited to a special composition or structural formula.

Suitable water-soluble salts, which can preferably be used together with the aforementioned finely divided water-insoluble solids, are primarily builder salts which contain polyanionic groups or have a tendency to form associated polyanionic groups, such as alkali metal silicates, in particular sodium silicate, of the composition Na₂O: SiO₂ = 1 : 1 to 1: 3.4, preferably 1: 2 to 1: 3.3, alkali metal phosphates or polyphosphates, in particular pentasodium triphosphate, borates, such as sodium metaborate or sodium tetraborate. Usable representatives of this class are also the salts of organic polyacids or polymeric acids, such as sodium nitrilotriacetate, sodium citrate, sodium carboxymethyl cellulose, sodium polyacrylate and the sodium salts of copolymers of acrylic acid and maleic acid. Such salts generally cause a very strong increase in viscosity in aqueous solution with increasing concentration. They are preferably used together with water-insoluble solids. In this case, their proportion, based on the total solids present, can be up to 50% by weight, preferably up to 35% by weight.

Together with the water-insoluble solids, such water-soluble salts can also be used or used instead of the aforementioned polyanionic salts, which can be characterized as strongly polar, are essentially mono-anionic or dianionic, and which in aqueous solution only have a small concentration with increasing concentration Cause an increase in viscosity. Typical representatives of this class are sodium sulfate, sodium carbonate, sodium acetate, sodium nitrate and sodium chloride as well as corresponding potassium salts. However, their proportion, based on the total solids present, can be at most 35% by weight, preferably at most 25% by weight and in particular less than 20% by weight. Under no circumstances can they be the sole component or main Be part of the solid component or be used in the absence of a water-insoluble solid, since this leads to the destruction of the gel phase and the formation of sludge-like to lumpy mixtures. Such liquefied mixtures or moist lumps can no longer be converted into granules by simple mechanical processing. For the same reason, it is advantageous, if their use cannot be dispensed with, to mix these salts beforehand with the powdery, water-insoluble solids in the production of the granules, or at the same time with these solids or as the last component of the mixture after adding all other solids to mix in the gel phase.

Finally, minor amounts of anionic, zwitterionic, ampholytic or cationic surfactants can be added to the gel phase as solids. Examples of suitable anionic surfactants are soaps derived from saturated or monounsaturated C₁₂₋₂₂ fatty acids, alkylbenzenesulfonates with a linear C₉₋₁₃ alkyl group, salts of alpha-sulfofatty acids derived from saturated or monounsaturated C₁₂₋₁₈ fatty acids and their esters with saturated C₁₋₃ alcohols, C₁₂₋₁₈ alkanesulfonates, C₁₂₋₁₈ olefin sulfonates and C₁₂₋₁₈ alkyl sulfates or alkyl ether sulfates, said surfactants preferably being in the form of Na salts. The proportion of these surfactants, preferably sulfonate surfactants, can be up to 25% by weight, preferably up to 15% by weight, of the solids. Based on nonionic surfactants in the gel phase, the weight ratio of nonionic surfactant to anionic surfactant should not be less than 3: 2 and should preferably be less than 2: 1. Higher proportions of anionic surfactants can impair the formation of the gel phase or hinder the conversion of the gel phase into granular, free-flowing granules.

Finally, further solids can be incorporated into the gel phase (A) or added in the granulation phase (B), which are usually contained in small amounts in detergents and cleaning agents, such as optical brighteners, graying inhibitors, complexing agents, dyes, pigments, enzymes, defoamers and fragrances. Their proportion is generally less than 1% by weight, which is why they do not adversely affect the conversion of the gel phase into the granules.

In the preparation of the gel phase, the nonionic surfactant is expediently not only mixed with water, although this is fundamentally possible, but preferably an aqueous solution or dispersion is used which already contains part of the total solids or solid mixtures to be used. If zeolite is used as a solid, the preparation of the gel phase is preferably based on a stabilized aqueous dispersion (master batch), as described, for. B. is described in DE 25 27 388. Such dispersions, which are obtained as water-moist filter cakes in the zeolite synthesis, usually contain 35 to 55% by weight, preferably 40 to 50% by weight, of zeolite, calculated as anhydrous active substance (ie dewatered at the annealing temperature), 0.5 to 5 % By weight, preferably 1 to 4% by weight, of a dispersion stabilizer, in particular a nonionic surfactant, and water (difference up to 100%). In the same way, instead of the aqueous zeolite dispersion or simultaneously or in a mixture with it, aqueous solutions of alkali silicates, e.g. B. water glass solutions, aqueous solutions of anionic surfactants or mixtures of such solutions can be used to form the gel phase.

