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EP0536110A1 - Process for manufacturing tenside-containing granulates. - Google Patents

Process for manufacturing tenside-containing granulates.

Info

Publication number
EP0536110A1
EP0536110A1 EP89911804A EP89911804A EP0536110A1 EP 0536110 A1 EP0536110 A1 EP 0536110A1 EP 89911804 A EP89911804 A EP 89911804A EP 89911804 A EP89911804 A EP 89911804A EP 0536110 A1 EP0536110 A1 EP 0536110A1
Authority
EP
European Patent Office
Prior art keywords
water
granules
gel phase
solids
soluble
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP89911804A
Other languages
German (de)
French (fr)
Other versions
EP0536110B1 (en
Inventor
Elmar Wilms
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 EP0536110A1 publication Critical patent/EP0536110A1/en
Application granted granted Critical
Publication of EP0536110B1 publication Critical patent/EP0536110B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites

Definitions

  • the invention relates to a process for the production of 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 subsequent drying. They can be used directly as detergents or cleaning agents or as additional powder components in composite detergents and cleaning agents.
  • Granules containing carrier substances and liquid or pasty 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.
  • DE 3444960-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% by weight of homo- or copolymers of acrylic acid, methacrylic acid and / or maleic acid, 8 to 18% by weight of water and optionally up to 5% by weight of nonionic surfactants and can be obtained by spray drying .
  • 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.
  • powdery precursors for example finely crystalline zeolites or crystalline, water-soluble carrier salts
  • 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.
  • the absorption capacity of such granules for nonionic surfactants is considerably lower than that of sprayed carrier grains.
  • nonionic surfactants 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 in the subsequent drying process with increased effort.
  • the gels also form in the wash liquor when dissolving wash pastes containing high levels of nonionic surfactants.
  • 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 nonionic surfactants adsorbed thereon, for example on the above-mentioned 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 detergent production 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 is 30:70 to 60:40.
  • 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) are alkoxylation products with 10 to 20 carbon atoms in the hydrophobic radical and 3 to 20 glycol ether groups.
  • ethoxylation products of alcohols 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.
  • block polymers of ethylene oxide and propylene oxide which are commercially available under the name Pluronics, are also suitable.
  • liquid to pasty nonionic surfactants derived from alcohols with 12 to 18 carbon atoms.
  • These alcohols can be saturated or olefinically unsaturated, linear or methyl-branched in the 2-position (oxo radical).
  • oxo radical oxo radical
  • examples of these are C 12-18 coco alcohol with 3 to 12 EO, C 16-18 tallow alcohol with 4 to 16 EO, oleyl alcohol with A 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 C 12-15 with 3 to 10 EO and C 14 - C 15 with 5 to 12 EO are suitable.
  • Mixtures of low and highly ethoxylated alcohols are characterized by increased detergency against both greasy and mineral soiling, for example those made of tallow alcohol with 3 to 6 E0 and tallow alcohol with 12 to 16 E0 or C 13-15 oxo alcohol with 3 to 5 EO and C 12-14 -0xoalcohol with 8 to 12 E0.
  • Ethoxylates which contain EO groups and PO groups are also suitable hold, e.g. B. C 12-18 alcohols of the formula R- (PO) a - (EO) b or R-
  • Preferred solids are water-insoluble compounds and their mixtures with water-soluble salts. In a further preferred version, at least 50% by weight of the solids consist of finely divided water-insoluble solids.
  • Silicic acid and silicates preferably zeolites and layered silicates (bentonites) and mixtures thereof are suitable as finely divided, water-insoluble solids (constituent of the granulation phase B and optionally the gel phase A).
  • Their grain size is preferably less than 100 ⁇ m, in particular less than 50 ⁇ m.
  • 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 according to the information in DE 24 12837, 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 carrier material is not limited to a special composition or structural formula.
  • alkali metal silicates in particular sodium silicate
  • 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.
  • 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 have only a small concentration in aqueous solution 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.
  • 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.
  • anionic, zwitterionic, ampholytic or cationic surfactants can be added to the gel phase as solids.
  • suitable anionic surfactants are soaps derived from saturated or monounsaturated C 12-22 fatty acids, alkylbenzenesulfonates with a linear C 9-13 alkyl group, salts of alpha sulfofatty acids derived from saturated or monounsaturated C 12-18 -Fatty acids and their esters with saturated C 1-3 alcohols, C 42-18 alkane sulfonates , C 12-18 olefin sulfonates and C 12-18 alkyl sulfates or alkyl ether sulfates, the surfactants mentioned preferably being in the form of Na salts.
  • the proportion of these surfactants can be up to 25% by weight, preferably up to 15% by weight, of the solids.
  • 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.
  • solids can be incorporated into the gel phase (A) or added to 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.
  • 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.
  • the nonionic surfactant is expediently not only mixed with water, although this is fundamentally possible, but an aqueous solution or dispersion is preferably used which already contains part of the total solids or solid mixtures to be used. If Zeoltth 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%).
  • 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 mixers which are arranged horizontally or inclined with respect to the horizontal and have an axial, rotatable shaft to which stirring and mixing elements are attached. You can add the nonionic surfactant and add the water or a water-containing solid mixture and mix until it forms a gel or proceed in reverse order. 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.
  • the gelling of the gel phase (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 pulverulent solid component is placed in the mixer and the immediately prepared one , 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. It is not necessary to heat or cool during processing.
  • the granules are formed spontaneously and require no special measures other than stirring or mixing.
  • the time until the formation of the uniform granules depends to a certain extent on the total amount of solids, in particular, however from the proportion of powdery solids added and is from 30 to 3 minutes for solids additions of 35 to 50% by weight, based on the finished granules.
  • 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.
  • the procedure is expediently such that 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.
  • the granules can be removed from the mixer without residue 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.
  • the granules produced in the stated manner are outstandingly 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 further mixed 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 resulting or the after-dried granules can also be dusted or coated with other powdery constituents, such as finely divided silica or pigments (including colored ones).
