DE19910789A1 - Granulation process - Google Patents

Abstract

Disclosed is a novel granulation method. A surfactant foam is obtained by foaming a free-flowing component that contains anionic surfactant acid with a gaseous medium. Said surfactant foam is used as granulation auxiliary and is preferably provided with mean pore sizes less than 10 mm, preferably less than 5 mm and especially less than 2 mm.

Description

The present invention relates to a method for producing surfactant granules. she relates in particular to a method which allows surfactant granules or surfactant-containing Components of detergent and cleaning agent compositions or complete Detergent and cleaning agent compositions without or with reduced use of spray drying steps.

Granular detergent compositions or components therefor are largely manufactured by spray drying. When spray drying who to the ingredients such as surfactants, builders, etc. with about 35 to 50 wt .-% water an aqueous slurry, the so-called slurry, mixed and in spray towers atomized in a hot gas stream, whereby the detergent and cleaning agent particles form. Both the facilities for this process and the implementation of Ver driving are expensive because most of the slurry water is evaporated in order to obtain particles with residual water contents of around 5 to 10% by weight. In addition ha ben the granules produced by spray drying usually excellent Solubility, but have only low bulk weights, which leads to higher packaging vo lumina as well as transport and storage capacities. The flowability also sprayed Dried granules are not optimal due to their irregular surface structure, which also affects their visual appearance. Spray drying process white list a number of other drawbacks, so that there has been no lack of attempts to  Manufacture of washing and cleaning agents completely without spray drying ren or at least the smallest possible proportion of spray drying products in the finished product to have a product.

This is how W. Hermann de Groot, I. Adami, G.F. Moretti "The Manufacture of Modern Detergent Powders ", Hermann de Groot Academic Publisher, Wassenaar, 1995, page 102 ff. various mixing and granulating processes for the production of washing and cleaning agents agents. These processes have in common that premixed solids granulated with the addition of the liquid ingredients and optionally post-dried the.

There is also a broad state of the art in non-tower technology in patent literature. Manufacture of washing and cleaning agents. Many of these procedures start from the Acid form of the anionic surfactants, since this surfactant class is the largest in terms of quantity Share of detersive substances and the anionic surfactants in the course of their manufacture Position arise in the form of free acids, which neutralizes to the corresponding salts Need to become.

A new way of producing surfactant granules, which has the disadvantages of the known Avoiding procedures is foam granulation, which is used in older German Pa tent registrations DE 198 44 523.7, DE 198 44 522.9 and DE 198 55 380.3 (all Henkel KGaA) is described.

DE 198 44 523.7 discloses a process for the production of surfactant granules in which is an anionic surfactant in its acid form and a highly concentrated, aqueous alkaline Component separately charged with a gaseous medium, then put together leads and neutralized, and both the anionic surfactant in its acid form as well the highly concentrated, aqueous alkaline component through the gaseous medium foamed and the resulting acidic and alkaline foams to neutralize foam are brought together, which is then pre-selected in a mixer placed solid bed is given. According to the teaching of this document, two foams (one  acidic and an alkaline foam) combined and the neutralized foam as granules tools used for solids.

The older German patent application DE 198 44 522.9 discloses foam granulation procedure in which the foam serving as granulation aid is not combined acidic and alkaline foam. Rather, a procedure ren for the production of surfactant granules, in which a surfactant-containing flowable Component is charged with a gaseous medium, the surfactant-containing flowable component foamed by the gaseous medium and the resulting surfactant-containing foam subsequently on a solid bed placed in a mixer will give. According to the information, the flowable components containing tenside can be read as this publication, for example, nonionic surfactants or the salts of anionic surfactant acids put. About the use of anionic surfactants in the form of a foam is in this Scripture mentioned nothing.

Foam granulation processes with foamed anionic surfactant acid are used in the older German patent application DE 198 55 380.3 disclosed. The subject of this document is a Process for the preparation of surfactant granules, in which an anionic surfactant in its acid form is neutralized with a solid neutralizing agent and granulated, the solid neutralizing agent added to the anionic surfactant in its acid form and to a Neutralisate foam is foamed, which is subsequently placed in a mixer placed solid bed is given. This is where the granulation aid forms neutral reacting foam from the anionic surfactant acid and the solid neutralisa agent. A process in which an acidic surfactant foam is used as granulation tool serves; is also not described in this document.

The present invention was based on the object, the field of foam granules lation further develop and provide a method that allows surfactant granules late for washing and cleaning agents without or with reduced use of spray drying steps and directly from the acid form of the anionic surfactants  approach. The drying of the granules formed should preferably also be full can always be dispensed with.

The present invention relates to a process for the preparation of surfactant gra nulates, in which a surfactant-containing flowable component with a gaseous medium to be acted upon and foamed and the resulting surfactant-containing foam subsequently is placed on a solid bed placed in a mixer and the surfactant-containing contains flowable component anionic surfactant acid (s).

In the method according to the invention, in contrast to the state cited above the art an acid foam, d. H. a foam with a pH below 7, as Granulation aids used. In preferred variants of the Ver driving, the granulated bed to be granulated contains alkaline ingredients, so that weh A neutralization reaction takes place during the granulation process. Here she invented procedure according to the invention compared to the well-known addition of anionic surfactant acids in liquid form the advantage that the acid is gently added to the mixer and very is distributed homogeneously. The formation of coarse clumps or the appearance of acid esters, which cause discoloration of the granules and undesirable reactions with sensitive Ingredients (e.g. perfume) of the ready-made washing and cleaning lead can be effectively avoided.

The term "foam" used in the context of the present invention denotes Formations made of gas-filled, spherical or polyhedral cells (pores), which flow through rivers fluid, semi-fluid or highly viscous cell bridges are limited.

If the volume concentration of the gas forming the foam at homodisperse Distribution is less than 74%, so the gas bubbles are because of the surface-shrinking Effect of the interfacial tension spherical. Above the limit of the densest Ku gel pack, the bubbles are deformed into polyhedral lamellae, which range from approx. 4-600 nm thin cuticles can be limited. The cell webs, connected via so-called nodes dots form a coherent framework. They stretch between the cell bars  Foam slats (closed-cell foam). Are the foam slats destroyed or if they flow back into the cell webs at the end of foam formation, an open cell is obtained foam. Foams are thermodynamically unstable because they are made smaller surface energy can be obtained. The stability and therefore the existence The foams according to the invention therefore depend on how far they succeed to prevent destruction.

To generate the foam, the gaseous medium is converted into the anionic surfactant flowable component is blown in, or the foaming is achieved by intensi ves whipping, shaking, splashing or stirring the liquid in the concerned Gas atmosphere. Because of the lighter and easier to control and perform In the context of the present invention, foaming is the generation of foam by Blowing in the gaseous medium ("gassing") compared to the other variants clearly preferred. Fumigation takes place depending on the desired process variant continuously or discontinuously via perforated plates, sintered discs, sieve inserts, Ven turi nozzles or other common systems.

