EP1123382B1 - Granulation method - Google Patents

Abstract

The invention relates to a neutralization and granulation method wherein a neutralizing foam is used as granulation adjuvant. The neutralizing foam was previously obtained by mixing an anionic surfactant in its acid form, which was expanded using a gaseous medium, and a highly concentrated, aqueous alkaline component, which was expanded using a gaseous medium. The neutralizing foam has an average pore size of 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 detergents and cleaning agents. In particular, it relates to a method which allows detergent and cleaning agent compositions without or with reduced use of spray drying steps manufacture.

Granular detergent and cleaning agent compositions are largely made by spray drying. When spray drying, the ingredients are like Surfactants, builders etc. with approx. 35 to 50% by weight water to form an aqueous slurry, the so-called slurry, mixed and in spray towers in a hot gas stream atomized, whereby the detergent and cleaning agent particles form. Either are the facilities for this process as well as the implementation of the process costly because most of the slurry water must be evaporated to remove particles with residual water content to get 5 to 10% by weight. They also have through Spray drying granules usually have excellent solubility but only have low bulk weights, resulting in higher packaging volumes as well Transport and storage capacities. The flowability of spray-dried granules is not optimal due to its irregular surface structure, which is also affects their visual appearance. Spray drying processes have another Series of disadvantages, so that there has been no lack of attempts to manufacture Carrying out detergents and cleaning agents completely without spray drying or at least to have the smallest possible proportions of spray drying products in the finished product.

For example, W. Hermann de Groot, I. Adami, GF Moretti "The Manufacture of Modern Detergent Powders" , Hermann de Groot Academic Publisher, Wassenaar, 1995, page 102 ff. Describes various mixing and granulating processes for the production of detergents and cleaning agents. These processes have in common that premixed solids are granulated with the addition of the liquid ingredients and, if necessary, subsequently dried.

There is also a broad state of the art in non-tower manufacturing in patent literature of detergents 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 detergent substances and the anionic surfactants in the course of their manufacture in the form of free acids, which neutralize to the corresponding salts Need to become.

For example, European patent application EP-A-0 678 573 (Procter & Gamble) describes a process for producing free-flowing surfactant granules with bulk densities above 600 g / l, in which anionic surfactant acids with an excess of neutralizing agent form a paste with at least 40% by weight of surfactant are reacted and this paste is mixed with one or more powder (s), at least one of which must be spray-dried and which contains anionic polymer and cationic surfactant, the resulting granules optionally being able to be dried. Although this document reduces the proportion of spray-dried granules in the washing and cleaning agents, it does not completely avoid spray drying.

European patent application EP-A-0 438 320 (Unilever) discloses a batch process for the production of surfactant granules with bulk densities above 650 g / l. Anionic surfactant acid is added to a solution of an alkaline inorganic substance in water, possibly with the addition of other solids, and granulated in a high-speed mixer / granulator with a liquid binder. Neutralization and granulation take place in the same apparatus, but in separate process steps, so that the process can only be operated in batches.

A continuous neutralization / granulation process for the production of FAS and / or ABS granules from the acid is known from the European patent application EP-A-0 402 112 (Procter & Gamble), in which the ABS acid contains at least 62% NaOH is neutralized and then granulated with the addition of auxiliaries, for example ethoxylated alcohols or alkylphenols or a polyethylene glycol melting above 48.9 ° C. with a molecular weight between 4000 and 50,000.

European patent application EP-A-0 508 543 (Procter & Gamble) mentions a process in which a surfactant acid is neutralized with an excess of alkali to form an at least 40% by weight surfactant paste, which is then conditioned and granulated, one Direct cooling with dry ice or liquid nitrogen takes place.

Dry neutralization processes in which sulfonic acids are neutralized and granulated are disclosed in EP 555 622 (Procter & Gamble). According to the teaching of this document, the anionic surfactant acids are neutralized in a high-speed mixer by means of an excess of finely divided neutralizing agent with an average particle size of less than 5 μm.

A similar process, which is also carried out in a high-speed mixer and in which sodium carbonate ground to 2 to 20 μm is used as the neutralizing agent , is described in WO98 / 20104 (Procter & Gamble).

