WO1994009110A1

WO1994009110A1 - Method of manufacturing a granular washing and cleaning agent

Info

Publication number: WO1994009110A1
Application number: PCT/EP1993/002800
Authority: WO
Inventors: Volker Bauer; Klaus Köster; Jochen Jacobs; Andreas Syldath; Ditmar Kischkel; Bert Gruber
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1992-10-21
Filing date: 1993-10-12
Publication date: 1994-04-28
Also published as: DE4235425A1

Abstract

The invention concerns granular washing and cleaning agents, or a component of such agents, which contain high quantities of surfactants and are manufactured by neutralizing a preparation containing the surfactants in their acid form and subsequent granulation with additional solid materials. Such agents frequently have a poor colour value if the anionic surfactants are pre-bleached in their acid form. Agents with a good colour value are obtained, however, if an acid surfactant preparation containing one or more anionic surfactants in their acid form is (a) neutralized with a stoichiometric amount, or an excess of, a neutralizing agent in an intimate-mixing device, and at the same time as the neutralization, bleached by the addition of a peroxide bleach and (b) granulated together with additional solid materials to obtain a dust-free product and, optionally, simultaneously or subsequently dried.

Description

"Process for the production of a granular detergent and cleaning agent '

The invention relates to a method for producing a granular washing and cleaning agent or a component therefor, wherein good color values are to be achieved.

Already in German patent application DE-A-3535 184 it is proposed to neutralize an acidic sulfofatty acid ester with carbonate and / or bicarbonate dry and then to dispense with other ingredients from washing powders.

European patent application EP-A-0 345090 describes a process for the production of detergents and cleaning agents, anionic surfactants in their acid form being neutralized with almost stoichiometric amounts of an aqueous sodium hydroxide solution or sodium carbonate solution, on an inorganic carrier such as bentonite, silicate or carbonate applied, dried and finally mixed with other detergent and cleaning agent components.

Neutralization reactions of anionic surfactants in their acid form are exothermic reactions, whereby the heat development, in particular in the case of drying neutralization or neutralization with highly concentrated aqueous mixtures, can impair the color quality of the neutralization products in such a way that yellowish products, even products with brown ones Discoloration can be obtained.

For this reason, the German patent application DE-A-1258864 already suggests to initially pre-bleach an acidic α-sulfofatty acid methyl ester and to neutralize it only after the bleaching with hydroxides, carbonates or hydrogen carbonates. Likewise, European patent application EP-A-0249846 proposes to first bleach an acidic α-sulfofatty acid methyl ester with hydrogen peroxide and then to neutralize it with a slight excess of alkali. The products obtained are dried and degassed in vacuo. However, the acidic pre-bleaching of anionic surfactants in their acid form has the disadvantage that the addition of hydrogen peroxide solutions in many cases results in such a high increase in viscosity that homogeneous incorporation of highly concentrated aqueous neutralizing agents or solid neutralizing agents is made difficult or impossible. However, homogeneous incorporation of the neutralizing agent is necessary in order to ensure complete neutralization of the anionic surfactant in acid form.

However, if the bleaching is only carried out after the neutralization, the problem of homogeneous incorporation of the neutralizing agent is avoided, but generally worse color values are obtained than by acidic pre-bleaching.

A neutralization of anionic surfactants in their acid form with simultaneous bleaching (alkaline bleaching) leads to the desired good color values, but is particularly useful for dry neutralization and neutralization with highly concentrated solutions, pasty to granular products being used as neutralizing products are associated with a number of other problems that have not yet been resolved. In particular, these problems include the difficulties in the homogeneous distribution of the bleaching agent in the pasty to granular neutralization mixtures and the destruction of the foam formed during the bleaching with a peroxy bleaching agent. In addition, care must also be taken here again that the neutralization with simultaneous alkaline bleaching can only be carried out in apparatuses with good heat dissipation, since otherwise, in spite of the bleaching, burns can occur again.

The object was therefore to develop a process for the production of detergents and cleaning agents or components therefor, as a result of which free-flowing granules having high active substance contents and good color values can be provided. At the same time, both the energy expenditure and the emissions during the production of these granules should be minimized. The invention accordingly relates to a process for producing a granular washing and cleaning agent or a component therefor, which includes a bleaching process, wherein a) an acidic surfactant preparation form, comprising one or more anionic surfactants in their acid form, with a stoichiometric The amount or excess of a neutralizing agent is neutralized in an intensive mixer and bleached at the same time with the neutralization by adding a peroxy bleaching agent, and b) then granulated with further solids until dust-free products are obtained, and optionally dried simultaneously or subsequently.