Any gases or gas mixtures can be used as the gaseous medium for foaming be used. Examples of gases used in technology are nitrogen and acid substance, noble gases and noble gas mixtures, carbon dioxide etc. For cost reasons, this will be Process according to the invention preferably with air as the gaseous medium leads.

The method according to the invention includes the sub-steps of FIG Generation of foam from a flowable component containing anionic surfactant acid and the subsequent addition to a solid bed moved in a mixer, the Foam is used as a granulation aid. The ingredients of the generated in the first step surfactant-containing foam is described below.

The surfactant-containing flowable component contains at least surface-active substances zen from the group of anionic surfactants, which at least partly in their acidity  form, d. H. not neutralized. In addition, the surfactant can flow Component further surface-active compounds from the groups of anionic, contain nonionic, zwitterionic or cationic surfactants. The salary of the flowable surfactant-containing component of surfactant (s) can be within broad limits zen vary. According to the invention, methods are preferred in which the surfactant-containing flowable component one or more anionic surfactant acid (s) in amounts of 20 to 100 % By weight, preferably from 50 to 95% by weight and in particular from 60 to 90% by weight, each based on the surfactant-containing component.

The method according to the invention includes the sub-steps of FIG Generation of foam from an anionic surfactant in its acid form on the one hand and the Zu on the other hand, put it on a solid bed moved in a mixer. The main inventions anionic surfactant acids which can be used according to the invention are described below.

One or more substances from the group are preferred as anionic surfactants in acid form the carboxylic acids, the sulfuric acid half-esters and the sulfonic acids, preferably from the Group of fatty acids, fatty alkyl sulfuric acids and alkylarylsulfonic acids puts. In order to have sufficient surface-active properties, these should be mentioned ten compounds have longer-chain hydrocarbon residues, i.e. in Al alkyl or alkenyl radical have at least 6 carbon atoms. Usually the C- Chain distributions of the anionic surfactants in the range from 6 to 40, preferably 8 to 30 and especially 12 to 22 carbon atoms.

Carboxylic acids, which are used in the form of their alkali metal salts as soaps in detergents and cleaning agents, are technically largely obtained from native fats and oils by hydrolysis. While the alkaline saponification that was carried out in the past century led directly to the alkali salts (soaps), today only water is used on a large technical scale to split the fats into glycerol and the free fatty acids. Large-scale processes are, for example, cleavage in an autoclave or continuous high-pressure cleavage. Carboxylic acids which can be used as anionic surfactants in acid form in the context of the present invention are, for example, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, etc. Use of fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetracoic acid (lignoceric acid), hexotonic acid (melotonic acid), hexotanoic acid, hexotonic acid, right) and the unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidic acid), 9c, 12c-octadecenoic acid (linadecic acid) , 9t, 12t-octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c-octadecatrein acid (linolenic acid) For reasons of cost, it is preferred not to use the pure species, but rather technical mixtures of the individual acids, as can be obtained from fat cleavage. Such mixtures are for example, coconut oil fatty acid (about 6 wt .-% C _8, 6 wt .-% C ₁₀ 48 wt .-% C ₁₂ 18 wt .-% _C14, 10 wt .-% C _16, 2 wt .-% _C18, 8 wt .-% _{C18 ',} 1 wt .-% C _{18 "),} palm kernel oil fatty acid (about 4 wt .-% C _8, 5 wt .-% C _10, 50 wt .-% C _12, 15 wt .-% C _14, 7 wt .-% C _16, 2 wt .-% C ₁₈ 15 wt .-% G _{18 ',} 1 wt .-% C _{18 "),} tallow fatty acid (ca. 3 wt% C ₁₄ , 26 wt% C ₁₆ , 2 wt% C _{16 '} , 2 wt% C ₁₇ , 17 wt% C ₁₈ , 44 wt% C _18' , 3% by weight C _{18 "} , 1% by weight C _{18 '''} ), hardened tallow fatty acid (approx. 2% by weight C ₁₄ , 28% by weight C ₁₆ , 2% by weight C ₁₇ , 63 wt .-% C _18: 1 wt .-% C _{18 '),} technical grade oleic acid (about 1 wt .-% C _12, 3 wt .-% C _14, 5 wt .-% C _16, 6 wt. % C _{16 '} , 1% by weight C ₁₇ , 2% by weight C ₁₈ , 70% by weight C _18' , 10% by weight C _{18 "} , 0.5% by weight C _{18 '''} ), technical palmitin / stearic acid (approx. 1 wt% C ₁₂ , 2 wt% C ₁₄ , 45 wt% C ₁₆ , 2 wt% C ₁₇ , 47 wt% C _18: 1 wt .-% C _{18 ')} and soybean oil fatty acid (about 2 wt .-% C _14, 15 % By weight C ₁₆ , 5% by weight C ₁₈ , 25% by weight C _{18 '} , 45% by weight C _{18 "} , 7% by weight C _18''' ).

Sulfuric acid semiesters of longer-chain alcohols are also anionic surfactants in their acid form and can be used in the process according to the invention. Your alkali metal, especially sodium salts, the fatty alcohol sulfates are commercially available from fatty alcohols which are converted with sulfuric acid, chlorosulfonic acid, amidosulfonic acid or sulfur trioxide to the relevant alkyl sulfuric acids and subsequently neutralized. The fatty alcohols are obtained from the fatty acids or fatty acid mixtures concerned by high-pressure hydrogenation of the fatty acid methyl esters. The most significant industrial process for the production of fatty alkyl sulfuric acids is the sulfonation of the alcohols with SO ₃ / air mixtures in special cascade, falling film or tube bundle reactors.

Another class of anionic surfactant acids used in the process of the invention can be used are the alkyl ether sulfuric acids, their salts, the alkyl ether sulfates, compared to the alkyl sulfates by a higher water solubility and lower Characterize sensitivity to water hardness (solubility of Ca salts). Alkyl ether Like the alkyl sulfuric acids, sulfuric acids are synthesized from fatty alcohols che be reacted with ethylene oxide to the fatty alcohol ethoxylates concerned. On Instead of ethylene oxide, propylene oxide can also be used. The subsequent sul Formation with gaseous sulfur trioxide in short-term sulfonation reactors gives yields over 98% of the relevant alkyl ether sulfuric acids.

Alkanesulfonic acids and olefin sulfonic acids are also within the scope of the present invention can be used as anionic surfactants in acid form. Alkanesulfonic acids can the sulfonic acid regruppe terminally bound (primary alkanesulfonic acids) or along the C chain ten (secondary alkanesulfonic acids), only the secondary alkanesulfonic acids have commercial importance. These are by sulfochlorination or sulfoxidati made on linear hydrocarbons. Reed sulfochlorination uses n- Correspond to paraffins with sulfur dioxide and chlorine under irradiation with UV light The sulfochlorides reacted, which, in the case of hydrolysis with alkalis, directly the alkanesulfo nate, when reacted with water, the alkanesulfonic acids. Because of sulfochloria tion di- and polysulfochlorides as well as chlorinated hydrocarbons as by-products of radical reaction can occur, the reaction is usually only up to Um Settlements of 30% carried out and then canceled.