Surfactant mixtures which are subsequently sprayed onto solid absorbents and which provide detergent compositions or components therefor are also described in EP 265 203 (Unilever). The liquid surfactant mixtures disclosed in this document contain sodium or potassium salts of alkylbenzenesulfonic acids or alkyl sulfuric acids in amounts of up to 80% by weight, ethoxylated nonionic surfactants in amounts of up to 80% by weight and a maximum of 10% by weight of water.

Similar surfactant mixtures are also disclosed in the older EP 211 493 (Unilever). According to the teaching of this document, the surfactant mixtures to be sprayed on contain between 40 and 92% by weight of a surfactant mixture and more than 8 to a maximum of 60% by weight of water. For its part, the surfactant mixture consists of at least 50% polyalkoxylated nonionic surfactants and ionic surfactants.

A method for producing a liquid surfactant mixture from the three components anionic surfactant, nonionic surfactant and water is described in EP 507 402 (Unilever). The surfactant mixtures disclosed here, which are said to contain little water, are prepared by combining equimolar amounts of neutralizing agent and anionic surfactant acid in the presence of nonionic surfactant.

German laid - open specification DE-A-42 32 874 (Henkel KGaA) discloses a process for producing washable and cleaning-active anionic surfactant granules by neutralizing anionic surfactants in their acid form. However, only solid, powdery substances are disclosed as neutralizing agents. The granules obtained have surfactant contents of around 30% by weight and bulk densities of less than 550 g / l.

European published patent application EP 642 576 (Henkel KGaA) describes a two-stage granulation in two consecutive mixers / granulators, in a first, low-speed granulator 40-100% by weight, based on the total amount of constituents used, of the solid and liquid constituents pre-granulated and in a second, high-speed granulator, the pre-granules are mixed with the remaining constituents, if necessary, and transferred into a granulate.

The German published application DE-A-43 04 062 discloses a method of making washing and cleaning-active surfactant granules in which a Anionic surfactant in the acid form and an aqueous one alkaline solution separated with a gaseous Medium (air). After the merge and neutralization becomes the starting product added to one or more inorganic solids, before the granulation starts in a mixer. However, the production looks ahead of the raw materials to be sprayed with the carrier gas through a nozzle.

European patent EP 772 674 (Henkel KGaA) describes a process for the production of surfactant granules by spray drying, in which anionic surfactant acid (s) and highly concentrated alkaline solutions are subjected separately to a gaseous medium and mixed in a multi-component nozzle, neutralized and sprayed into one Hot gas stream can be spray dried. The finely divided surfactant particles obtained in this way are then agglomerated in a mixer to give granules with bulk densities above 400 g / l.

• Bei der Neutralisation mit NaOH wie sie im Stand der Technik beschrieben wird, entsteht eine erhebliche Wärmemenge, wobei Überhitzung zur unerwünschten Dunkelfärbung der Produkte führt;
• Eine direkte Kühlung mit Trockeneis oder flüssigem Stickstoff verursacht hohe Betriebskosten;
• Eine Kühlung durch indirekten Wärmeübergang erfordert eine langsame oder gar batchweise Reaktionsführung mit langen Verweilzeiten und großen Behältervolumina, was sich in hohen Investitionskosten niederschlägt;
• Bei indirekter Kühlung steigt die Viskosität der Neutralisationsmischung oft stark an, was einen Wasserzusatz und eine spätere Nachtrocknung erforderlich macht;
• Hohe Konzentrationen an Aktivsubstanzen erhöhen in der Regel die Viskosität, wodurch die homogene Einarbeitung des Neutralisats bei nachfolgenden Agglomerationsschritten auf feste Träger erschwert wird;
• Beim Einsatz fester Neutralisations- und Agglomerationsmittel (beispielsweise Natriumcarbonat) verläuft die Neutralisationsreaktion verlangsamt und/oder zunächst unvollständig, so daß säureempfindliche Feststoffe wie Silikate oder Zeolithe im Feststoffbett nicht zugegen sein dürfen.