The granules can be produced in customary mixing and granulating devices, for example in cylindrical, horizontally or inclinedly arranged mixers with an axial, rotatable shaft, to which stirring and mixing elements are attached. The nonionic surfactant can be initially introduced and the water or a water-containing solid mixture can be added and mixed until it forms a gel or the reverse procedure can also be used. With further mixing, the dry, powdery solid component is then added to the gel formed and the mixing is continued until the desired granules have formed. Since the gelling of the geiphase (A) often takes some time, for example 10 to 30 seconds, to reach the maximum viscosity, in many cases it is also possible to work in such a way that the powdery solid component is placed in the mixer and immediately before prepared, still flowable gel phase is added and the mixing also continues until the formation of free-flowing granules. The variants mentioned can be carried out batchwise or continuously. In the discontinuous mode of operation, it is fundamentally possible and preferred to add the solids completely and not in portions over a longer period of time, which simplifies the method of operation.

The mixing and granulation can be carried out at room temperature, for example at 15 to 30 ° C. Heating or cooling during processing is not necessary.

The granules are formed spontaneously and, apart from stirring or mixing, do not require any special measures. The time until the formation of the uniform granules depends to a certain extent on the total amount of solids, in particular, however depends on the proportion of powdered solids added and, with solids additions of 35 to 50% by weight, based on the finished granules, is 30 seconds to 3 minutes. With a further increase in the solids content, the granulation time increases exponentially and takes 10 to 15 minutes for solids contents of 65 to 75% by weight. In general, higher solids contents than 75% by weight are not necessary and in many cases are not appropriate either. Furthermore, it is neither necessary nor advantageous to continue mixing after the formation of uniform, free-flowing granules. It has been shown, in particular in the case of mixtures with low solids contents, that the formation of the granules passes through an optimum in terms of their flow behavior and their uniformity. A further mechanical processing then leads to softening of the already formed grains and to clumping or sticking to the mixer tools, combined with a clear decrease in the pourability and the bulk weight.

In practice, the procedure is expediently such that the granulation is continued until the bulk density of the granules has reached a maximum. This maximum is also characterized by an optimal grain structure and flowability and can be determined by a simple preliminary test if necessary. This state is easily recognizable visually, since the granules appear particularly uniform in the mixer and trickle easily and no material adheres to the mixer wall or the mixing tools. At the same time, this condition is characterized by a minimal power requirement for operating the mixer and can also be easily determined in this way.

In the area of the optimum, the granules can be removed from the mixer without residues and removed from the outflow opening. The inside wall of the empty mixer and the mixing tools are usually bare afterwards. This effect is extremely surprising, especially when you recall the initial stage when the gel sticks to the tools and the mixer shaft as a tough, pasty or lumpy mass.

In spite of their high content of liquid constituents, for example more than 50% of water and liquid nonionic surfactants, the granules produced in the manner indicated are extremely free-flowing and generally do not require any aftertreatment or drying. If a lower water content of the granules is desirable, for example if they are to be mixed further with moisture-sensitive components or powder mixtures, drying can also be carried out. This drying can take place, for example, in a fluidized bed dryer. In this case, it is not necessary to use heated air. Furthermore, the granules obtained or the post-dried granules can also be dusted or coated with other powdery constituents, such as finely divided silica or pigments (including colored ones). They have bulk densities of 600 to 1,000 g / l, preferably 650 to 900 g / l, and are outstandingly suitable as a basic component or additional powder component in detergents of the so-called "heavy powder" type. These heavy powders are enjoying growing interest, since they require much less packaging volume and save packaging material compared to conventional spray powders with the same washing performance. Regardless of their high density, the granules have excellent dissolving power in cold tap water and draw are characterized by good "washing-in behavior", ie they do not form residues in the washing-in devices in automatic washing machines.