The acidic surfactant formulation may contain one or more anionic surfactants in their acid form. Preferred anionic surfactants in their acid form are the corresponding acids of fatty alkyl sulfates, fatty alkenyl sulfates, fatty alkyl ether sulfates, alkyl benzene sulfonates, alkyl sulfo fatty acid alkyl esters, fatty acid soaps or mixtures of these.

It is particularly advantageous to use esters of α-sulfofatty acids (ester sulfonates) which, by α-sulfonation of the methyl esters of fatty acids of plant and / or animal origin with 8 to 20 C atoms in the fatty acid molecule and subsequent neutralization to give water-soluble mono-salt zen are manufactured. These are preferably the α-sulfonated esters of hydrogenated coconut, palm kernel or tallow fatty acids, with sulfonation products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3% by weight. , may be present. In particular, the use of acidic α-sulfofatty acid alkyl esters which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters, is preferred. The acidic methyl esters of oc-sulfofatty acids (MES) are used with particular advantage. Other suitable anionic surfactants in their acid form are the α-sulfofatty acids obtainable by ester cleavage of the α-sulfofatty acid alkyl esters. The mono-acids of the α-sulfofatty acid alkyl esters are obtained in their industrial production as an aqueous mixture with limited amounts of oc-sulfofatty acids. Further preferred anionic surfactants in their acid form are also Cg-Ci8-alkylbenzenesulfonic acids, in particular those which mainly contain a C12-Mkyl radical and are mostly referred to as dodecylbenzenesulfonic acid.

In particular, however, the corresponding acids of the alkyl sulfates and the alkenyl sulfates are also preferred, with particular preference given to the fatty alkyl sulfonic acids and the fatty alkenyl sulfonic acids. Suitable fatty alkyl sulfonic acids are the acidic sulfuric acid monoesters of the C.sub.2 -C.sub.18 fatty alcohols, such as lauryl, myristyl, cetyl alcohol or stearyl alcohol, and the fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil, which additionally contain proportions of unsaturated Alcohols, for example oleyl alcohol, may contain. Mixtures in which the proportion of the alkyl radicals are 50 to 70% by weight on C12, 18 to 30% by weight on C14, 5 to 15% by weight on C15, less than 3% are preferred. - Are distributed on C10 and less than 10% by weight on C g. Likewise, the use of a mixture of fatty alkyl sulfonic acids of the specified C chain distribution with fatty alkenyl sulfonic acids, in particular with oleyl sulfonic acid, is preferred. Also preferred is the use of the acid sulfonation products of mixtures of saturated and unsaturated fatty alcohols which are known under the name HD-0cenol ( ^R ) (commercial product of the applicant) and consist, for example, of approximately 50% by weight or more of oleyl alcohol, while the proportion of saturated fatty alcohol in these mixtures consists predominantly of Ci fatty alcohol. In the sulfation of unsaturated fatty alcohols, internal sulfonates are formed under normal reaction conditions in addition to the unsaturated fatty alcohol sulfates, the proportion of internal sulfonates being around 10%. The acidic sulfuric acid monoesters of the alcohols and fatty alcohols ethoxylated in particular with 1 to 6 moles of ethylene oxide (E0), that is to say the corresponding acids of the fatty alkyl ether sulfates, are also used with preference in the acidic surfactant preparation form.

The use of the corresponding acids of methyl α-sulfofatty acid esters or mixtures of methyl α-sulfofatty acid esters with fatty alkyl sulfates, fatty alkenyl sulfates or alkylbenzenesulfonates is very particularly preferred. It is particularly advantageous if the anionic surfactants in their Acid form in amounts of 70 to 100 wt .-%, based on the acidic surfactant preparation form, are used.

In principle, saturated and unsaturated fatty acids such as lauric acid, myristic acid, palmitic acid or stearic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or taig fatty acids, derived mixtures. In particular, those fatty acid mixtures are preferred which are composed of 50 to 100% by weight of saturated Ci2-Ci8 fatty acids and 0 to 50% by weight of oleic acid. However, it is preferred that these fatty acids are used in combination with one or more of the above-mentioned anionic surfactant acids.

The acidic surfactant preparation form can be in solid, pasty or foamy form.