The object of the present invention was to provide a method which makes it possible to produce detergents and cleaning agents without or with reduced use of spray drying steps. The process to be provided should also enable direct and economically attractive processing of the acid forms of detergent raw materials, but largely avoid the disadvantage of energy-intensive water evaporation. Solutions that solve the described fields of activity are described in the prior art mentioned above. Nevertheless, the methods mentioned have a number of disadvantages:

• During the neutralization with NaOH as described in the prior art, a considerable amount of heat is generated, overheating leading to the undesired darkening of the products;
• Direct cooling with dry ice or liquid nitrogen causes high operating costs;
• Cooling by indirect heat transfer requires a slow or even batch reaction with long dwell times and large container volumes, which is reflected in high investment costs;
• With indirect cooling, the viscosity of the neutralization mixture often rises sharply, which requires the addition of water and subsequent drying;
• High concentrations of active substances generally increase the viscosity, which makes it more difficult to incorporate the neutralizate homogeneously in subsequent agglomeration steps on solid supports;
• When solid neutralization and agglomeration agents (for example sodium carbonate) are used, the neutralization reaction is slowed down and / or initially incomplete, so that acid-sensitive solids such as silicates or zeolites must not be present in the solid bed.

Avoiding the disadvantages mentioned above and providing a process the rapid and complete neutralization of anionic surfactant acids without the risk overheating and particularly easy processing into surfactants Including granules were further objects of the present invention.

The problem is solved in a mixing and granulating process in which foamed Anionic surfactant acids and alkali solutions combined to form a neutralizate foam which serves as a granulating aid. The invention thus relates to Process for the preparation of surfactant granules, in which an anionic surfactant is in its acid form and a highly concentrated aqueous alkaline component separated with a gaseous one Medium, then merged and neutralized, and both the anionic surfactant in its acid form and the highly concentrated, aqueous alkaline Component foamed by the gaseous medium and the resulting acidic and alkaline foams are combined to form a neutralized foam, which is subsequently placed on a solid bed placed in a mixer.

The term "foam" used in the context of the present invention denotes Formations made of gas-filled, spherical or polyhedral cells (pores), which are separated by liquid, semi-fluid or highly viscous cell bridges can be 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 ball packing the bubbles are deformed into polyhedral lamellae, which are from about 4-600 nm thin cuticles can be limited. The cell bridges, connected via so-called nodes, 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-celled cell is obtained Foam. Foams are thermodynamically unstable because the surface area is reduced Surface energy can be obtained. The stability and therefore the existence The foams according to the invention are therefore dependent on the extent to which they succeed in self-destruction to prevent.

To produce the foams, the gaseous medium is placed in the liquids mentioned blown in, or the foaming is achieved by violent beating, shaking, Spray or stir the liquid in the gas atmosphere in question. Due to the lighter and more controllable and feasible foaming is within the scope of present invention the foam generation by blowing in the gaseous medium ("Fumigation") clearly preferred over the other variants. The fumigation Depending on the desired process variant, this is carried out continuously or discontinuously via perforated plates, sintered discs, sieve inserts, Venturi nozzles, inline mixers, homogenizers 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, oxygen, Noble gases and noble gas mixtures such as helium, neon, argon and their Mixtures, carbon dioxide etc. The method according to the invention is used for reasons of cost preferably carried out with air as the gaseous medium. If the to be frothed Components are stable to oxidation, the gaseous medium can also be entirely or partially consist of ozone, which causes oxidatively destructible contamination or discoloration in the fluid components to be foamed which are to be foamed or germ contamination of these components can be prevented.

The method according to the invention includes the sub-steps of FIG Generation of foams from an anionic surfactant in its acid form on the one hand and from a highly concentrated, aqueous alkaline component on the other hand. The two Foams are then combined to form a neutralized foam, which is subsequently added to Addition to a solid bed moving in a mixer serves as a granulating aid. The Ingredients of the intermediate products of the first two steps 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 used. In order to have sufficient surface-active properties, the above should Compounds have longer-chain hydrocarbon residues, i.e. in the alkyl or alkenyl radical have at least 6 carbon atoms. The C chain distributions are usually the anionic surfactants in the range of 6 to 40, preferably 8 to 30 and especially 12 to 22 carbon atoms.