The method offers further advantages in that it permits the gentle processing of those substances which lose their effect when spray-dried or which interact with other substances. The decomposable or ineffective additives include enzymes, bleaching agents, bleach activators, foam inhibitors and fragrances. Mixtures of zeolite and alkali silicate, which react during spray drying to form coarse-particle and poorly redispersible agglomerates, can be processed well together without these disadvantages. The use of nonionic surfactants with a low degree of ethoxylation, which, owing to their volatility in water vapor, lead to smoke formation in the exhaust air from the spray towers ("pluming"), is completely unproblematic in the process according to the invention.

Examples

• 1. Im Labormischer wurden 30 GT einer wäßrigen Zeolith-Dispersion, enthaltend 15 GT Zeolith (wasserfrei gerechnet), 0,5 GT ethoxy­lierten Talgalkohols (5 EO-Gruppen) als Dispersionsstabilisator und 14,5 GT Wasser mit 20 GT eines ethoxylierten C₁₂₋₁₈-Fettal­kohols + 5 EO (Cocos-Talgalkohol 1 : 4) vermischt. Im Verlauf von 20 - 30 sec bildete sich eine Gelphase aus. Diesem Gel wurden unter ständigem weiteren Mischen 50 GT eines sprühge­trockneten Zeoliths (Wassergehalt 21 Gew.-%) zugesetzt. Nach einer Mischzeit von ca. 20 sec setzte die spontane Granulat­bildung ein. Der Anstieg des Schüttgewichts (in g/l) in Abhän­gigkeit von der Granulierzeit in sec nach Zusatz des trockenen Zeoliths verlief wie folgt:

sec 20 30 40 50 60 70 80 100 g/l 650 730 790 835 875 900 900 840 In the following examples, both a laboratory mixer with a capacity of 2 liters and a mixer (type: Lödige) with a capacity of 135 liters were used. Both mixers consisted of a cylindrical, horizontally arranged container with an axially arranged shaft equipped with mixing blades. Their rotation speed was 300 rpm in the laboratory mixer and 120 rpm in the large mixer. With regard to the mode of operation, the time required for granulation and the properties of the granules, there were no significant differences in the two test series. In the following examples, "GT" stands for parts by weight, "sec" for seconds.

• 1. In the laboratory mixer, 30 pbw of an aqueous zeolite dispersion containing 15 pbw of zeolite (calculated as anhydrous), 0.5 pbw of ethoxylated tallow alcohol (5 EO groups) as a dispersion stabilizer and 14.5 pbw of water with 20 pbw of an ethoxylated C₁₂₋₁₈ -Fatty alcohol + 5 EO (coconut tallow alcohol 1: 4) mixed. A gel phase formed in the course of 20-30 seconds. 50 pbw of a spray-dried zeolite (water content 21% by weight) were added to this gel with constant further mixing. After a mixing time of approx. 20 seconds, the spontaneous formation of granules started. The increase in bulk density (in g / l) as a function of the granulation time in seconds after adding the dry zeolite was as follows:

sec 20th 30th 40 50 60 70 80 100 g / l 650 730 790 835 875 900 900 840

After 50 seconds, the granules were already free-flowing. Up to a mixing time of 70 seconds, ie until the maxi paint bulk density, the flowability increased even further. After mixing for a long time, the granules softened and clumped, at the same time the bulk density decreased again and the energy requirement of the mixer increased.

The granules obtained after mixing times of 60 seconds had the following grain spectrum determined by sieve analysis. The proportions are those which remain on a sieve of the specified mesh size or which fall through the sieve at "below 0.1". mm 1.6 0.8 0.4 0.2 0.1 less than 0.1 % By weight 3rd 32 38 24th 2nd 1