Another process for producing alkanesulfonic acids is sulfoxidation, in which n- Paraffins reacted with sulfur dioxide and oxygen under irradiation with UV light become. In this radical reaction, successive alkylsulfonyl radicals are formed, which also  Oxygen react further to the alkyl persulfonyl radicals. The reaction with unumge Set paraffin provides an alkyl radical and the alkyl persulfonic acid, which are converted into an alkyl peroxysulfonyl radical and a hydroxyl radical decays. The reaction of the two radicals with unreacted paraffin provides the alkyl sulfonic acids or water, which with Al kylpersulfonic acid and sulfur dioxide to sulfuric acid. To the yield on the to keep the two end products alkyl sulfonic acid and sulfuric acid as high as possible and Suppressing side reactions, this reaction is usually only up to implementation degrees of 1% and then terminated.

Olefin sulfonates are produced industrially by the reaction of α-olefins with sulfur trioxide posed. Intermediate hermaphrodites form here, which become so-called sulto cyclize. React under suitable conditions (alkaline or acid hydrolysis) these sultones to hydroxylalkanesulfonic acids or alkenesulfonic acids, both of which are just if can be used as anionic surfactant acids.

Alkylbenzenesulfonates as powerful anionic surfactants have been around since the 1930s of our century. At that time, monochlorination of kogasin Fractions and subsequent Friedel-Crafts alkylation prepared using alkylbenzenes Oleum sulfonated and neutralized with sodium hydroxide solution. Early 1950s was used to produce alkylbenzenesulfonates propylene to branched α-dodecylene tetramerized and the product via a Friedel-Crafts reaction using Aluminum trichloride or hydrogen fluoride converted to tetrapropylene benzene, which after subsequently sulfonated and neutralized. This economical way of manufacturing of tetrapropylene benzene sulfonates (TPS) led to the breakthrough of this class of surfactants, the subsequently displaced the soaps as the main surfactant in washing and cleaning agents.

Due to the lack of biodegradability of TPS, there was a need to to represent new alkylbenzenesulfonates, which are characterized by an improved ecological ver keep honoring. These requirements are met by linear alkylbenzenesulfonates fills, which are the almost exclusively manufactured alkylbenzenesulfonates and with the abbreviation ABS.  

Linear alkylbenzenesulfonates are made from linear alkylbenzenes, which like which are accessible from linear olefins. For this purpose, petroleum is used on an industrial scale Fractions with molecular sieves separated into the n-paraffins of the desired purity and dehydrogenated to the n-olefins, resulting in both α- and i-olefins. The ent standing olefins are then in the presence of acidic catalysts with benzene to the Al implemented kylbenzenes, the choice of Friedel-Crafts catalyst having an influence the distribution of isomers of the linear alkylbenzenes formed has: When using Aluminum trichloride is the content of the 2-phenyl isomers in the mixture with the 3-, 4-, 5- and other isomers at about 30 wt .-%, however, hydrogen fluoride as Kataly used sator, the content of 2-phenyl isomer can be reduced to about 20 wt .-%. The Finally, sulfonation of linear alkylbenzenes is now possible on an industrial scale using oleum, Sulfuric acid or gaseous sulfur trioxide, the latter being by far the largest has interpretation. Special film or tube bundle reactors are used for sulfonation sets that deliver as a product a 97 wt .-% alkylbenzenesulfonic acid (ABSS), which in Within the scope of the present invention it can be used as anionic surfactant acid.

By choosing the neutralizing agent, a wide variety of salts, ie alkylbenzenesulfonates, can be obtained from the ABSS. For reasons of economy, it is preferred to prepare and use the alkali metal salts and, among them, the sodium salts of the ABSS. These can be described by the general formula I:

in which the sum of x and y is usually between 5 and 13. Processes according to the invention in which C _8-16 -, preferably C _9-13 - alkylbenzenesulfonic acids are used as the anionic surfactant in acid form are preferred. In the context of the present invention, it is further preferred to use C _8-16 -, preferably C _9-13- alkylbenzenesulfonic acids which are derived from alkylbenzenes which have a tetralin content below 5% by weight, based on the alkylbenzene. It is further preferred to use alkylbenzenesulfonic acids whose alkylbenzenes have been prepared by the HF process, so that the C _8-16 -, preferably C _9-13- alkylbenzenesulfonic acids used contain a 2-phenyl isomer below 22% by weight. %, based on the alkylbenzenesulfonic acid.

The above-mentioned anionic surfactants in their acid form can be used alone or in Mi who used and foamed together in the process according to the invention the. But it is also possible and preferred that the anionic surfactant in acid form before Foaming up other, preferably acidic, ingredients of washing and cleaning agents in amounts of 0.1 to 40% by weight, preferably 1 to 15% by weight and in particular dere from 2 to 10 wt .-%, each based on the weight of the foamed Mi be added.

According to the invention, methods are preferred in which the surfactant-containing flowable com component alkylbenzenesulfonic acids in amounts of 20 to 99 wt .-%, preferably of 30 up to 95 wt .-% and in particular from 40 to 90 wt .-%, each based on the surfactant containing component.

Suitable acidic reactants in the context of the present invention are, in addition to the "Surfactic acids" also the fatty acids, phosphonic acids, polymer acids or some neutralized polymer acids as well as "builder acids" and "complex builder acids" (single later in the text) alone as well as in any mixtures. As ingredients of Washing and cleaning agents; which the anionic surfactant acid before foaming can be mixed, especially acidic detergents and cleaning agents Ingredients, for example phosphonic acids, which in neutralized form (Phosphonates) as incrustation inhibitors, part of many detergents and cleaning agents are. The use of (partially neutralized) polymer acids such as Po  lyacrylic acids, is possible according to the invention. But it is also possible to have acid-stable content Mix substances with the anionic surfactant acid before foaming. Here offer themselves For example, so-called small components, which are otherwise in complex other Steps would have to be added, for example optical brighteners, dyes etc., whereby the acid stability must be checked in individual cases.

In preferred processes, the surfactant-containing flowable component additionally contains fat acids and / or soaps in amounts of 1 to 30% by weight, preferably 2 to 25% by weight and in particular from 5 to 20% by weight, in each case based on the surfactant-containing compo nente.