Carboxylic acids, which are used as soaps in detergents and cleaning agents in the form of their alkali metal salts, are technically largely obtained from native fats and oils by hydrolysis. While the alkaline saponification which was carried out in the past century led directly to the alkali salts (soaps), only water is used on an industrial 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 an anionic surfactant 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. The preferred compound in the context of the present compound is 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), tetracosanoic acid (lignoceric acid), triacidic acid (melotonic acid), trisonic acid (melotic acid) 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 ((elaidinic acid), 9c, 12c-octadecenoic acid) (9c -Octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c-octadecatreic 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''), Palmkemölfettsäure (about 4 wt .-% C _8, 5 wt .-% C _10, 50 wt % C ₁₂ , 15% by weight C ₁₄ , 7% by weight C ₁₆ , 2% by weight C ₁₈ , 15% by weight C _{18 '} , 1% by weight C _{18 "} ), tallow fatty acid (approx 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 oleic acid (approx. 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 (approx. 2 wt% C ₁₄ , 15 wt .-% C _16, 5 wt .-% C _18, 25 wt .-% C _{18 ',} 45 wt .-% C _{18 ",} 7 wt .-% 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. Their alkali metal, in particular sodium salts, the fatty alcohol sulfates, are commercially available from fatty alcohols which are reacted with sulfuric acid, chlorosulfonic acid, amidosulfonic acid or sulfur trioxide to give the alkyl sulfuric acids concerned and are 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. In terms of quantity, the most important 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 according to the invention 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 are synthesized like fatty acids from alkyl alcohols, which be reacted with ethylene oxide to give the fatty alcohol ethoxylates in question. Instead of of ethylene oxide, propylene oxide can also be used. The subsequent sulfonation with gaseous sulfur trioxide in short-term sulfonation reactors gives yields over 98% of the relevant alkyl ether sulfuric acids.

Alkane sulfonic acids and olefin sulfonic acids can also be used as anionic surfactants in acid form in the context of the present invention. Alkanesulfonic acids can contain the sulfonic acid group in a terminal bond (primary alkanesulfonic acids) or along the C chain (secondary alkanesulfonic acids), only the secondary alkanesulfonic acids being of commercial importance. These are made by sulfochlorination or sulfoxidation of linear hydrocarbons. In Reed sulfochlorination, n-paraffins are reacted with sulfur dioxide and chlorine under irradiation with UV light to give the corresponding sulfochlorides, which give the alkanesulfonates directly when hydrolysed with alkalis and the alkanesulfonic acids when reacted with water. Since di- and polysulfochlorides and chlorinated hydrocarbons can occur as by-products of the radical reaction in the sulfochlorination, the reaction is usually only carried out up to degrees of conversion of 30% and then terminated.

Another process for the production of alkanesulfonic acids is sulfoxidation, in which n-paraffins implemented under irradiation with UV light with sulfur dioxide and oxygen become. In this radical reaction, successive alkylsulfonyl radicals are formed, which also React oxygen further to the alkylpersulfonyl radicals. The reaction with unreacted Paraffin provides an alkyl radical and the alkyl persulfonic acid, which are converted into an alkyl peroxysulfonyl radical and a hydroxyl radical breaks down. The reaction of the two radicals with unreacted paraffin provides the alkyl sulfonic acids or water, which with alkyl persulfonic acid and sulfur dioxide reacts 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 degrees of implementation of 1% and then canceled.

Olefin sulfonates are produced industrially by the reaction of α-olefins with sulfur trioxide. Intermediate hermaphrodites are formed, which become so-called sultons cyclize. React under suitable conditions (alkaline or acid hydrolysis) these sultones to hydroxylalkanesulfonic acids or alkenesulfonic acids, both of which can also 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 alkylbenzenes using 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, the following was 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 improved ecological behavior distinguished. These requirements are met by linear alkyl benzene sulfonates, which are the almost exclusively manufactured alkylbenzenesulfonates today and with the abbreviation ABS.

Linear alkylbenzenesulfonates are made from linear alkylbenzenes, which in turn are accessible from linear olefins. Large-scale petroleum fractions are used for this separated with molecular sieves into the n-paraffins of the desired purity and dehydrogenated to the n-olefins, resulting in both α- and i-olefins. The resulting In the presence of acidic catalysts, olefins then become the alkylbenzenes with benzene implemented, the choice of Friedel-Crafts catalyst having an impact 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, is hydrogen fluoride as a catalyst used, the content of 2-phenyl isomer can be reduced to approximately 20% by weight. 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 most important Has. Special film or tube bundle reactors are used for sulfonation. which 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.