Further constituents of the acidic surfactant preparation form can be, for example, nonionic surfactants. Liquid ethoxylated, in particular primary alcohols with preferably 9 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (E0) per mole of alcohol are preferably used in which the alcohol radical is linear or methyl-branched in the 2-position can, or can contain linear and methyl-branched radicals in the mixture, as is usually present in oxo alcohol radicals. However, linear residues of alcohols of native origin with 12 to 18 C atoms are particularly preferred, e.g. from coconut, tallow or oleyl alcohol. In particular, alcohol ethoxylates are preferred which have an average of 2 to 8 E0. The preferred ethoxylated alcohols include, for example, Ci2-Ci4 alcohols with 3 E0 or 4 E0 Cg-Cn alcohol with 7 E0, Ci3-Ci5 alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, Ci2-Ci8 -Alcohols with 3 E0, 5 E0 or 7 E0 and mixtures thereof, such as mixtures of C12-C1 - alcohol with 3 E0 and Ci2-Ci8 alcohol with 5 E0.

The degrees of ethoxylation given represent statistical means which, for a special product, can be an integer or a fraction. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). Furthermore, the liquid, acidic surfactant preparation forms in particular can contain further ingredients and in particular those which influence the viscosity. These include primarily polyethylene glycols, for example those with a relative molecular weight between 200 and 2000, of which those with a relative molecular weight between 200 and 600 are particularly preferred, and electrolytes, preferably inorganic salts such as sodium or potassium chloride or sulfate, but also organic salts such as sodium or potassium acetate.

Highly concentrated aqueous solutions and / or solids are preferably used as the neutralizing agent in stage a). The use of highly concentrated aqueous sodium hydroxide solution or highly concentrated aqueous potassium hydroxide solution with a content of at least 50% by weight of alkali hydroxide and in particular aqueous sodium hydroxide solution with a content of above 50% by weight of sodium hydroxide and solids such as Sodium carbonate, sodium bicarbonate and powdered sodium hydroxide are preferred. The use of solid sodium carbonate is particularly advantageous. The neutralizing agent is used in stage a) in stoichiometric amounts or in an up to 40% excess, based on the anionic surfactants in acid form, preferably in a 5 to 30% excess, based on the anionic surfactants in acid form , for example in a 5 to 20% excess, based on the anionic surfactants in acid form. It is particularly preferred that the bleaching process is carried out with cooling.

Bleaching agents preferably used in process step a) are hydrogen peroxide, sodium perborate monohydrate, sodium perborate tetrahydrate and / or sodium percarbonate, an aqueous hydrogen peroxide solution being particularly preferred. It is advantageous to obtain the bleach in quantities of 0.1 to 10% by weight, preferably in quantities of 0.5 to 8% by weight and in particular in quantities of 1 to 5% by weight on the amount of anionic surfactants in acid form.

In a preferred embodiment of the invention, in process stage a) an acidic surfactant preparation form, which is in solid form and contains anionic surfactants in solid form, is added by adding a solid neutralizing agent and an aqueous bleaching solution, preferably a concentrated centered aqueous hydrogen peroxide solution, converted into a granular or powdered surfactant preparation form.

In a further embodiment of the invention, an acidic surfactant preparation form, which contains in solid form and anionic surfactants in solid form, in particular by adding a highly concentrated or a solid, in particular a solid neutralizing agent and an aqueous hydrogen peroxide solution a dilute aqueous hydrogen peroxide solution, for example with a content of 10 to 25% by weight of hydrogen peroxide and preferably with a content of 15 to 20% by weight of hydrogen peroxide, is converted into a pasty to foamy surfactant preparation form .

In both embodiments, in which acidic surfactant preparations are used in solid form, the procedure is preferably such that the solid acidic surfactant preparation form presented initially liquefies at temperatures at which the anionic surfactants used melt in acid form and then neutralized and bleached at the same time. It is preferred to carry out the neutralization and simultaneous alkaline bleaching with cooling.

In a further embodiment of the invention, it is preferred that an acidic surfactant preparation form, which is in foamy to pasty form, by adding a highly concentrated aqueous or solid neutralizing agent and an aqueous bleaching solution, preferably an aqueous hydrogen peroxide solution a paste-like to granular or powdery surfactant preparation form is transferred.

It is particularly preferred that the alkaline bleached surfactant pastes obtained in process step a) have a water content of between 1 and 10% by weight, based on the paste.