• 2. In gleicher Weise wie in Beispiel 1 beschrieben, wurden 10 GT des gleichen nichtionischen Tensids mit 40 GT der Zeolith-Dis­persion unter Gelbildung vermischt. Anschließend wurden 50 GT feinpulvriger Bentonit zugemischt. Das nach 50 sec Granulier­dauer erhaltene Granulat wies ein Schüttgewicht von 660 g/l auf.
• 3. 20 GT eines mit 5 Mol EO umgesetzten Oleyl-Stearyl-Alkoholge­misches (Jodzahl = 50) wurden mit 30 GT der wäßrigen Zeolith-­Dispersion unter Gelbildung vermischt. Das unter Zusatz von 50 GT sprühgetrockneten Zeoliths innerhalb von 50 sec hergestellte Granulat wies ein Schüttgewicht von 840 g/l auf.
• 4. 20 GT c₁₂₋₁₄-Fettalkohol + 3 EO wurden mit 30 GT wäßriger Zeo­lith-Dispersion zu einem Gel vermischt und anschließend mit 50 GT sprühgetrocknetem Zeolith versetzt. Das nach 50 sec Granu­lierzeit erhaltene Granulat wies ein Schüttgewicht von 820 g/l auf.
• 5. 18 GT des in Beispiel 1 verwendeten Fettalkohol-Ethoxylates und 27 GT Zeolith-Dispersion wurden zu einem Gel vermischt. Nach Zumischen von 45 GT sprühgetrocknetem Zeolith und 10 GT calci­nierter Soda und einer Granulationszeit von 60 sec wurde ein rieselfähiges Granulat mit einem Schüttgewicht von 800 g/l er­halten.
• 6. Ein durch Mischen von 20 GT des in Beispiel 1 verwendeten Fett­alkohol-Ethoxylates, 20 GT wäßriger Zeolith-Dispersion und 10 GT einer Wasserglaslösung (Na₂O : SiO₂ = 1 : 3,3, Wassergehalt 65,5 Gew.-%) erhaltenes Gel wurde unter Zusatz von 50 GT sprüh­getrocknetem Zeolith im Verlauf von 60 sec granuliert. Die gut rieselfähigen, in Wasser schnell und ohne Anzeichen einer Agglo­merat-Bildung zerfallenden Granulate wiesen ein Schüttgewicht von 850 g/l auf.
• 7. Aus 12 GT des Fettalkoholethoxylates gemäß Beispiel 1 und 20 GT einer wäßrigen Tensidaufschlämmung, enthaltend 31 Gew.-% eines Gemisches aus Alpha-Sulfofettsäuremethylester (Na-Salz) und Alphasulfofettsäure (Di-Na-Salz) aus gesättigetem C₁₆₋₁₈-Fett­säuren (Mischungsverhältnis Mono-Na-Salz zu Di-Na-Salz 4 : 1), wurde ein Gel hergestellt. Nach Zusatz von 68 GT sprühgetrock­netem Zeolith und Granulation (50 sec) wurde ein rieselfähiges Granulat mit einem Schüttgewicht von 810 g/l erhalten.
• 8. Das Beispiel 1 wurde in einem Granuliermischer (Lödige-Mi­scher^(R)) mit einem Fassungsvermögen von 135 Litern in der Weise wiederholt, daß der Mischer zunächst mit dem sprühge­trockneten Zeolith-Pulver gefüllt wurde. In einem weiteren Mischgefäß wurde das Fettalkoholethoxylat mit der wäßrigen Zeolith-Dispersion vorgemischt und das sich bildende Gel in­nerhalb 10 - 15 sec im noch fließfähigen Zustand in den Gra­nuliermischer überführt. Nach einer Misch- und Granulierzeit von 70 sec wurde ein homogenes, ausgezeichnet rieselfähiges Granulat mit einem Schüttgewicht von 900 g/l erhalten, das in seinen übrigen Korneigenschaften dem Granulat gemäß Beispiel 1 entsprach.

The clump test (loading a powder fill in a cylindrical container with a weight) gave the optimum value O. The mixer had no adhering residues and could be loaded again without intermediate cleaning.