in der die Summe aus x und y üblicherweise zwischen 5 und 13 liegt. Erfindungsgemäße Verfahren, in denen als Aniontensid in Säureform C_8-16-, vorzugsweise C_9-13-Alkylbenzolsulfonsäuren eingesetzt werden, sind bevorzugt. Es ist im Rahmen der vorliegenden Erfindung weiterhin bevorzugt, C_8-16-, vorzugsweise C_9-13-Alkybenzolsulfonsäuren einzusetzen, die sich von Alkylbenzolen ableiten, welche einen Tetralingehalt unter 5 Gew.-%, bezogen auf das Alkylbenzol, aufweisen. Weiterhin bevorzugt ist es, Alkylbenzolsulfonsäuren zu verwenden, deren Alkylbenzole nach dem HF-Verfahren hergestellt wurden, so daß die eingesetzten C_8-16-, vorzugsweise C_9-13-Alkybenzolsulfonsäuren einen Gehalt an 2-Phenyl-Isomer unter 22 Gew.-%, bezogen auf die Alkylbenzolsulfonsäure, aufweisen.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 of less than 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 have a 2-phenyl isomer content of less than 22% by weight. , based on the alkylbenzenesulfonic acid.

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

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 partially neutralized Polymer acids as well as "builder acids" and "complex builder acids" (details later in the text) alone as well as in any mixtures. As ingredients of Washing and cleaning agents; which is mixed with the anionic surfactant acid before foaming acid detergent and cleaning agent ingredients are particularly suitable on, for example phosphonic acids, which are in neutralized form (Phosphonates) as incrustation inhibitors, part of many detergents and cleaning agents are. The use of (partially neutralized) polymer acids such as polyacrylic acids, is possible according to the invention. However, it is also possible to use acid-stable ingredients mix 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.

Preference is given to nonionic anionic surfactants in acid form before foaming Surfactants in amounts from 0.1 to 40% by weight, preferably from 1 to 15% by weight and in particular from 2 to 10% by weight, based in each case on the weight of the foam to be foamed Mixture, mixed. This addition can affect the physical properties of the anionic surfactant foam improve and a later incorporation of nonionic surfactants in the Eliminate the surfactant granules or the entire detergent and cleaning agent. The Different representatives from the group of nonionic surfactants are shown below described.

As highly concentrated, aqueous alkaline components, which are also in an independent Partial step is foamed, concentrated solutions are more water-soluble Alkalis in water. In principle, there are a wide variety of alkalis such as Alkanolamines and metal hydroxides can be used, from practical and economical For reasons, however, alkali metal hydroxide solutions are used as the aqueous alkaline component, preferably sodium hydroxide solutions with concentrations of at least 40 % By weight NaOH, preferably at least 50% by weight NaOH and in particular at least 65% by weight of NaOH, in each case based on the aqueous alkaline component to be foamed, used.

Here, the concentration of sodium hydroxide in the solution can be increased if at the same time the temperature of the solution is increased. This is problem-free according to the invention possible.

Further ingredients of detergents and cleaning agents can also be added to the aqueous alkaline component before foaming. In this case, it is preferred that these further ingredients of detergents and cleaning agents are obtained in amounts of 0.1 to 80% by weight, preferably 10 to 75% by weight and in particular 25 to 70% by weight to the weight of the mixture to be foamed. By adding further ingredients of detergents and cleaning agents to the alkaline component to be foamed, its viscosity can be increased and the viscosity of the anionic surfactant acid can be adjusted. For the later mixing of the two foams produced in the partial steps, it is advantageous if the two liquid components to be foamed (surfactant acid and alkali component) have similar, preferably even identical, viscosity values before the foaming. Viscosities are measured in a manner known per se using the Ford flow cup or spindle viscometer such as the Brookfield viscometer. The viscosity of the alkaline component to be foamed can be adjusted using commercially available viscosity regulators. In addition to synthetic polymers such as polyacrylates, polyurethanes, etc., natural or semi-synthetic products such as xanthans, celluloses and cellulose derivatives, starch and starch derivatives, etc. are also suitable. These organic high-molecular substances, which are also called swelling agents, absorb liquids, swell and finally convert into viscous real or colloidal solutions, come from the groups of natural polymers, modified natural polymers and fully synthetic polymers.
Polymers derived from nature that are used as thickeners are, for example, agar agar, carrageenan, tragacanth, acacia, alginates, pectins, polyoses, guar flour, carob flour, starch, dextrins, gelatin and casein.
Modified natural products come primarily from the group of modified starches and celluloses, examples include carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and core meal ether.
A large group of thickeners that are widely used in a wide variety of applications are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes.