  • 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-grained and poorly redispersible agglomerates, can be processed well together without these disadvantages.
  • 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.
  • the granules were already free-flowing. Up to a mixing time of 70 seconds, ie until the maxi paint bulk density, the pourability 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",
  • the clump test (loading a powder fill in a cylindrical container with a weight) gave the optimum value 0.
  • the mixer had no adhering residues and could be loaded again without intermediate cleaning.
  • Example 2 In the same way as described in Example 1, 10 parts by weight of the same nonionic surfactant were mixed with 40 parts by weight 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.
  • 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.
  • the fatty alcohol ethoxylate was premixed with the aqueous zeolite dispersion and the gel which was formed was transferred to the granulating mixer in the flowable state within 10-15 seconds.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Medicinal Preparation (AREA)
  • Cosmetics (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Glanulating (AREA)
  • Colloid Chemistry (AREA)

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

"Verfahren zur Herstellung von tensidhaltioen Granulaten"  "Process for the production of surfactant-containing granules"
Die Erfindung betrifft ein Verfahren zur Herstellung von Granulaten, die ungeachtet ihres hohen Gehaltes an nichtionischen Tensiden und adsorbiertem Wasser gut rieselfähig sind, ein hohes Schüttgewicht und ein sehr homogenes Kornspektrum aufweisen. Die Granulate sind durch einen vergleichsweise einfachen Mischprozeß erhältlich und bedürfen keiner Nachtrocknung. Sie können unmittelbar als Wasch- oder Reinigungsmittel oder als zusätzliche Pulverkomponente in zusammengesetzten Wasch- und Reinigungsmitteln eingesetzt werden. The invention relates to a process for the production of 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 subsequent drying. They can be used directly as detergents or cleaning agents or as additional powder components in composite detergents and cleaning agents.
Granulate mit einem Gehalt an Trägersubstanzen und daran adsorbierten flüssigen oder pastenförmigen nichtionischen Tensiden, sind bekannt. Zu ihrer Herstellung wurden Verfahren entwickelt, bei denen das flüssige bzw. geschmolzene nichtionische Tensid auf ein zuvor sprühgetrocknetes Pulver aufgesprüht oder mit einer pulverförmigen Trägersubstanz unter granulierenden Bedingungen vermischt wird. Als Trägersubstanz wurden lockere, insbesondere sprühgetrocknete, wasserlösliche Salze, wie Phosphate, Silikate, Borate bzw. Perborate oder in bestimmter Weise zuvor hergestellte Salzgemische, z. B. solche aus Natriumtriphosphat und Natriumsilikat oder aus Natriumcarbonat und Natriumbicarbonat ebenso vorgeschlagen wie wasserunlösliche Verbindungen, z. B. Zeolithe, Bentonite und Siliciumdioxid (Aerosil) sowie Gemische der genannten Stoffe. Auch Geraische aus wasserlöslichen und wasserunlöslichen Trägermaterialien wurden verwendet. In DE 32 06 265 sind phosphatfreie Tragerkörner beschrieben, die aus 25 bzw. 52 % Natriumcarbonat bzw. -hydrogencarbonat, 10 bis 50 % Zeolith, 0 bisGranules containing carrier substances and liquid or pasty 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. those made of 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. Also Geraische from 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 % Natriumcarbonat und 1 bis 20 % Bentonit bzw. 0,05 bis 2 % Polyacrylat bestehen. Aus DE 3444960-A1 ist ein körniges Adsorptionsmittel bekannt, das hohe Anteile an flüssigen bis pastösen Waschmittelbestandteilen, insbesondere nichtionischen Tensiden aufzunehmen vermag und (auf wasserfreie Substanz bezogen) aus 60 bis 80 Gew.-% Zeolith, 0,1 bis 8 Gew.-% Natriumsilikat, 3 bis 15 Gew.-% an Homo- oder Copolymeren der Acrylsäure, Methacrylsäure und/oder Maleinsäure, 8 bis 18 Gew.-% Wasser und gegebenenfalls bis zu 5 Gew.-% an nichtionischen Tensiden enthält und durch Sprühtrocknung erhältlich ist. Das EP 149 264 lehrt, daß man für den gleichen Zweck handelsübliche sprühgetrocknete Zeolithe und deren Gemische mit anorganischen Salzen, wie Natriumsulfat, verwenden kann, wobei die Korngröße und das Schüttgewicht dieser Sprühprodukte im üblichen Rahmen liegen. 18% sodium carbonate and 1 to 20% bentonite or 0.05 to 2% polyacrylate. DE 3444960-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% by weight of homo- or copolymers of acrylic acid, methacrylic acid and / or maleic acid, 8 to 18% by weight of water and optionally up to 5% by weight of nonionic surfactants and can be obtained by spray drying . 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.
Alle diese Verfahren sind vergleichsweise aufwendig, da zunächst ein wäßriger Slurry der Trägersubstanz hergestellt und dieser durch Sprühtrocknung, d. h. mit erheblichem Energieaufwand, in ein körniges, poröses Vorprodukt überführt werden muß. Auch die zweite Verfahrensstufe, nämlich das Besprühen der Trägerkörner mit dem nichtionischen Tensid, erfordert einen zusätzlichen apparativen und zeitlichen Aufwand, zumal das Eindiffundieren des nichtionischen Tensides mit Verzögerung erfolgt und Adsorbate mit hohem Anteil an nichtionischen Tensiden erst nach einer gewissen Behandlungs- und Ruhezeit hinreichend rieselfähig sind. Geht man hingegen von pulverförmigen Vorprodukten aus, beispielsweise von fein- kristallinen Zeolithen oder kristallinen, wasserlöslichen Trägersalzen und behandelt diese mit flüssigen oder geschmolzenen nichtionischen Tensiden unter granulierenden Bedingungen, d. h. unter Verkleben und Verkitten der Pulverpartikel zu größeren Granulaten, so werden meist Granulate mit sehr ungleichem Kornspektrum und verminderten Rieseleigenschaften erhalten. Außerdem ist das Aufnahmevermögen derartiger Granulate für nichtionische Tenside erheblich geringer als die von gesprühten Trägerkörnern. 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 spraying 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 become sufficiently free-flowing after a certain treatment and rest period are. If, on the other hand, one starts with 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.