Optionally, the anionic surfactant can be nonionic in acid form before foaming Surfactants in amounts of 0.1 to 60 wt .-%, preferably from 0.5 to 55 wt .-% and ins in particular from 2.5 to 10% by weight, based in each case on the weight of the foam to be foamed Mixture to be mixed. This addition can affect the physical properties of the Improve anionic surfactant foam and a later incorporation of nonionic surfactants into the surfactant granules or all detergents and cleaning agents. The different representatives from the group of nonionic surfactants will continue to exist described below. In preferred processes, the surfactant contains flowable compo nente additionally non-ionic surfactant (s) in amounts of 1 to 50 wt .-%, preferably from 2 to 40 wt .-% and in particular from 5 to 30 wt .-%, each based on the ten component containing sid.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol residue is linear or preferably in the 2-position May be methyl branched or may contain linear and methyl branched radicals in the mixture, as are usually present in oxoalko radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

The use of alkoxylated nonionic surfactants is preferred in the context of the present invention. Process variants in which the surfactant-containing flowable component alkoxylated, preferably ethoxylated nonionic surfactants in amounts of 20 to 90 wt .-%, preferably from 30 to 85 wt .-% and in particular from 40 to 80 wt .-%, each based on the surfactant-containing component has advantages, processes being particularly preferred in which the surfactant-containing flowable component as ethoxylated nonionic surfactants contains the reaction products of C _8-22 fatty alcohols, preferably C _12-20 fatty alcohols and in particular C _{14 -18} fatty alcohols with 1 to 30 moles of ethylene oxide, preferably 2 to 20 mol ethylene oxide and more preferably 5 to 10 mol ethylene oxide in quantities of 10 to 80 wt .-%, preferably from 20 to 75 wt .-% and in particular from 30 to 70 wt .-%, each based on the surfactant-containing component.

Another class of preferred nonionic surfactants, which are used either as allei some nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and pro poxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as described, for example, in Japanese Pa tentanmeldung JP 58/217598 are described or which preferably according to the in ternational patent application WO-A-90/13533 who produced the.  

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Alkypolyglycosides that can be used satisfy the general formula RO (G) _z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol which stands for a glycosyl unit with 5 or 6 carbon atoms, preferably for glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.5.

Linear alkyl polyglucosides, ie alkyl polyglycosides, are preferably used in de the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.

The surfactant granules according to the invention can preferably contain alkyl polyglycosides where the APG granules contain more than 0.2% by weight, based on the total granules, are preferred. Particularly preferred surfactant granules contain APG in amounts of 0.2 up to 10% by weight, preferably 0.2 to 5% by weight and in particular from 0.5 to 3% by weight.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N- dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alka nolamides may be suitable. The amount of these nonionic surfactants is before preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of it.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),

in the RCO stands for an aliphatic acyl radical having 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups . The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

in the R for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ¹ for a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R ² for a linear, branched or cyclic alkyl radical or is an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example, according to the teaching of international application WO-A-95/07331 by reaction with fatty acid remethyl esters in the presence of an alkoxide as a catalyst in the desired polyhy droxy fatty acid amides are transferred.

In preferred processes according to the invention, the surfactant-containing flowable component contains alkoxylated, preferably ethoxylated, nonionic surfactants, preferably the reaction products of C _8-22 fatty alcohols, preferably C _12-20 fatty alcohols and in particular special C _14-18 fatty alcohols with 1 to 30 moles of ethylene oxide , preferably 2 to 20 moles of ethylene oxide and in particular 5 to 10 moles of ethylene oxide.

According to the invention, the surfactant-containing flowable component can consist entirely of one or several surfactants and are therefore free of non-surfactant compounds. According to the invention, however, it is also possible to use further ingredients of washing and cleaning agents to incorporate agents into the surfactant-containing component. In addition to active and Active ingredients can cause the surfactant-containing component ent water hold, this water for setting advantageous viscosity values or for opti Mation of the foaming process of the surfactant-containing component can also be added can. In preferred processes, the surfactant-containing flowable component contains all dings less than 20 wt .-%, preferably less than 15 wt .-% and in particular we less than 10% by weight of water, in each case based on the surfactant-containing component.

In particular, so-called "small components" can according to the Ver drive advantageously over the foam serving as granulating liquid into the surfactant granule be introduced late. In preferred processes according to the invention, the surfactant contains containing flowable component further ingredients of washing and cleaning agents, especially substances from the group of complexing agents, polymers, optical brighteners, Dyes, fragrances and alkalis. This prefers the surfactant-containing flowable com Small components to be added are described below.

The foaming of the flowable surfactant-containing component can, depending on the desired Properties of the foam at room temperature or with cooling or heating respectively. Preferred process variants are carried out so that the foam flowable component containing surfactant before foaming temperatures of 20 up to 120 ° C, preferably from 30 to 90 ° C and in particular from 50 to 75 ° C. The viscosity of the surfactant-containing component can be selected by selecting the ingredients wide limits can be varied, with thinner components containing surfactant in the Usually deliver less stable foams.  

As already mentioned above, it is an advantage of the method according to the invention that in In contrast to conventional granulation processes, granulation liquids are also used can be set, the viscosity is high. So are in the method according to the invention Liquid components containing surfactants can be used, their viscosity above 100 mPa.s but also liquid components with viscosities over 1000 mPa.s, even over 5000 mPa.s, can be foamed according to the invention and in the form of the "granulating foam" can easily be used as a granulation aid.

The flowable surfactant-containing component becomes one through the gaseous medium Foam foamed, with liquid and gaseous medium in varying menus conditions or relationships can be used. For procedural reasons From a viewpoint, it is preferred to use the gaseous medium in each case in quantities for foam generation of at least 20 vol .-%, based on the amount of liquid to be foamed put.

If, for example, a liter of a surfactant-containing component is to be foamed, preferably at least 200 ml of gaseous medium for foaming turns. In preferred processes, the amount of gaseous medium is significantly higher this value, so that methods are preferred in which the foaming set the amount of gas one to three hundred times, preferably five to two hundred times che and in particular ten to one hundred times the volume of the foamed Amount of liquid. As already mentioned above, as a gaseous medium to preferably use air. But it is also possible to use other gases or gas use mixtures for foaming. For example, it may be preferred to air or pass oxygen-enriched air over an ozonizer before the gas to open foaming is used. In this way, you can produce gas mixtures that at for example 0.1 to 4 wt .-% ozone. The ozone content of the foaming gas leads then for the oxidative destruction of undesirable constituents in those to be foamed Liquids. Particularly in the case of partially discolored anionic surfactant acids, the A significant brightening can be achieved by adding ozone.  

For foaming the liter of the surfactant-containing component cited above as an example are thus preferably 1 to 300 liters, preferably 5 to 200 liters and in particular 10 up to 100 liters of air.

About the temperature of the liquid to be foamed on the one hand and the temperature of the gaseous medium on the other hand, the temperature of the resulting foam can ge be controlled. In preferred variants of the method according to the invention, the resulting foam temperatures below 115 ° C, preferably between 20 and 80 ° C. and in particular between 30 and 70 ° C.

The resulting foam, which is used as a granulation aid in the next process step, can be characterized by further physical parameters. For example, it is preferred that the foam have a density below 0.80 gcm ^-3 , preferably from 0.10 to 0.6 gcm ^-3 and in particular from 0.30 to 0.55 gcm ^-3 . It is further preferred that the foam has average pore sizes below 10 mm, preferably below 5 mm and in particular below 2 mm.

The mentioned physical parameters of temperature, density and mean Po The size of the foam characterizes the foam at the time it is created. Preferably the procedure is chosen so that the foam meets the criteria also fulfilled when added to the mixer.

Procedures are possible in which the foam only one or two of the mentioned criteria when added to the mixer met, but preferably both the temperature, as well as the density and pore size in the ranges mentioned, if the foam gets into the mixer.