With regard to the improvement of the color values of the agents that can be produced by the process according to the invention, a process variant is preferred, wherein in process step a) an acidic surfactant preparation form is used which has already been acid-bleached. It is preferred use the bleach, preferably hydrogen peroxide, in amounts of 0.1 to 2.5% by weight, in particular 0.2 to 2% by weight, based in each case on the amount of anionic surfactants in acid form, the acidic pre-bleaching in one Perform time of about 10 to 60 minutes and then produce the surfactant preparation form by adding the neutralizing agent and further bleaching agent. In particular, it is preferred that the acidic pre-bleaching and the alkaline bleaching, if any, are based on no more than 10% by weight, preferably no more than 8% by weight and in particular no more than 5% by weight on the anionic surfactants in acid form, on bleaching agents.

The neutralized and at the same time bleached surfactant preparation produced in process step a) is then, in a further process stage b), optionally with further typical solid ingredients of detergents and cleaners, preferably inorganic or organic builder substances, alkaline or neutral salts further amounts of bleaching agents, the peroxy compounds already mentioned such as perborate monohydrate, perborate tetrahydrate and percarbonate being preferred, bleach activators, graying and discoloration inhibitors, foam regulators, in particular in granular form and / or granulated enzyme granules.

A preferred inorganic builder substance is finely crystalline, synthetic and bound water-containing zeolite, preferably zeolite NaA in detergent quality. However, zeolite NaX and mixtures of NaA and NaX are also suitable. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 8 -fatty alcohols with 2 to 5 ethylene oxide groups. Suitable powdered zeolites have an average particle size of less than 10 μ (volume distribution; measurement method: Coulter Counter) and preferably contain 20 to 22% by weight of bound water. Suitable substitutes or partial substitutes for zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x 02χ ₊ yH20, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x is 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application 164 514. Preferred crystalline layered silicates are those in which M represents sodium and x assumes the values 2 or 3. In particular, ^'sodium disilicates Na2Si2θ5 * yH2θ are both .beta.- and δ preferred, with beta-sodium disilicate being obtainable for example by the method / described in the international patent application WO-A-91 08,171th

Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons. and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

Other suitable builder substances or constituents which can be used as cobuilders are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. Also particularly preferred are biodegradable terpolymers, for example those which, as monomer units, comprise acrylic acid or acrylate, maleic acid or Maleate and vinyl alcohol or a vinyl alcohol derivative or as monomers acrylic acid or acrylate, 2-alkylallylsulfonic acid or 2-alkylallylsulfonate and a carbohydrate, in particular Sucrose. The (co) polymeric polycarboxylates or the terpolymers can be used either as a powder or as an aqueous solution, with 20 to 55% by weight aqueous solutions being preferred.

Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to.7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0280 223. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Water-soluble inorganic salts such as bicarbonates or carbonates, but preferably silicates or mixtures thereof, can be used as alkaline salts. In particular, alkali carbonate and alkali silicate, especially sodium silicate with a molar ratio Na2θ: Siθ2 from 1: 1 to 1: 4.5 and in particular from 1: 2.0 to 1: 3.3 are used. Other inorganic salts that can be used as feedstock in process stage b) are neutral salts such as sulfates and chlorides in the form of their sodium or potassium salts.

Suitable bleach activators are N-acyl or 0-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine (TAED) and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT).

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing graying. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Furthermore, soluble ones Use starch preparations and other starch products than those mentioned above, eg degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, cellulose ethers such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof are preferably used.

When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of Ci8-C24 ~ fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Mixtures of different foam inhibitors are also advantageously used, e.g. those made of silicone, paraffins or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or water-dispersible carrier substance.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Their proportion can be about 0.2 to about 2% by weight. The enzymes are preferably adsorbed on carrier substances and / or embedded in coating substances.