Eine bekannte Eigenschaft nichtionischer Tenside (NT) vom Typ der Polyglykoletherderivate ist die Ausbildung hochviskoser Gele, wenn man sie mit Wasser etwa im Verhältnis NT : Wasser wie 5 : 1 bis 1 : 2 vermischt. Solche Gele entstehen z. B., wenn man nichtionische Tenside vor einer Sprühtrocknung in den Waschmittelslurry einarbeitet. Sie führen dort zu einem erheblichen Viskositätsanstieg und belasten somit den Sprühtrocknungsprozeß, da man zusätzlich Wasser zwecks Viskositätsverminderung zunächst zusetzen und dieses im anschließenden Trocknungsprozeß mit erhöhtem Aufwand wieder verdampfen muß. Die Gele entstehen auch beim Auflösen von Waschpasten, die hohe Anteile an nichtionischen Tensiden enthalten, in der Waschlauge. Je nach Zusammensetzung der Paste können sich dabei zähe Schleimbrocken bilden, die sich nur sehr langsam oder, falls sie zu Boden sinken, überhaupt nicht in der Waschlauge auflösen. Sie können sich auch auf der Oberfläche von Waschmittelpartikeln mit daran adsorbierten nichtionischen Tensiden ausbilden, beispielsweise auf den vorerwähnten Trägerkörnern, wenn man diese Trägerkörner bzw. deren Gemische mit anderen Waschmitteln in Wasser löst. Die Gele verschlechtern das Einspülverhalten der Mittel, d. h. es können erhebliche Mengen an Waschmittel in den Dosierkammern der Waschmaschinen ungelöst zurückbleiben. Die Neigung der nichtionischen Tenside zur Gelbildung gilt daher in Fachkreisen als unerwünscht und die Anstrengungen konzentrieren sich darauf, ihre Entstehung bei der Waschmittelproduktion ebenso wie bei der Anwendung möglichst zu verhindern. Es war daher im hohen Maße überraschend, daß man die Entstehung solcher Gele mit Vorteil dazu ausnutzen kann, Waschmittelgranulate mit einer Reihe hervorragender Eigenschaften in besonders einfacher Weise herzustellen. 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 in the subsequent drying process with increased effort. The gels also form in the wash liquor when dissolving wash pastes containing high levels of nonionic surfactants. 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 nonionic surfactants adsorbed thereon, for example on the above-mentioned 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 detergent production 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.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von rieselfähigen Granulaten mit hohem Schüttgewicht, enthaltend nichtionische Tenside aus der Klasse der Polyglykoletherderivate, feinteilige, wasserlösliche und/oder wasserunlösliche Feststoffe und Wasser, dadurch gekennzeichnet, daß man (A) das nichtionische Tensid mit Wasser, das ggf. einen Teil, jedoch weniger als 50 Gew.-% der Gesamtmenge der wasserlöslichen bzw. wasserunlöslichen Feststoffe in gelöster bzw. dispergierter Form enthalten kann, bis zur Ausbildung einer viskosen Gelphase vermischt, worauf man (B) die verbleibende Hauptmenge der wasserlöslichen bzw. wasserunlös- lichen Feststoffe in pulvriger Form hinzumischt und bis zur Ausbildung von Granulaten mechanisch Bearbeitet, wobei das Gewichtsverhältnis von nichtionischem Tensid und Wasser in der Gelphase zu insgesamt anwesenden Feststoffen (berechnet als wasserfreie Substanz) 25 : 75 bis 65 : 35 beträgt. 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.
Vorzugsweise beträgt das Gewichtsverhältnis von nichtionischem Tensid und Wasser in der Gelphase zu insgesamt anwesenden Feststoffen (berechnet als wasserfreie Substanz), 30 : 70 bis 60 : 40. Im allgemeinen werden 0 bis 40 Gew.-%, vorzugsweise 0 bis 30 Gew.-% und insbesondere 5 bis 25 Gew.-% der insgesamt verwendeten Feststoffe als wäßrige Lösung und/oder wäßrige Dispersion bei der Bildung der Gelphase (A) eingesetzt und die verbleibende Hauptmenge als trockenes Pulver in der Granulierphase (B) hinzugemischt und granuliert. Geeignete nichtionische Tenside (Bestandteil der Gelphase A) gemäß Erfindungsdefinition sind Alkoxylierungsprodukte mit 10 bis 20 Kohlenstoffatomen im hydrophoben Rest und 3 bis 20 Glykolethergruppen. Hierzu zählen Ethoxylierungsprodukte von Alkoholen, vicinalen Diolen, Aminen, Thioalkoholen, Fettsäureamiden und Fettsäuren. Weiterhin sind Alkylphenolpolyglykolether mit 5 bis 12 C-Atomen im Alkylrest und 3 bis 15 Ethylenglykolethergruppen brauchbar. Die genannten Ethoxylate können auch vom Propylenoxid abgeleitete Glykolethergruppen enthalten, beispielsweise als Block-Gruppen oder in statistischer Verteilung. Schließlich kommen auch Blockpolymere aus Ethylenoxid und Propylenoxid, die unter der Bezeichnung Pluronics handelsüblich sind, in Betracht. 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.