• 2. In the same way as described in Example 1, 10 pbw of the same nonionic surfactant was mixed with 40 pbw of the zeolite dispersion to form a gel. 50 pbw of finely powdered bentonite were then mixed in. The granules obtained after a granulation time of 50 seconds had a bulk density of 660 g / l.
• 3. 20 pbw of an oleyl-stearyl-alcohol mixture reacted with 5 mol of EO (iodine number = 50) were mixed with 30 pbw of the aqueous zeolite dispersion to form a gel. The granules produced with the addition of 50 pbw of spray-dried zeolite within 50 seconds had a bulk density of 840 g / l.
• 4. 20 pbw of c₁₂₋₁₄ fatty alcohol + 3 EO were mixed with 30 pbw of aqueous zeolite dispersion to form a gel and then mixed with 50 pbw of spray-dried zeolite. The granules obtained after a granulation time of 50 seconds had a bulk density of 820 g / l.
• 5. 18 pbw of the fatty alcohol ethoxylate used in Example 1 and 27 pbw of the zeolite dispersion were mixed to form a gel. After 45 pbw of spray-dried zeolite and 10 pbw of calcined soda and a granulation time of 60 sec, free-flowing pellets with a bulk density of 800 g / l were obtained.
• 6. A gel obtained by mixing 20 pbw of the fatty alcohol ethoxylate used in Example 1, 20 pbw of aqueous zeolite dispersion and 10 pbw of a water glass solution (Na₂O: SiO₂ = 1: 3.3, water content 65.5% by weight) was granulated with the addition of 50 pbw of spray-dried zeolite over the course of 60 seconds. The free-flowing granules, which disintegrate quickly in water and show no signs of agglomerate formation, had a bulk density of 850 g / l.
• 7. From 12 pbw of the fatty alcohol ethoxylate according to Example 1 and 20 pbw of an aqueous surfactant slurry containing 31% by weight of a mixture of alpha-sulfofatty acid methyl ester (sodium salt) and alpha-sulfofatty acid (di-sodium salt) from saturated C₁₆₋₁₈ fatty acids (Mixing ratio mono-Na salt to di-Na salt 4: 1), a gel was prepared. After the addition of 68 pbw of spray-dried zeolite and granulation (50 sec), free-flowing granules with a bulk density of 810 g / l were obtained.
• 8. Example 1 was repeated in a granulating mixer (Lödige mixer ^(R) ) with a capacity of 135 liters in such a way that the mixer was first filled with the spray-dried zeolite powder. In a further mixing vessel, the fatty alcohol ethoxylate was premixed with the aqueous zeolite dispersion and the gel which formed was transferred to the granulating mixer in the still free-flowing state within 10-15 seconds. After a mixing and granulating time of 70 sec, homogeneous, free-flowing granules with a bulk density of 900 g / l were obtained, which corresponded to the granules according to Example 1 in their other grain properties.

Claims (10)

1. A process for the production of free-flowing granules with a high bulk density, containing nonionic surfactants from the class of polyglycol ether derivatives and finely divided, water-soluble and / or water-insoluble solids and water, characterized in that (A) the nonionic surfactant with water, which may be a Part, but less than 50 wt .-% of the total amount of water-soluble or water-insoluble solids in dissolved or dispersed form, mixed until a viscous gel phase is formed, whereupon (B) the remaining majority of the water-soluble or water-insoluble solids in solid, powdery form and mechanically processed until the formation of granules, the weight ratio of nonionic surfactant and water in the gel phase to total solids present (calculated as anhydrous substance) being 25:75 to 65:35. 2. The method according to claim 1, characterized in that the ratio of nonionic surfactant and water in the gel phase (A) to the total solids present is 30:70 to 60:40. 3. The method according to claim 1 and 2, characterized in that 0 to 40 wt .-%, preferably 0 to 30 wt .-% and in particular 5 to 25 wt .-% of the total solids used in the formation of the gel phase (A ) is used and the remaining main amount is added as a dry powder in the granulation phase (B). 4. The method according to claim 3, characterized in that one uses water-insoluble solids with a grain size below 100 microns, preferably below 50 microns. 5. The method according to claim 4, characterized in that fine crystalline zeolite, bentonite or mixtures thereof are used as the water-insoluble solid. 6. The method according to claim 1 to 4, characterized in that the mixing of the gel phase with the powdery solid is mixed until the bulk density of the granules formed has reached a maximum value. 7. The method according to one or more of claims 1 to 4, characterized in that the nonionic surfactant is mixed with an aqueous dispersion of finely crystalline zeolite to form the gel phase, the aqueous dispersion 35 to 55 wt .-% zeolite, based on anhydrous Substance containing 0.5 to 5 wt .-% of a nonionic surfactant acting as a dispersion stabilizer and 64.5 to 40 wt .-% water. 8. Granules produced according to one or more of claims 1 to 6. 9. Granules according to claim 8, characterized by a bulk density of 600 to 1000 g / l, preferably from 650 to 900 g / l. 10. Granular washing and cleaning agent containing granules according to claims 8 to 9.