The neutralization and alkaline bleaching according to a) is carried out in an intensive mixer, for example in an Eirich mixer, a Vomm mixer or a Pari mixer. It is preferred that the neutralized and alkaline-bleached surfactant preparation according to a) is produced at peripheral speeds of the mixer tools up to 25 m / s, preferably between 9 and 20 m / s. The granulation b) is preferably carried out with the aid of a granulation liquid. Water, the described aqueous solutions or suspensions, nonionic surfactants, in particular mixtures of nonionic surfactants and polyethylene glycol with a relative molecular weight between 200 and 600, and mixtures of nonionic surfactants and water or nonionic surfactants, polyethylene glycols and water are suitable as the granulating liquid. The amount of the granulating liquid is such that non-adhesive granules are obtained. In particular, it is preferred that in the granulation according to b) free, unbound water is used in a total amount of 1 to 20% by weight, based on the mixture to be granulated. It is irrelevant whether the water and / or the nonionic surfactants are already introduced into the granulation process by the pasty surfactant preparation form prepared in a) or are additionally added in process step b). The total amount of unbound water used is advantageously linked to the temperature during the granulation. Thus, it is preferred that during the granulation at temperatures between 20 ° C. and about 60 ° C. about 3 to 10% by weight of free, non-bound water and at temperatures above 60 ° C. to about 150 ° C. about 1 up to 5% by weight of free, unbound water are used. The granulation according to b) can be carried out according to all known methods and in suitable devices. Reference is made here, by way of example only, to the disclosure of the international patent application WO-A-92/01036, which describes a granulation process for converting aqueous detersive and cleaning-active surfactants into storage-stable dry granules. Following the granulation, drying, preferably fluidized bed drying, can be carried out, if necessary, but this is not absolutely necessary in the process, which is preferably carried out with only small amounts of water.

In particular, however, a method is preferred in which the granulation according to b) can be carried out with simultaneous drying and is preferably carried out. Such processes can be carried out in all heatable mixers and granulators. Granulators of the Turbo-Dryer ( ^R ) type (device from Vomm, Italy) are particularly preferred. In a further preferred embodiment However, the invention proposes that the granulation according to b) is carried out in a batch-wise or continuous fluidized bed. It is particularly preferred to carry out the process continuously in the fluidized bed. The procedure described in the older German patent application DE-A-41 27 323 can be used here. The surfactant preparation form can be introduced into the fluidized bed via a nozzle. Fluidized bed granulators which are preferably used are systems for granulation drying (AGT) from Glatt, Federal Republic of Germany. It is preferred that in a plant for granulation drying the supply air temperature is at least about 20 ° C below the ignition temperature determined for the respective final concentrations, while in the case of a turbo dryer both the wall temperature and the supply air temperature are set so that they are below the ascertained browning temperature of the product. It is possible to granulate and simultaneously dry both in the granulation drying system and in the turbo dryer in a hot gas stream from superheated steam, for example analogously to the disclosure of the international patent application W0-A-92 / 05849.

The granular detergents and cleaning agents produced according to the invention or the granular components for detergents and cleaning agents are distinguished in particular by the good color values of the products. At the same time, both the energy expenditure and the emission in the production of these granules have been minimized compared to granules produced by traditional spray drying. The granules produced in this way preferably contain 5 to 55% by weight, in particular 10 to 50% by weight, and with particular advantage 10 to 45% by weight of anionic and nonionic surfactants, the proportion of nonionic surfactants preferably 1 to 15 % By weight and in particular 2 to 10% by weight. The granules are non-dusting, ie they preferably have less than 3% by weight and in particular less than 2% by weight of particles with a particle size which is less than or equal to 0.1 mm. The granules are also non-tacky and have a bulk density of preferably 600 to 1000 g / 1 and in particular 700 to 850 g / 1. If desired, they can be mixed and processed with other components of conventional washing and cleaning agents, for example bleaching agents and bleach activators. Examples

Example 1 :

In an intensive mixer (Pari mixer), 50 kg per hour of a melt of 2/3 dodecylbenzenesulfonic acid and 1/3 of an acidic methyl oc-sulfofatty acid (Ciss-Ciδ-palm stearic acid) were continuously cooled at 11.2 kg per hour Sodium carbonate (0.56 mol carbonate / mol acid) and 3.0 kg per hour of a 35% by weight aqueous hydrogen peroxide solution (2.1% by weight hydrogen peroxide, based on anionic surfactant in acid form) are mixed. The resulting foam was mechanically destroyed in a paddle screw device and degassed and dewatered in vacuo. The light yellow reaction product solidified below 50 ° C. and was ground into powder. The surfactant content of the mixture was 87% by weight, the water content 4% by weight; the pH of a 1% aqueous solution was 6.8; the Velcro color number (5% surfactant) was 120.

The surfactant preparation form was processed with the addition of 8% by weight (based on the mixture to be granulated) and further solids in a ploughshare mixer from Lödige to give granules of the composition given below.