Bevorzugt sind flüssige bis pastöse nichtionische Tenside, die von Alkoholen mit 12 bis 18 C-Atomen abgeleitet sind. Diese Alkohole können gesättigt oder olefinisch ungesättigt, linear oder in 2- Stel lung methyl verzweigt (Oxo-Rest) sein. Beispiele hierfür sind C12-18-Cocosalkohol mit 3 bis 12 EO, C16-18-Talgalkohol mit 4 bis 16 EO, Oleylalkohol mit A bis 12 EO sowie aus anderen nativen Fettalkoholgemischen erhältliche Ethoxylierungsprodukte entsprechender Ketten- und EO-Verteilung. Aus der Reihe der ethoxylierten Oxoalkohole sind beispielsweise solche der Zusammensetzung C12-15 mit 3 bis 10 EO und C14 - C15 mit 5 bis 12 EO geeignet. Durch eine erhöhte Waschkraft sowohl gegenüber fettartigen und mineralischen Anschmutzungen zeichnen sich Gemische aus niedrig und hoch ethoxylierten Alkoholen aus, beispielsweise solche aus Talgalkohol mit 3 bis 6 E0 und Talgalkohol mit 12 bis 16 E0 oder C13-15-Oxoalkohol it 3 bis 5 EO und C12-14-0xoalkohol mit 8 bis 12 E0. Weiterhin sind auch Ethoxylate geeignet, die EO-Gruppen und PO-Gruppen ent halten, z. B. C12-18-Alkohole der Formel R-(PO)a-(EO)b bzw. R-Preferred are liquid to pasty nonionic surfactants derived from alcohols with 12 to 18 carbon atoms. These alcohols can be saturated or olefinically unsaturated, linear or methyl-branched in the 2-position (oxo radical). Examples of these are C 12-18 coco alcohol with 3 to 12 EO, C 16-18 tallow alcohol with 4 to 16 EO, oleyl alcohol with A 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 C 12-15 with 3 to 10 EO and C 14 - C 15 with 5 to 12 EO are suitable. Mixtures of low and highly ethoxylated alcohols are characterized by increased detergency against both greasy and mineral soiling, for example those made of tallow alcohol with 3 to 6 E0 and tallow alcohol with 12 to 16 E0 or C 13-15 oxo alcohol with 3 to 5 EO and C 12-14 -0xoalcohol with 8 to 12 E0. Ethoxylates which contain EO groups and PO groups are also suitable hold, e.g. B. C 12-18 alcohols of the formula R- (PO) a - (EO) b or R-
(EO)b-(PO)c, worin a Zahlen von 1 bis 3, b solche von 3 bis 20 und c solche von 1 bis 10 (b größer als a bzw. c) bedeuten. (EO) b - (PO) c , in which a is a number from 1 to 3, b is from 3 to 20 and c is from 1 to 10 (b is greater than a or c).
Als Feststoffe kommen bevorzugt wasserunlösliche Verbindungen sowie deren Gemische mit wasserlöslichen Salzen infrage. In einer weiteren bevorzugten Version bestehen wenigstens 50 Gew.-% der Feststoffe aus feinteiligen wasserunlöslichen Feststoffen. Preferred solids are water-insoluble compounds and their mixtures with water-soluble salts. In a further preferred version, at least 50% by weight of the solids consist of finely divided water-insoluble solids.
Als feinteilige, wasserunlösliche Feststoffe (Bestandteil der Granulierphase B sowie fakultativ der Gelphase A) kommen Kieselsäure und Silikate, vorzugsweise Zeolithe und Schichtsilikate (Bentonite) sowie deren Gemische in Frage. Ihre Korngröße liegt vorzugsweise unter 100 μm, insbesondere unter 50 μm. Silicic acid and silicates, preferably zeolites and layered silicates (bentonites) and mixtures thereof are suitable as finely divided, water-insoluble solids (constituent 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.
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 μm auf und bestehen zu wenigstens 80 % aus Teilchen einer Größe von weniger als 10 μm. Ihre mittlere Teilchengrδße (Volumenverteilung, Meßmethode: Coulter Counter) beträgt 1 bis 10 μm. Ihr Calciumbindevermögen, das nach den Angaben der DE 24 12837 bestimmt wird, liegt im Bereich von 100 bis 200 mg CaO/g. 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 according to the information in DE 24 12837, is in the range from 100 to 200 mg CaO / g.
Geeignete Schichtsilikate sind solche natürlichen und synthetischen Ursprungs, wie sie z. B. aus DE 23 34 899 B2, EP 26 529 A1 und DE 35 26 405 A1 bekannt sind. Ihre Verwendbarkeit als Trägermaterial ist nicht auf eine spezielle Zusammensetzung bzw. Strukturformel beschränkt. Geeignete wasserlösliche Salze, die bevorzugt zusammen mit den vorgenannten feinteiligen wasserunlöslichen Feststoffen verwendet werden können, sind in erster Linie Buildersalze, die polyanionische Gruppen enthalten bzw. eine Neigung zur Bildung assoziierter polyanionischer Gruppen besitzen, wie Alkalimetallsilikate, insbesondere Natriumsilikat der Zusammensetzung Na2O : SiO2 = 1 : 1 bis 1 : 3,4, vorzugsweise 1 : 2 bis 1 : 3,3, Alkalimetallphosphate bzw. -polyphosphate, insbesondere Pentanatriumtriphosphat, Borate, wie Natriummetaborat bzw. Natriumtetraborat. Brauchbare Vertreter dieser Klasse sind ferner die Salze organischer Polysäuren bzw. polymerer Säuren, wie Natriumnitrilotriacetat, Natriumeitrat, Natriumcarboxymethylcellulose, Natriumpolyacrylat sowie die Natriumsalze von Copolymeren der Acrylsäure und Maleinsäure. Derartige Salze bewirken im allgemeinen in wäßriger Lösung mit steigender Konzentration einen sehr starken Viskositätsanstieg. Sie werden vorzugsweise zusammen mit wasserunlöslichen Feststoffen eingesetzt. In diesem Fall kann ihr Anteil, auf insgesamt anwesende Feststoffe bezogen, bis zu 50 Gew.%, vorzugsweise bis zu 35 Gew.-% betragen. 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 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 Na 2 O: SiO 2 = 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.