After its formation, the foam is applied to a solid placed in a mixer Given in bed and serves as a granulation aid. This process stage can be in the various mixing and granulating devices are carried out, as well  is described in detail below. The solid bed placed in the mixer can contain all substances used in detergents and cleaning agents. In this way can manufacture finished detergents and cleaning agents with the method according to the invention be put. Usually, however, certain ingredients of washing and Rei detergents not granulated to prevent undesirable reactions of these components to avoid each other under the mechanical influence of the granulating tools. Ingredients that are usually added to the resulting surfactant granules, i.e. H. in the Following a granulation, bleaching agents are, for example, Bleach activators, enzymes and foam inhibitors.

It is preferred that the surfactant granules produced according to the invention in addition to the Ten sid contain substances which are later used as active substances in washing and cleaning agents act. In preferred processes, the solid bed placed in the mixer therefore contains one or more substances from the builder group, in particular the alkali metal car bonates, sulfates and silicates, zeolites and polymers.

To produce surfactant granules that will later be manufactured with additional components Allow washing and cleaning agents to mix without causing undesirable reactions occur, it is preferred according to the invention that the surfactant granules have no residues contain anionic surfactant acid (s). This can easily be achieved in that the solid bed placed in the mixer contains alkaline components which contain the anion Neutralize surfactant acids. Here come in particular carbonates and hydrogen carbonates in question, but also other alkaline components such as oxides, hydroxides etc. or orga African neutralizing agents such as amines etc. can be used. In the invention preferred process contains the solid bed placed in the mixer one or more Substances from the group of alkali metal carbonates and / or hydrogen carbonates, preferred wise sodium carbonate, in an amount added to neutralize the over the foam led amount of acid sufficient.

It is particularly preferred here if the solid bed placed in the mixer contains the alkali contains components in an amount necessary to neutralize the over the foam  imported quantity of acid is sufficient. For example, about the anionic surfactant foam introduced 2 moles of monobasic acid, so should at least 2 neutralizations equivalents, d. H. for example 2 moles of NaOH or 1 mole of sodium carbonate, in the solid bed included. Processes according to the invention in which the solid bed is more than the stoichiometric amount required to neutralize the amount of acid introduced Contains bases are preferred. It is particularly preferred if the solid bed more than twice, preferably more than three times, particularly preferably more than four times and in particular more than five times that used to neutralize the over contains the amount of alkalinity required for the amount of acid added.

In addition to the washing-active substances, builders are the most important ingredients of Detergents and cleaning agents. In the process according to the invention, all the usual Builders usually used in detergents and cleaning agents in a solid bed be contained, in particular thus zeolites, silicates, carbonates, organic cobuilders and - if there are no ecological concerns about their use - including the phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, 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 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in the international patent application WO-A-91/08171 .

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compaction / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted in such a way that the products have microcrystalline ranges of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to the conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula

n Na ₂ O. (1-n) K ₂ O. Al ₂ O _3. (2-2.5) SiO _2. (3.5-5.5) H ₂ O

can be described. Suitable zeolites have an average particle size of we less than 10 µm (volume distribution; measurement method: Coulter Counter) on and included preferably 18 to 22% by weight, in particular 20 to 22% by weight of bound water.

It goes without saying that the generally known phosphates are also used as buildersub punching possible, provided that such use is not avoided for ecological reasons  should be. Among the large number of commercially available phosphates, the Alka limetal phosphates with particular preference for pentasodium or pentapotassium tri phosphate (sodium or potassium tripolyphosphate) in detergents and cleaning agents Industry the most important.

Alkali metal phosphates is the general term for the alkali metal (in particular sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts or lime incrustations in tissues and also contribute to cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; it occurs when phosphoric acid is adjusted to pH 4.5 with caustic soda and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33 gcm ^-3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is easily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O), becomes water-free at 100 ° and changes to diphosphate Na ₄ P ₂ O ₇ when heated more strongly. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator.

Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm ^-3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 gcm ^-3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises e.g. B. when he heats of Thomas slag with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) . Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed by heating disodium phosphate to <200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dehydrating the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. In 100 g of water about 17 g dissolve at room temperature, at 20 ° approx. 20 g, at 100 ° around 32 g of the salt free of crystalline water; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (<23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

According to the invention, these are exactly like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two can be used; also mixtures of sodium tripolyphos phate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and Sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tri Polyphosphate and sodium potassium tripolyphosphate can be used according to the invention.

As organic cobuilders in the process according to the invention as part of the Solid bed especially polycarboxylates / polycarboxylic acids, polymeric polycarboxyla  te, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) see above how phosphonates are used. These classes of substances are described below.

Usable organic builders are, for example, those in the form of their sodium salt ze usable polycarboxylic acids, such polycarboxylic acids among polycarboxylic acids can be understood that carry more than one acid function. For example, these are Citro Nenoic acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, Fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if one such use is not objectionable for ecological reasons, as well as mixtures from these. Preferred salts are the salts of polycarboxylic acids such as citric acid, Adi Pinic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of the sen.

The acids themselves can also be used. The acids have besides their buil the effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or Detergents. In particular, citric acid, succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.

Polymeric polycarboxylates are also suitable as builders, for example those Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the investigated polymers. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard.

The molar masses measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. Because of their superior solubility, the This group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, preferably his.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As a special copolymers of acrylic acid with maleic acid, 50 to Contain 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative mole Cooling mass, based on free acids, is generally from 2000 to 70,000 g / mol preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be either as a powder or as an aqueous solution be used. The content of (co) polymeric polycarboxylates in the agent is before preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

To improve water solubility, the polymers can also allylsulfonic acids, such as for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer ten.

Biodegradable polymers of more than two ver. Are also particularly preferred different monomer units, for example those that act as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives contain.  

Further preferred copolymers are those which are described in German patent applications DE- A-43 03 320 and DE-A-44 17 734 are described and preferably as monomers Have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise, further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors. Polyas are particularly preferred paraginic acids or their salts and derivatives, of which in the German patent application dung DE-A-195 40 086 discloses that, in addition to cobuilder properties, it also has a have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which are produced by the implementation of Dial dehyden with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl have groups that can be obtained. Preferred polyacetals are from Dialde hyden such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from Obtained polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be. The hydrolysis can be carried out according to conventional methods, for example acid or enzyme lysed procedures are carried out. It is preferably hydrolysis pro Products with average molecular weights in the range of 400 to 500,000 g / mol. There is a poly saccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30 preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dry glu can be used cosesirupe with a DE between 20 and 37 as well as so-called yellow dextrins and White dextrins with higher molar masses in the range from 2000 to 30000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 and international patent applications WO 92/18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608 are known. An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenedia mindisuccinate are other suitable cobuilders. Here, ethylenediamine-N, N'- disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts.

Glycerol disuccinates and Gly are also preferred in this context cerintrisuccinate. Suitable amounts are in zeolite and / or silicate salts gene formulations at 3 to 15 wt .-%.