The mixture was granulated for 5 minutes, then dried in the fluidized bed at 80 ° C. for 1.5 minutes and cooled with air for 1.5 minutes. The resulting light-colored and dust-free granules, which had less than 1% of particles with a particle diameter below 0.1 mm (sieve analysis), had a bulk density of 710 g / l. Composition of the granules:

Anionic surfactant sulfonates 20% by weight

Ci2-Ci8 ~ fatty acid soap 3.5% by weight

Sodium carbonate 20% by weight

Water glass (Na2θ: Siθ2 1: 2.0) 7% by weight

Zeolite NaA 31.2% by weight

Tallow fatty alcohol with 5 E0 0.4% by weight Sokalan ( ^R ) CP 5 (copoly eres of the salts of acrylic acid and maleic acid,

Commercial product from BASF) 6% by weight

CMC / MC 1.6% by weight

Optical brightener 0.2% by weight

Sodium sulfate 8.8% by weight

Unbound water rest

Example 2:

According to Example 1, a foamy and pasty surfactant preparation was prepared by melting molten acidic α-sulfofatty acid methyl ester (Ci-cis-palrostearic acid) and dodecylbenzenesulfonic acid together with C12-Cis fatty acid in a ploughshare mixer from Lödige at a rotating speed of the cutter heads of 20 m / s submitted, neutralized with sodium carbonate (0.6 mol sodium carbonate per mol acid) and during the neutralization with 35 wt .-% aqueous hydrogen peroxide solution (2.2 wt .-% hydrogen peroxide, based on acid) was bleached . The surfactant preparation form was granulated without further preliminary degassing with the other constituents according to Example 1 with the addition of 4% by weight of water and dried according to Example 1. The light-colored granules had a bulk density of 695 g / 1 and the grain size distribution given below (sieve analysis). > 1.6 mm 4% by weight

> 0.8 mm 86% by weight

> 0.4 mm 6% by weight

> 0.1 mm 3% by weight 0.1 mm and below 1% by weight

Example 3:

In a heatable turbo dryer from Vomm (diameter 220 mm; length 1.5 m), at a speed of rotation of the tools from 1600 rpm to 110 kg per hour, alkylbenzenesulfonic acid (Marlon ( ^R ) AS 3, hand-made product from Hüls AG) , 20 kg per hour of sodium carbonate and 10 kg per hour of a 17.5% aqueous hydrogen peroxide solution. The jacket temperature of the turbo dryer was initially set to 65 ° C. The jacket heating was switched off immediately after the product had been added and the reaction had started. A white paste was obtained almost immediately. The product temperature was 90 ° C. 19.5 parts by weight of the paste obtained in this way, which contained 8% by weight of water, based on the paste, was in a turbo dryer from Vomm (diameter 350 mm, speed 2000 rpm) at a wall temperature of 140 ° C and a supply air temperature of 150 ° C and dried with 21 parts by weight of sodium carbonate, 29 parts by weight of hydrated zeolite, 25 parts by weight of sodium sulfate, 2.0 parts by weight of water glass (Na2θ to Siθ2 1: 3.0) and 3.5 parts by weight of Sokalan ( ^R ) CP 5 granulated. The content of anionic surfactant in the finished granules was 17% by weight and the amount of unbound water was 4% by weight. The granules had the following grain size distribution (sieve analysis):

> 1.6 mm 0.5% by weight

> 0.8 mm 7.2% by weight

> 0.6 mm 13.3% by weight

> 0.4 mm 28.1% by weight

> 0.2 mm 39.1% by weight

> 0.1 mm 10.7% by weight 0.1 mm and below 1.1% by weight

Claims

Patent claims:

1. A process for the preparation of a granular washing and cleaning agent or a component therefor, which includes a bleaching process, characterized in that a) an acidic surfactant preparation form comprising one or more anionic surfactants in their acid form, with a stoichiometric amount or an excess of one Neutralizing agent neutralized in an intensive mixer and bleached simultaneously with the neutralization by adding a peroxy bleaching agent and b) then granulated with further solids until dust-free products are obtained and optionally dried simultaneously or subsequently.