Zusammen mit den wasserunlöslichen Feststoffen können auch solche wasserlöslichen Salze mitverwendet bzw. anstelle der vorgenannten polyanionischen Salze eingesetzt werden, die als stark polar charakterisiert werden können, im wesentlich mono-anionisch bzw. dianionisch aufgebaut sind und die in wäßriger Lösung mit steigender Konzentration nur einen geringen Viskositätsanstieg bewirken. Typische Vertreter dieser Klasse sind Natriumsulfat, Natriumcarbonat, Natriumacetat, Natriumnitrat und Natriumchlorid sowie entsprechende Kaliumsalze. Ihr Anteil, auf insgesamt anwesende Feststoffe bezogen, kann jedoch höchstens 35 Gew.-%, vorzugsweise höchstens 25 Gew.-% und insbesondere weniger als 20 Gew.-% betragen. Keinesfalls können sie alleiniger Bestandteil oder Haupt bestandteil der Feststoffkomponente sein bzw. in Abwesenheit eines wasserunlöslichen Feststoffes eingesetzt werden, da dies zu einer Zerstörung der Gelphase und zur Bildung schlammartiger bis klumpiger Gemische führt. Solche verflüssigten Gemische bzw. feuchten Klumpen lassen sich nicht mehr durch eine einfache mechanische Bearbeitung in Granulate überführen. Aus dem gleichen Grunde ist es vorteilhaft, diese Salze, sofern auf ihren Einsatz nicht verzichtet werden kann, bei der Herstellung der Granulate zuvor mit den pulvrigen, wasserunlöslichen Feststoffen zu vermischen oder sie gleichzeitig mit diesen Feststoffen oder auch als letzten Mischungsbestandteil nach Zugabe aller anderen Feststoffe der Gelphase zuzumischen. 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 have only a small concentration in aqueous solution 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.
Schließlieh können der Gelphase als Feststoffe untergeordnete Mengen anionischer, zwitterionischer, ampholytischer oder kationischer Tenside zugemischt werden. Beispiele für geeignete anionische Tenside sind Seifen, abgeleitet von ges-ättigien oder einfach ungesättigten C12-22-Fettsäuren, Alkylbenzolsulfonate mit einer linearen C9-13-Alkylgruppe, Salze von Alpha-sulfofettsäuren, abgeleitet von gesättigten oder einfach ungesättigten C12-18-Fettsäuren sowie deren Ester mit gesättigten C1-3-Alkoholen, C42-18- Alkansulfonate, C12-18-Olefinsulfonate und C12-18-Alkylsulfate bzw. Alkylethersulfate, wobei die genannten Tenside vorzugsweise als Na-Salze vorliegen. Der Anteil dieser Tenside, vorzugsweise Sulfonat-Tenside, kann bis zu 25 Gew.-%, vorzugsweise bis zu 15 Gew.-% der Feststoffe betragen. Auf nichtionische, in der Gelphase befindliche Tenside bezogen soll das Gewichtsverhältnis nichtionisches Tensid zu anionisches Tensid 3 : 2 nicht unterschreiten und vorzugsweise unter 2 : 1 liegen. Höhere Anteile an Aniontensiden können die Ausbildung der Gelphase beeinträchtigen bzw. die Umwandlung der Gelphase in körnige, rieselfähige Granulate behindern. Schiießlich können noch weitere Feststoffe in die Gelphase (A) eingearbeitet oder in der Granulierphase (B) zugefügt werden, die in Wasch- und Reinigungsmitteln üblicherweise in geringer Menge enthalten sind, wie optische Aufheller, Vergrauungsinhibitoren, Komplexbildner, Farbstoffe, Pigmente, Enzyme, Entschäumer und Duftstoffe. Ihr Anteil liegt im allgemeinen unter 1 Gew.-%, weshalb sie die Umwandlung der Gelphase in das Granulat nicht nachteilig beeinflussen. 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 C 12-22 fatty acids, alkylbenzenesulfonates with a linear C 9-13 alkyl group, salts of alpha sulfofatty acids derived from saturated or monounsaturated C 12-18 -Fatty acids and their esters with saturated C 1-3 alcohols, C 42-18 alkane sulfonates , C 12-18 olefin sulfonates and C 12-18 alkyl sulfates or alkyl ether sulfates, the surfactants mentioned 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 to 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.
Zweckmäßigerweise wird das nichtionische Tensid bei der Herstellung der Gelphase nicht ausschließlich mit Wasser vermischt, obwohl dies grundsätzlich möglich ist, sondern bevorzugt wird eine wäßrige Lösung bzw. Dispersion verwendet, die bereits einen Teil der insgesamt anzuwendenden Feststoffe bzw. Feststoffgemische enthält. Wird Zeoltth als Feststoff verwendet, geht man bei der Herstellung der Gelphase vorzugsweise von einer stabilisierten wäßrigen Dispersion (master batch) aus, wie er z. B. in DE 25 27 388 beschrieben ist. Derartige Dispersionen, die als wasserfeuchte Filterkuchen bei der Zeolith-Synthese anfallen, enthalten üblicherweise 35 bis 55 Gew.-%, vorzugsweise 40 bis 50 Gew.-% Zeolith, berechnet als wasserfreie Aktivsubstanz (d. h. bei Glühtemperatur entwässert), 0,5 bis 5 Gew.-%, vorzugsweise 1 bis 4 Gew.