Other useful organic cobuilders are, for example, acetylated hydroxycarbon acids or their salts, which may optionally also be in lactone form, and which have at least 4 carbon atoms and at least one hydroxyl group and maxi contain two acid groups. Such cobuilders are used, for example, in the inter national patent application WO 95/20029.

Another class of substances with cobuilder properties are the phosphonates it is in particular hydroxyalkane or aminoalkanephosphonates. Under the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) from of particular importance as a cobuilder. It is preferably used as the sodium salt the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). As Aminoalkane phosphonates preferably come from ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher Ho mologist in question. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP, used. HEDP is preferred as a builder from the phosphonate class turns. The aminoalkanephosphonates also have a pronounced heavy metal bin  de assets. Accordingly, it can, especially if the agent also ent bleach hold, be preferred to use aminoalkane phosphonates, in particular DTPMP, or To use mixtures of the phosphonates mentioned.

In addition, all compounds that are capable of complexing with alkaline earth train ions as cobuilders.

The solid bed in the mixer can also contain compounded raw materials, d. H. Ingredients that are themselves the end product of previous process steps. No Granulated, compacted or extruded raw materials are spray-dried Base powder as part of the solid bed placed in the mixer. This spray dried base powders can be free of surfactants (e.g. polymer compounds), but preferably contain surfactants. Such spray-dried base powder should be used are set, the solid bed in the mixer contains based on that in Mi. sheared solids in preferred process variants the spray-dried Base powder, preferably the surfactant-containing spray-dried base powder, in quantities from 10 to 80% by weight, preferably from 15 to 70% by weight and in particular from 20 to 60% by weight.

By adding the foam and under the influence of the mixer tools, a Surfactant granules formed. Methods according to the invention are preferred in which the Surfactant foam in the foam: solid weight ratio of 1: 100 to 9: 1, preferably from 1: 30 to 2: 1 and in particular from 1: 20 to 1: 1, on the feast presented in the mixer cloth bed is given. With the preferred amounts of granulation aid (Ten sid foam) optimal granulation results are achieved.

As already mentioned, the method according to the invention can be used in a variety of ways Carry out mixing and granulating devices. For the implementation of the fiction Mixers suitable according to the process are, for example, Eirich® mixers of the R series or RV (trademark of the machine factory Gustav Eirich, Hardheim), the Schugi® Flexomix, the Fukae® FS-G mixer (trademark of Fukae Powtech, Kogyo Co., Ja  pan), the Lödige® FM, KM and CB mixers (trademark of Lödige Maschinenbau GmbH, Paderborn) or the Drais® series T or K-T (trademark of Drais-Werke GmbH, Mannheim). Some preferred embodiments of the invention Procedures are described below.

For example, it is possible and preferred to use the process according to the invention in one low-speed mixer / granulator at peripheral speeds of the tools of 2 m / s to 7 m / s to carry out, the anionic surfactant-containing foam in a time between 0.5 and 10 minutes, preferably between 1 and 7 minutes and in particular between 2 and 5 minutes, is added to the solid bed placed in the mixer.

Alternatively, in preferred process variants, the foam containing anionic surfactant acid can be added a high-speed mixer / granulator at peripheral speeds of 8 m / s to 35 m / s in a time between 0.1 and 30 seconds, preferably up to 10 seconds and in particular between 0.5 and 2 seconds, against the solid bed placed in the mixer be.

While the two process variants described above use each describe a mixer, it is also possible according to the invention to combine two mixers to combine. For example, methods are preferred in which the anion acidic foam in a first, low-speed mixer / granulator on a be away solid bed is given, 40 to 100 wt .-%, based on the total amount of the components used, the solid and liquid components pre-granulated and in a second, high-speed mixer / granulator, the pre-granulate from the first Process stage with the remaining solid and / or liquid components if necessary is mixed and transferred into granules. In this process variant, the Foam containing anionic tenside in the first mixer / granulator against a solid bed ben and the mixture pre-granulated. The composition of the foam and the im Most mixers placed in the solid bed are selected so that 40 to 100 wt .-%, preferably 50 to 90 wt .-% and in particular 60 to 80 wt .-%, the solid and fluids sigen components, based on the total amount of components used, in the  "Pregranules" are located. This "pre-granulate" is now mixed with others in the second mixer Solids mixed and with the addition of further liquid components to the finished Ten pelletized granules. Here it is possible and preferred according to the invention that in the second process step, the liquid components were not sprayed on as liquid be, but in the form of a foam as a granulation aid ("Granulating liquid") serve. The composition of the foam in the second Mixer is given, the composition of the in the first mixer set foam differ, so that the methods described above are preferred, where in the second, high-speed mixer / granulator the pre-granulate from the first Process stage also with the addition of a surfactant-containing foam, the combination of which setting may differ from the foam used in the first stage of the process finished granules is granulated. The second foam can of course be free from anionic surfactant acids.

According to the invention, the sequence of low-speed, high-speed mixers mentioned can can also be reversed, so that a method according to the invention results in which the Foam containing anionic surfactant acid in a first, high-speed mixer / granulator Moving solid bed is given, 40 to 100 wt .-%, based on the total amount of the components used, the solid and liquid components pre-granulated and in a second, low-speed mixer / granulator, the pre-granulate from the first Process stage with the remaining solid and / or liquid components if necessary is mixed and transferred into granules.

In this variant of the method, what has been said above is to be applied analogously, so that here too Methods are preferred in which in the second, low-speed mixer / granulator Pregranulate from the first stage of the process, also with the addition of an anionic surfactant acid containing foam, the composition of which in the first stage foam can deviate, is granulated to the finished granulate.

All of the above-described design variants of the Ver driving can be carried out batchwise or continuously. In the above  Design variants of the method according to the invention described are used for Some high-speed mixers / granulators used. It is within the scope of the present the invention particularly preferred that a mixer used as a high-speed mixer is, which has both a mixing and a comminution device, the Mixing shaft at speeds of 50 to 150 revolutions / minute, preferably as from 60 to 80 revolutions / minute and the shaft of the comminution device at speeds of 500 to 5000 revolutions / minute, preferably from 1000 to 300 revolutions / minute, is operated.

The method according to the invention is with regard to the selection of the content to be used substances and their concentration can be varied over a wide range. Regardless it is preferred if surfactant granules are produced according to the invention, the surfactants keep above 10 wt .-%, preferably above 15 wt .-% and in particular above 20% by weight, based in each case on the granules, and bulk weights above 600 g / l preferably above 700 g / l and in particular above 800 g / l.

The granulation process according to the invention can be carried out in such a way that particles predetermined size distribution result. Here are methods according to the invention preferred in which the surfactant granules have a particle size distribution in which at least 50% by weight, preferably at least 60% by weight and in particular at least 70% by weight of the particles have sizes in the range from 400 to 1600 μm. The rest too The moisture content of the surfactant granules produced according to the invention can be selected of the raw materials are predetermined, so that subsequent drying steps are dispensed with can be. In preferred processes, the surfactant granules have residual free levels Water from 2 to 15 wt .-%, preferably from 4 to 10 wt .-%, based on the Ten granules, on. The remaining free water content can, for example, by means of a modified UX method (Sartorius MA 30, program 120 ° C over 10 minutes) be communicated.