2. The method according to claim 1, characterized in that in the acidic surfactant preparation form as anionic surfactants in their acid form, the kor¬ corresponding acids of fatty alkyl sulfates, fatty alkenyl sulfates, fatty alkyl ether sulfates, alkylbenzenesulfonates, α-sulfofatty acid alkyl esters, fatty acid soaps or mixtures of these, preferably the Corresponding acids of α-sulfofatty acid methyl esters or mixtures of α-sulfofatty acid methyl esters with fatty alkyl sulfates, fatty alkenyl sulfates or alkylbenzenesulfonates are used, the anionic surfactants in their acid form preferably in amounts of 70 to 100% by weight, based on the acidic surfactant Form of preparation, are used.

3. The method according to claim 1 or 2, characterized in that an acidic surfactant preparation form is used which contains nonionic Ten¬ side.

4. The method according to any one of claims 1 to 3, characterized in that as a neutralizing agent highly concentrated aqueous solutions, preferably aqueous sodium hydroxide solution containing sodium hydroxide of at least 50 wt .-%, and / or solids, preferably sodium carbonate, sodium bicarbonate and powdered sodium hydroxide, and as Bleaching agents hydrogen peroxide, sodium perborate monohydrate, sodium perborate tetrahydrate and / or sodium percarbonate, an aqueous hydrogen peroxide solution being preferred.

5. The method according to any one of claims 1 to 4, characterized in that the neutralizing agent in stoichiometric amounts up to a 40% excess, based on the anionic surfactants in acid form, preferably in a 5 to 30% excess, based on the Anion¬ surfactants in acid form, and the bleach in amounts of 0.1 to 10 wt .-%, preferably from 0.5 to 8 wt .-% and in particular from 1 to 5 wt .-%, each based on the amount Anionic surfactants in acid form can be used, the bleaching process preferably being carried out with cooling.

6. The method according to any one of claims 1 to 5, characterized in that an acidic surfactant preparation form, which is in solid form, by adding a solid neutralizing agent and an aqueous bleaching solution, preferably an aqueous hydrogen peroxide solution, in a granular or powdered surfactant preparation form is transferred.

7. The method according to any one of claims 1 to 5, characterized in that an acidic surfactant preparation form, which is in solid form, is converted into a pasty to foamy Ten¬ sid preparation form by adding a solid neutralizing agent and a dilute aqueous hydrogen peroxide solution.

8. The method according to claim 6 or 7, characterized in that the submitted solid acidic surfactant preparation is first liquefied and then neutralized and bleached at the same time.

9. The method according to any one of claims 1 to 5, characterized in that an acidic surfactant preparation form, which is in foamy to pasty form, by adding a solid neutralizing agent and an aqueous bleaching solution, preferably an aqueous peroxide solution, in a pasty to granular or powdery ten- sid preparation form is transferred.

10. The method according to claim 7 or 9, characterized in that the alkali bleached surfactant pastes have a water content between 1 and 10 wt .-%, based on the paste.

11. The method according to any one of claims 1 to 10, characterized in that the acidic surfactant preparation is pre-bleached acid, the bleaching agent preferably in amounts of 0.1 to 2.5 wt .-%, in particular 0.2 up to 2% by weight, based in each case on the anionic surfactants in acid form.

12. The method according to any one of claims 1 to 11, characterized in that the neutralized and at the same time alkaline bleached surfactant preparation form b) with other typical solid ingredients of detergents and cleaning agents, preferably inorganic or organic builders, alkaline or neutral salts, optionally further bleaching agents, bleach activators, graying and discoloration inhibitors, foam regulators, preferably in granular form and / or enzyme granules.

13. The method according to any one of claims 1 to 12, characterized in that in the granulation according to b) unbound water is used in amounts of 1 to 20 wt .-%, based on the mixture to be granulated.

14. The method according to any one of claims 1 to 13, characterized in that the neutralization and alkaline bleaching in an intensive mixer is preferably carried out at peripheral speeds of the tools up to 25 m / s, in particular between 9 and 20 m / s.

15. The method according to any one of claims 1 to 14, characterized in that the granulation according to b) can be carried out with simultaneous drying and is preferably carried out.

16. The method according to any one of claims 1 to 14, characterized in that drying, preferably fluidized bed drying, is carried out after the granulation.

17. Granular washing and cleaning agent or a component therefor, produced according to one of claims 1 to 16, characterized in that the granules 5 to 55 wt .-%, preferably 10 to 50 wt .-% and in particular 10 to 45 wt. -% contains anionic and nonionic surfactants, is non-dusting and non-sticky and has a bulk density of preferably 600 to 1000 g / 1, in particular 700 to 850 g / 1.