-% eines Dispersionsstabilisators, insbesondere ein nichtionisches Tensid, sowie Wasser (Differenz bis 100 %). In gleicher Weise können anstelle der wäßrigen Zeolithdispersion oder gleichzeitig bzw. im Gemisch mit ihr wäßrige Lösungen von Alkalisilikaten, z. B. Wasserglas-Lösungen, wäßrige Lösungen anionischer Tenside oder auch Gemische solcher Lösungen zur Bildung der Gelphase verwendet werden. Die Herstellung der Granulate kann in üblichen Misch- und Granuliervorrichtungen durchgeführt werden, beispielsweise in zylindrischen, horizontal oder gegen die Horizontale geneigt angeordneten Mischern mit einer axialen, drehbaren Welle, an der Rühr- und Mischorgane angebracht sind. Man kann das nichtionische Tensid vorlegen und das Wasser bzw. ein wasserhaltiges Feststoffgemisch hinzufügen und bis zur Gelbildung mischen oder auch in umgekehrter Reihenfolge vorgehen. Unter weiterem Mischen wird dann zu dem gebildeten Gel die trockene, pulverförmige Feststoffkomponente hinzugefügt und das Mischen solange fortgeführt, bis sich das gewünschte Granulat gebildet hat. Da das Gelieren der Gelphase (A) bis zum Erreichen der maximalen Viskosität vielfach einige Zeit, beispielsweise 10 bis 30 Sekunden, in Anspruch nimmt, läßt sich in vielen Fällen auch so arbeiten, daß man in dem Mischer die pulverförmige Feststoffkomponente vorlegt und die unmittelbar zuvorhergestellte, noch fließfähige Gelphase hinzufügt und das Mischen ebenfalls bis zur Ausbildung gut rieselfähiger Granulate fortsetzt. Die genannten Varianten lassen sich sowohl diskontinuierlich als auch kontinuierlich durchführen. Bei der diskontinuierlichen Arbeitsweise ist es grundsätzlich möglich und bevorzugt, die Feststoffe komplett und nicht portionsweise über einen längeren Zeitraum verteilt hinzuzufügen, wodurch sich die Arbeitsweise vereinfacht. In the preparation of the gel phase, the nonionic surfactant is expediently not only mixed with water, although this is fundamentally possible, but an aqueous solution or dispersion is preferably used which already contains part of the total solids or solid mixtures to be used. If Zeoltth 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 mixers which are arranged horizontally or inclined with respect to the horizontal and have an axial, rotatable shaft to which stirring and mixing elements are attached. You can add the nonionic surfactant and add the water or a water-containing solid mixture and mix until it forms a gel or proceed in reverse order. 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 gel phase (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 pulverulent solid component is placed in the mixer and the immediately prepared one , 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.
Das Mischen und Granulieren kann bei Raumtemperatur, beispielsweise bei 15 bis 30 °C, durchgeführt werden. Ein Erwärmen oder Kühlen während der Verarbeitung ist nicht erforderlich. The mixing and granulation can be carried out at room temperature, for example at 15 to 30 ° C. It is not necessary to heat or cool during processing.
Die Ausbildung der Granulate erfolgt spontan und bedarf außer des Rührens bzw. des Mischens keiner besonderen Maßnahmen. Die Zeit bis zur Ausbildung der gleichförmigen Granulate hängt in gewissem Umfange von der Gesamtmenge der Feststoffe, insbesondere jedoch von dem Anteil der zugefügten pulverförmigen Feststoffe ab und liegt bei Feststoffzusätzen von 35 bis 50 Gew.-%, bezogen auf das fertige Granulat, bei 30 Sekunden bis 3 Minuten. Mit weiter steigendem Feststoffanteil nimmt die Granulierzeit exponentiell zu und nimmt bei Feststoffanteilen von 65 bis 75 Gew.-% 10 bis 15 Minuten in Anspruch. Im allgemeinen sind höhere Feststoffanteile als 75 Gew.-% nicht erforderlich und vielfach auch nicht zweckmäßig. Weiterhin ist es weder erforderlich noch vorteilhaft, das Mischen nach Ausbildung einheitlicher, rieselfähiger Granulate noch weiter fortzusetzen. Es zeigt sich nämlich, insbesondere bei Gemischen mit niedrigen Feststoffgehalten, daß die Ausbildung der Granulate hinsichtlich ihres Rieselverhaltens und ihrer Gleichförmigkeit ein Optimum durchläuft. Eine weitere mechanische Bearbeitung führt dann zu einer Erweichung der bereits ausgebildeten Körner und zu einem Verklumpen bzw. Ankleben an den Mischerwerkzeugen, verbunden mit einer deutlichen Abnahme der RieseTfähigkeit und des Schüttgewichtes. The granules are formed spontaneously and require no special measures other than stirring or mixing. The time until the formation of the uniform granules depends to a certain extent on the total amount of solids, in particular, however from the proportion of powdery solids added and is from 30 to 3 minutes for solids additions of 35 to 50% by weight, based on the finished granules. 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 is 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 significant decrease in the gigantic capability and the bulk density.
In der Praxis verfährt man zweckmäßigerweise so, daß man die Granulation solange fortsetzt, bis das Schüttgewicht des Granulates ein Maximum erreicht hat. Dieses Maximum ist auch durch eine optimale Kornstruktur und Rieselfähigkeit gekennzeichnet und läßt sich ggf. durch einen einfachen Vorversuch ermitteln. Dieser Zustand ist optisch leicht erkennbar, da die Granulate in dem Mischer besonders gleichförmig erscheinen und leicht rieseln und auch kein Material mehr an der Mischerwandung bzw. an den Mischwerkzeugen haftet. Gleichzeitig ist dieser Zustand durch einen minimalen Kraftbedarf für das Betreiben des Mischers gekennzeichnet und läßt sich auch auf diese Weise leicht bestimmen. Im Bereich des Optimums lassen sich die Granulate rückstandsfrei aus dem Mischer entnehmen und aus der Ausflußöffnung ausräumen. Die Innenwand des entleerten Mischers und die Mischwerkzeuge sind danach in der Regel blank. Dieser Effekt ist im höchsten Maße überraschend, insbesondere wenn man sich das Anfangsstadium in Erinnerung ruft, bei dem das Gel als zähe, pastöse bzw. klumpige Masse an den Werkzeugen und der Mischerwelle klebt. In practice, the procedure is expediently such that 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 residue 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.