It is possible according to the inventive method, components for washing and To produce cleaning agents, which only after mixing with other ingredients  the finished detergent and cleaning agent. Of course, fiction but also surfactant granules can be produced, which in themselves already a finished detergent and cleaning agent (for example a textile color detergent) are.

The surfactant granules produced by the process according to the invention can subsequently be mixed with further ingredients of detergents and cleaning agents to give the finished product. However, these ingredients can also be incorporated directly into the surfactant granules via the solid bed or via the surfactant foam and are described below:
In addition to the constituents mentioned, surfactant and builders are, in particular in washing and cleaning agents, the usual ingredients from the group of bleaching agents, bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors , Color transfer inhibitors and corrosion inhibitors are important.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as per benzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Typical organic bleaches are the diacyl peroxides, such as. B. Dibenzoylpero xid. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkyl peroxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidanoic acid paprooxyacrylic acid ], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxydiperoxyacidoxydiperbutylacid, 4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Can also be used as bleach in machine dishwashing compositions Chlorine or bromine releasing substances are used. Among the appropriate chlorine or bromine-releasing materials come, for example, heterocyclic N-bromine and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with Cations such as potassium and sodium are considered. Hydantoin compounds such as 1,3-dichloro- 5,5-dimethylhydanthoin are also suitable.

To be a better choice when washing or cleaning at temperatures of 60 ° C and below To achieve the greatest bleaching effect, bleach activators can be incorporated. As Bleach activators can be compounds that are aliphatic under perhydrolysis conditions Peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms Atoms, and / or optionally substituted perbenzoic acid can be used. Substances containing O and / or N-acyl groups of the number of carbon atoms mentioned are suitable and / or optionally substituted benzoyl groups. Multiple are preferred acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated tri Azine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acy gelled Glycolurile, in particular tetraacetylglycoluril (TAGU), N-acylimide, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonat (n- or iso-NOBS), carboxylic anhydrides, in particular Phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol koldiacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, too so-called bleaching catalysts can be incorporated. These substances are to bleach-enhancing transition metal salts or transition metal complexes as in for example Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also  Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.

Enzymes come from the class of proteases, lipases, amylases, cellulases or their mixtures in question. Bacterial strains or are particularly well suited Mushrooms such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus enzymatic agents. Proteases of the subtilisin type and esp special proteases obtained from Bacillus lentus. Here are En enzyme mixtures, for example of protease and amylase or protease and lipase or Protease and cellulase or from cellulase and lipase or from protease, amylase and Li pase or protease, lipase and cellulase, but especially cellulase-containing Mi of particular interest. Peroxidases or oxidases are also in one proven cases. The enzymes can be adsorbed on carriers and / or be embedded in coating substances to protect them against premature decomposition.

In addition, components can be used, which the oil and fat positively affect washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times with a detergent according to the invention, this oil and fat-dissolving component contains, was washed. The preferred oil and fat dissolving components include for example nonionic cellulose ethers such as methyl cellulose and methyl hydroxy propyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and Hy droxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic Cellulose ether, as well as the polymers of phthalic acid known from the prior art and / or terephthalic acid or its derivatives, in particular polymers of ethyl lenterephthalates and / or polyethylene glycol terephthalates or anionic and / or not tionically modified derivatives of these. Of these, the sul are particularly preferred Formed derivatives of phthalic and terephthalic polymers.

The detergents and cleaning agents can, as optical brighteners, derivatives of the diaminostyle Contain bendisulfonic acid or its alkali metal salts. Are suitable for. B. salts of 4,4'-  Bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or the same well-structured compounds that a diethanolamino instead of the morpholino group group, a methylamino group, an anilino group or a 2-methoxyethylamino wear group. Brighteners of the substituted diphenylstyryl type can also be used be essential, e.g. B. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3- sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures too the aforementioned brighteners can be used.

Dyes and fragrances are added to detergents and cleaning agents to improve the aesthetics to improve the impression of the products and the consumer in addition to the softness a visually and sensorially "typical and unmistakable" product supply. As perfume oils or fragrances, individual fragrance compounds, e.g. B. the synthetic products of the type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons are used. Fragrance compounds of the ester type are z. B. benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate tat, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalylbenzoate, benzyl formate, Ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzylsa licylate. The ethers include, for example, benzyl ethyl ether, the aldehydes z. B. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cy clamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones z. B. the Jono ne, ∝-isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, citronellol, Eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbon The terpenes such as limes and pinene belong mainly to fen. However, are preferred Mixtures of different fragrances are used, which together make an appealing Generate fragrance. Such perfume oils can also contain natural fragrance mixtures ten, as they are accessible from plant sources, e.g. B. Pine, Citrus, Jasmine, Pat chouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, Ka millen oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, Vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, Orange peel oil and sandalwood oil.  

The content of detergents and cleaning agents is usually lower than that of colorants 0.01% by weight, while fragrances make up up to 2% by weight of the total formulation can.

The fragrances can be incorporated directly into the washing and cleaning agents But it can also be advantageous to apply the fragrances to carriers that increase the adhesion of the Reinforcing perfumes on the laundry and slower fragrance release for longer maintain the fragrance of the textiles. Such carrier materials have, for example se cyclodextrins have proven themselves, with the cyclodextrin-perfume complexes additionally other auxiliaries can be coated.

To improve the aesthetic impression of detergents and cleaning agents, you can they are dyed with suitable dyes. Preferred dyes, their selection the expert has no difficulty, have a high storage stability and Un sensitivity to the other ingredients of the agent and to light as well no pronounced substantivity towards textile fibers in order not to dye them.

The foam produced in the process according to the invention and its use as granules tion aids have not been described in the prior art. Another counter The present invention is therefore a surfactant foam available from Beaufschla a surfactant-containing flowable component with a gaseous medium, because characterized in that the foam contains anionic surfactant acid (s) and medium pore size below 10 mm, preferably below 5 mm and in particular below 2 mm, having.

As already emphasized in the description of the method according to the invention, is a surfactant foam is preferred in which the gaseous medium is at least 20% by volume drew on the amount of liquid to be foamed. With one especially before tenside foam makes the gaseous medium one to three hundred times preferably five to two hundred times and in particular ten to one hundred times the volume of the amount of liquid to be foamed.  

The surfactant foam according to the invention is preferably high in surfactant. Surfactant foams, the surfactant contents from 50 to 99% by weight, preferably from 60 to 95% by weight, and in particular have from 70 to 90% by weight, based in each case on the weight of the foam, are preferred here.

Another object of the present invention is the use of the Invention appropriate surfactant foams as a granulation liquid in the production of surfactant granules laten. Regarding the proportions between granulation aids (surfactant foam) and solid bed, the mixer to be used and the In used in the solid bed Solids are referred to the above explanations.  

Examples

A tower powder containing surfactant was produced by spray drying and was introduced together with soda in a 20 liter ploughshare mixer from Lödige. The composition of the tower powder is given in Table 1. With the mixing tools running, C _9-13 -alkylbenzenesulfonic acid (ABS acid) was added to the mixer as a granulation aid, causing the mixture to granulate. In the process variants E1 and E2 according to the invention, the anionic surfactant acid was brought up to five times the volume by foaming with compressed air before addition to the mixer; in the comparative examples V1 and V2, the anionic surfactant acid was added to the mixer in liquid form. In all four cases, the ABS acid (foam or liquid) had a temperature of 60 ° C. After four minutes of granulation, the granules were sprayed with perfume oil. After 7 days of storage at 20 ° C, the fragrance impression was assessed by a perfumer. Table 2 shows the composition of the granules, the oversize fraction formed during the granulation and the fragrance impression after storage.

Table 1

Composition of the tower powder [% by weight]

Table 2

Composition of the granules [% by weight]

Table 2 shows that the coarse fraction ver is reduced, on the other hand, the more uniform distribution of the acid formation acidic nests and the resulting impairment of the fragrance impression avoided.

Claims (26)

1. A process for the production of surfactant granules, wherein a surfactant-containing flowable component is acted upon and foamed with a gaseous medium and the resulting surfactant-containing foam is subsequently added to a solid bed placed in a mixer, characterized in that the surfactant-containing flowable component is anionic surfactant acid (n ) contains. 2. The method according to claim 1, characterized in that the surfactant-containing flowable Component one or more anionic surfactant acid (s) in amounts of 20 to 100% by weight, preferably from 50 to 95% by weight and in particular from 60 to 90% by weight, each because based on the surfactant-containing component. 3. The method according to claim 2, characterized in that the surfactant-containing flowable Component alkylbenzenesulfonic acids in amounts of 20 to 99 wt .-%, preferably two se from 30 to 95 wt .-% and in particular from 40 to 90 wt .-%, each based on contains the surfactant-containing component. 4. The method according to any one of claims 1 to 3, characterized in that the surfactant containing flowable component additionally fatty acids and / or soaps in amounts of 1 up to 30% by weight, preferably from 2 to 25% by weight and in particular from 5 to 20 % By weight, based in each case on the surfactant-containing component. 5. The method according to any one of claims 1 to 4, characterized in that the surfactant containing flowable component additionally nonionic surfactant (s) in amounts of 1 up to 50% by weight, preferably from 2 to 40% by weight and in particular from 5 to 30 % By weight, based in each case on the surfactant-containing component. 6. The method according to claim 5, characterized in that the surfactant-containing flowable component alkoxylated, preferably ethoxylated nonionic surfactants, preferably as the reaction products of C _8-22 fatty alcohols, preferably C _12-20 fatty alcohols and in particular C _14-18 fatty alcohols Contains 1 to 30 moles of ethylene oxide, preferably 2 to 20 moles of ethylene oxide and in particular 5 to 10 moles of ethylene oxide. 7. The method according to any one of claims 1 to 6, characterized in that the surfactant containing flowable component less than 20 wt .-%, preferably less than 15 % By weight and in particular less than 10% by weight of water, in each case based on the ten contains component. 8. The method according to any one of claims 1 to 7, characterized in that the surfactant containing flowable component further ingredients of washing and cleaning agents teln, in particular substances from the group of complexing agents, polymers, optical Brightener, color and fragrance and alkalis. 9. The method according to any one of claims 1 to 8, characterized in that the for Foaming used amount of gas one to three hundred times, preferably that five to two hundred times and especially ten to one hundred times the volume the amount of the surfactant-containing flowable component to be foamed makes. 10. The method according to any one of claims 1 to 9, characterized in that as gas feed medium air is used. 11. The method according to any one of claims 1 to 10, characterized in that the up foaming surfactant-containing flowable component before foaming Temperatu ren from 20 to 120 ° C, preferably from 30 to 90 ° C and in particular from 50 to 75 ° C. 12. The method according to any one of claims 1 to 11, characterized in that the ten sidewise foam temperatures below 115 ° C, preferably between 20 and 80 ° C and in particular between 30 and 70 ° C.   13. The method according to any one of claims 1 to 12, characterized in that the ten-side foam has a density below 0.80 gcm ^-3 , preferably from 0.10 to 0.60 gcm ^-3 and in particular from 0.30 to 0 , 55 gcm ^-3 . 14. The method according to any one of claims 1 to 13, characterized in that the ten Sid-containing foam average pore sizes below 10 mm, preferably below 5 mm and in particular below 2 mm. 15. The method according to any one of claims 14 to 14, characterized in that the ten Foam containing sid fulfills the criteria mentioned when added to the mixer. 16. The method according to any one of claims 1 to 15, characterized in that the Mixer submitted solid bed one or more substances from the group builder fe, in particular the alkali metal carbonates, sulfates and silicates, the zeolites and Polymers. 17. The method according to any one of claims 1 to 16, characterized in that the Mixer submitted solid bed one or more substances from the group of alkali metal carbonates and / or hydrogen carbonates, preferably sodium carbonate, in one Contains the amount needed to neutralize the amount of acid supplied via the foam is sufficient. 18. The method according to any one of claims 1 to 17, characterized in that the Mixer placed solid bed spray-dried base powder, preferably surfactant containing spray-dried base powder, in amounts of 10 to 80 wt .-%, preferably from 15 to 70 wt .-% and in particular from 20 to 60 wt .-%, based on the Mixer submitted solids, contains. 19. The method according to any one of claims 1 to 18, characterized in that the ten Sid-containing foam in the foam: solid weight ratio of 1: 100 to 9: 1  preferably from 1:30 to 2: 1 and in particular from 1:20 to 1: 1, to that in the mixer placed solid bed is given. 20. The method according to any one of claims 1 to 19, characterized in that the ten sidgranulate surfactant contents above 10% by weight, preferably above 15% by weight and in particular above 20% by weight, based in each case on the granules, and bulk weights above 600 g / l, preferably above 700 g / l and in particular above 800 g / l. 21. The method according to any one of claims 1 to 20, characterized in that the ten sidgranulate residual free water contents of 2 to 15% by weight, preferably of 4 up to 10% by weight, based on the surfactant granules. 22. Surfactant foam, obtainable by applying a flowable surfactant Component with a gaseous medium, characterized in that the Foam contains anionic surfactant acid (s) and average pore sizes below 10 mm preferably below 5 mm and in particular below 2 mm. 23. surfactant foam according to claim 22, characterized in that the gaseous medium by at least 20 vol .-%, based on the amount of liquid to be foamed makes. 24. surfactant foam according to claim 23, characterized in that the gaseous medium by one to three hundred times, preferably five to two hundred times and in particular ten to one hundred times the volume of the rivers to be foamed amount of liquid. 25. surfactant foam according to any one of claims 22 to 24, characterized in that it Anionic surfactant acid contents from 50 to 99% by weight, preferably from 60 to 95% by weight and in particular from 70 to 90 wt .-%, each based on the weight of the Foam.   26. Use of surfactant foams according to one of claims 22 to 25, as granules tion liquid in the manufacture of surfactant granules.