Die in der angegebenen Weise hergestellten Granulate sind trotz ihres hohen Gehaltes an flüssigen Bestandteilen, beispielsweise von mehr als 50% an Wasser und flüssigen nichtionischen Tensiden, hervorragend rieselfähig und bedürfen im allgemeinen keiner Nachbehandlung oder Trocknung. Sofern ein niedrigerer Wassergehalt der Granulate wünschenswert ist, beispielsweise dann, wenn sie mit feuchtigkeitsempfindl ichen Bestandteilen oder Pulvergemischen weitervermischt werden sollen, kann auch eine Trocknung angeschlossen werden. Diese Trocknung kann beispielsweise in einem Wirbelschichttrockner erfolgen. Eine Anwendung erhitzter Luft ist in diesem Falle nicht erforderlich. Weiterhin können die anfallenden oder auch die nachgetrockneten Granulate auch mit weiteren pulverförmigen Bestandteilen, wie feinteiliger Kieselsäure oder Pigmenten (auch farbigen) bestäubt bzw. beschichtet werden. Sie weisen Schüttgewichte von 600 bis 1 000 g/l, vorzugsweise von 650 bis 900 g/l auf und eignen sich hervorragend als Grundbestandteil bzw. zusätzliche Pulverkomponente in Waschmitteln vom Typ der sogenannten "Schwerpulver". Diese Schwerpulver erfreuen sich wachsenden Interesses, da sie bei gleicher Waschleistung im Vergleich zu herkömmlichen Sprühpulvern sehr viel weniger Verpackungsvolumen beanspruchen und Verpackungsmaterial einsparen. Ungeachtet ihrer hohen Dichte weisen die Granulate ein hervorragendes Lösungsvermögen in kaltem Leitungswasser auf und zeichnen sich durch ein gutes "Einspülverhalten" aus, d. h. sie bilden in automatischen Waschmaschinen keine Rückstände in den Einspülvorrichtungen. Despite their high content of liquid constituents, for example more than 50% of water and liquid nonionic surfactants, the granules produced in the stated manner are outstandingly 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 further mixed 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 resulting or the after-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, as 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 any residues in the washing-in devices in automatic washing machines.
Weitere Vorteile bietet das Verfahren dadurch, daß es gestattet, solche Stoffe schonend zu verarbeiten, die bei einer Sprühtrocknung ihre Wirkung verlieren bzw. in Wechselwirkung mit anderen Stoffen treten. Zu den zersetzlichen bzw. ihre Wirkung verlierenden Hilfsstoffen zählen Enzyme, Bleichmittel, Bleichaktivatoren, Schauminhibitoren und Duftstoffe. Gemische aus Zeolith und Alkalisilikat, die bei der Sprühtrocknung unter Bildung grobteiliger und schlecht redispergierbarer Agglomerate reagieren, lassen sich ohne diese Nachteile gut gemeinsam verarbeiten. Auch der Einsatz von nichtionischen Tensiden mit niedrigem Ethoxylierungsgrad, die auf Grund ihrer Waeserdampf-Flüchtigkeit zur Rauchbildung in der Abluft der Sprühtürme führen ("pluming"), ist bei dem erfindungsgemäßen Verfahren völlig unprobeematisch. 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-grained 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 untestematic in the process according to the invention.
Beispiele Examples
In den folgenden Beispielen wurde sowohl ein Labormischer mit einem Fassungsvermögen von 2 Litern als auch ein Mischer (Bauart: Lödige) mit einem Fassungsvermögen von 135 Litern verwendet. Beide Mischer bestanden aus einem zylindrischen, horizontal angeordneten Behälter mit axial angeordneter, mit Mischschaufeln ausgerüsteter Welle. Deren Rotationsgeschwindigkeit betrug bei dem Labormischer 300 Upm und bei dem Großmischer 120 Upm. Hinsichtlich der Funktionsweise, des Zeitaufwandes bei der Granulation und der Eigenschaften der Granulate gab es bei beiden Versuchsreihen keine wesentlichen Unterschiede. In den folgenden Beispielen steht "GT" für Gewichtsteile, "sec" für Sekunden. 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. 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 E0 (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: 1. 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 C 12- 18 fatty alcohols + 5 E0 (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:
Nach 50 sec waren die Granulate bereits gut rieselfähig. Bis zu einer Mischzeit von 70 sec, d. h. bis zum Erreichen des maxi malen Schüttgewichtes, nahm die Rieselfähigkeit noch weiter zu. Nach längerem Mischen trat ein Erweichen und Verklumpen der Granulate ein, wobei gleichzeitig das Schüttgewicht wieder abnahm und der Energiebedarf des Mischers anstieg. 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 pourability 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.
Die nach Mischzeiten von 60 sec erhaltenen Granulate wiesen das folgende, durch Siebanalyse bestimmte Kornspektrum auf. Angegeben sind die Anteile, die auf einem Sieb der angegebenen Maschenweite verbleiben bzw. bei "unter 0,1" durch das Sieb fallen, 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",
Der Klumptest (Belastung einer Pulveraufschüttung in einem zylindrischen Behälter mit einem Gewicht) ergab den Optimalwert 0. Der Mischer wies keine anhaftenden Rückstände auf und konnte ohne Zwischenreinigung erneut beschickt werden.  The clump test (loading a powder fill in a cylindrical container with a weight) gave the optimum value 0. The mixer had no adhering residues and could be loaded again without intermediate cleaning.
2. In gleicher Weise wie in Beispiel 1 beschrieben, wurden 10 GT des gleichen nichtionischen Tensids mit 40 GT der Zeolith-Dis- persion 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. 2. In the same way as described in Example 1, 10 parts by weight of the same nonionic surfactant were mixed with 40 parts by weight 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 GT eines mit 5 Mol EO umgesetzten Oleyl-Stearyl-Alkoholgemisches (Jodzahl = 50) wurden mit 30 GT der wäßrigen ZeolithDispersion 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. 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 C 12-14 fatty alcohol + 3 EO were mixed with 30 pbw of aqueous zeolite dispersion to form a gel and then 50 pbw of spray-dried zeolite were added. The granules obtained after a granulation time of 50 seconds had a bulk density of 820 g / l.
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. 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, a free-flowing granulate with a bulk density of 800 g / l was obtained.
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 55,5 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. 6. A 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 (Na 2 O: SiO 2 = 1: 3.3, water content 55.5% by weight ) Gel obtained was granulated with the addition of 50 pbw of spray-dried zeolite in 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. 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-Fett- säuren (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. 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 (Na salt) and alpha-sulfofatty acid (di-Na salt) from saturated C 16-18 - 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 was formed was transferred to the granulating mixer in the flowable 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

Patentansprüche Claims
1. Verfahren zur Herstellung von rieselfähigen Granulaten mit hohem Schüttgewicht, enthaltend nichtionische Tenside aus der Klasse der Polyglykoletherderivate sowie feinteilige, wasserlösliche und/oder wasserunlösliche Feststoffe und Wasser, dadurch gekennzeichnet, daß man (A) das nichtionische Tensid mit Wasser, das ggf. einen Teil, jedoch weniger als 50 Gew.-% der Gesamtmenge der wasserlöslichen bzw. wasserunlöslichen Feststoffe in gelöster bzw. dispergierter Form enthalten kann, bis zur Ausbildung einer viskosen Gelphase vermischt, worauf man (B) die verbleibende Hauptmenge der wasserlöslichen bzw. wasserunlöslichen Feststoffe in fester, pulvriger Form hinzumischt und bis zur Ausbildung von Granulaten mechanisch bearbeitet, wobei das Gewichtsverhältnis von nichtionischem Tensid und Wasser in der Gelphase zu insgesamt anwesenden Feststoffen (berechnet als wasserfreie Substanz) 25 : 75 bis 65 : 35 beträgt. 1. A process for the preparation of free-flowing granules with 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 can be 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 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.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Verhältnis von nichtionischem Tensid und Wasser in der Gelphase (A) zu insgesamt anwesenden Feststoffen 30 : 70 bis 60 : 40 beträgt. 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. Verfahren nach Anspruch 1 und 2, dadurch gekennzeichnet, daß man 0 bis 40 Gew.-% vorzugsweise 0 bis 30 Gew.-% und insbesondere 5 bis 25 Gew.-% der insgesamt verwendeten Feststoffe bei der Bildung der Gelphase (A) einsetzt und die verbleibende Hauptmenge als trockenes Pulver in der Granulierphase (B) zumischt. 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. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß man wasserunlösliche Feststoffe mit einer Korngröße unter 100 μm, vorzugsweise unter 50 μm einsetzt. 4. The method according to claim 3, characterized in that one uses water-insoluble solids with a grain size below 100 microns, preferably less than 50 microns.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß man als wasserunlöslichen Feststoff feinkristallinen Zeolith, Bentonit oder dessen Gemische einsetzt. 5. The method according to claim 4, characterized in that finely crystalline zeolite, bentonite or mixtures thereof are used as the water-insoluble solid.
6. Verfahren nach Anspruch 1 bis 4, dadurch gekennzeichnet, daß man das Mischen der Gelphase mit dem pulverförmigen Feststoff maximal solange mischt, bis das Schüttgewicht des sich ausbildenden Granulates einen Maximalwert erreicht hat. 6. The method according to claim 1 to 4, characterized in that the mixing of the gel phase with the powdery solid is mixed at most until the bulk density of the granules formed has reached a maximum value.
7. Verfahren nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man das nichtionische Tensid mit einer wäßrigen Dispersion von feinkristallinem Zeolith unter Ausbildung der Gelphase vermischt, wobei die wäßrige Dispersion 35 ins 55 Gew.-% Zeolith, bezogen auf wasserfreie Substanz, 0,5 bis 5 Gew.-% eines als Dispersionsstabilisator wirkenden nichtionischen Tensids und 64,5 bis 40 Gew.-% Wasser enthält. 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 in 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. Granulate, hergestellt nach einem oder mehreren der Ansprüche 1 bis 6. 8. Granules produced according to one or more of claims 1 to 6.
9. Granulate nach Anspruch 8, gekennzeichnet durch ein Schüttgewicht von 600 bis 1000 g/l, vorzugsweise von 650 bis 900 g/l. 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. Granuläres Wasch- und Reinigungsmittel, enthaltend Granulate gemäß Anspruch 8 bis 9. 10. Granular washing and cleaning agent containing granules according to claim 8 to 9.
EP89911804A 1988-10-21 1989-10-12 Process for manufacturing tenside-containing granulates Expired - Lifetime EP0536110B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE3835918 1988-10-21
DE3835918A DE3835918A1 (en) 1988-10-21 1988-10-21 METHOD FOR PRODUCING TENSIDE CONTAINING GRANULES
PCT/EP1989/001206 WO1990004629A2 (en) 1988-10-21 1989-10-12 Process for manufacturing tenside-containing granulates

Publications (2)

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EP0536110A1 true EP0536110A1 (en) 1993-04-14
EP0536110B1 EP0536110B1 (en) 1995-01-25

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EP89118962A Pending EP0364881A3 (en) 1988-10-21 1989-10-12 Process for preparing granules containing surface-active agents

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EP (2) EP0536110B1 (en)
JP (1) JP2704020B2 (en)
KR (1) KR970001224B1 (en)
AT (1) ATE117718T1 (en)
DE (2) DE3835918A1 (en)
DK (1) DK71791D0 (en)
ES (1) ES2067569T3 (en)
PT (1) PT92060A (en)
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WO (1) WO1990004629A2 (en)

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DK71791A (en) 1991-04-19
ES2067569T3 (en) 1995-04-01
EP0536110B1 (en) 1995-01-25
TR24142A (en) 1991-04-09
EP0364881A2 (en) 1990-04-25
PT92060A (en) 1990-04-30
DE58908952D1 (en) 1995-03-09
WO1990004629A3 (en) 1991-05-30
KR900701988A (en) 1990-12-05
JPH04501129A (en) 1992-02-27
DK71791D0 (en) 1991-04-19
US5354493A (en) 1994-10-11
JP2704020B2 (en) 1998-01-26
EP0364881A3 (en) 1990-06-06
ATE117718T1 (en) 1995-02-15
KR970001224B1 (en) 1997-02-04
WO1990004629A2 (en) 1990-05-03
DE3835918A1 (en) 1990-04-26

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