Thickeners from the classes of substances mentioned are widely available commercially and are, for example, under the trade names Acusol®-820 (Methacrylic acid (stearyl alcohol-20-EO) ester-acrylic acid copolymer, 30% in water, Rohrn & Haas), Dapral®-GT-282-S (alkyl polyglycol ether, Akzo), Deuterol®-Polymer-11 (Dicarboxylic acid copolymer, Schönes GmbH), Deuteron®-XG (anionic Heteropolysaccharide based on β-D-glucose, D-manose, D-glucuronic acid, more beautiful GmbH), Deuteron®-XN (non-ionic polysaccharide, Schönes GmbH), Dicrylan®-Thickener-O (ethylene oxide adduct, 50% in water / isopropanol, Pfersse Chemistry), EMA®-81 and EMA®-91 (ethylene-maleic anhydride copolymer, Monsanto), Thickener-QR-1001 (polyurethane emulsion, 19-21% in water / diglycol ether, Rohm & Haas), Mirox®-AM (anionic acrylic acid-acrylic acid ester copolymer dispersion, 25%) in water, Stockhausen), SER-AD-FX-1100 (hydrophobic urethane polymer, Servo Delden), Shellflo®-S (high molecular polysaccharide, stabilized with formaldehyde, Shell) and Shellflo®-XA (xanthan biopolymer, stabilized with formaldehyde, Shell) available.

A preferred polymeric thickener is xanthan, a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and having a molecular weight of 2 to 15 million daltons. Xanthan is formed from a chain with β-1,4-bound glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan.
Xanthan can be described by the following formula:

Carboxymethyl cellulose (CMC) has also proven particularly useful as a viscosity regulator, which, for example, also makes sodium hydroxide solution sufficient without any further additives foaming stably.

Although it is possible in principle, the aqueous alkaline component without further additives foam and this foam with the anionic surfactant foam to a neutralized foam To unite is the addition of foam stabilizing agents to the aqueous Alkali solution preferred before foaming. In preferred processes, the aqueous alkaline component before foaming surfactants, especially anionic and / or nonionic surfactants, preferably ethoxylated alcohols and / or soaps.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly 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.

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, such as them are described, for example, in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533 .

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Alkypolyglycosides which 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 Is symbol which stands for a glycose 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 1.4.
Linear alkyl polyglucosides, ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.

The surfactant granules produced according to the invention can preferably alkyl polyglycosides contain, with contents of the granules of APG over 0.2 wt .-%, based on the total Granules are preferred. Particularly preferred surfactant granules contain APG in Quantities of 0.2 to 10% by weight, preferably 0.2 to 5% by weight and in particular 0.5 up 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 alkanolamides can be suitable. The amount of these nonionic surfactants is preferably not more than that of ethoxylated fatty alcohols, especially not more than half of it.

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zukkers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Other suitable surfactants are polyhydroxy fatty acid amides of the formula (II),

in which RCO stands for an aliphatic acyl radical with 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.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula (III)

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or 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 rest.

[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, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Since the alkaline component serves to neutralize the anionic surfactant acid, however with regard to the molecular weight differs significantly from this, exist when using the each pure, i.e. only the respective active substance (anionic surfactant or alkali component) containing foams significant differences in the amounts of foam, so that a relatively large amount of anionic surfactant foam with a relatively small amount of alkali foam is united. One is due to the foaming of both components homogeneous, quick and complete neutralization without risk of overheating and discoloration possible, but in order to achieve further optimized process results, the quantities, i.e. Align volumes of anionic surfactant and alkali foam. This is possible, for example, via the amount of gaseous medium. So can for the foaming of the alkali component a larger based on the liquid Amount of gaseous medium are foamed, which leads to an increase in Foam volume runs. Another way is the incorporation of alkali-stable washing and Detergent ingredients in the solution of the alkaline component, taking non-ionic surfactants are particularly suitable because they also have a foam-stabilizing effect. In this way, before foaming - based on the liquid to be foamed - If larger amounts of nonionic surfactants are added to the alkali component, they will be the same Foam volumes of the two foams to be combined together, which optimized Results of the procedure.

Regardless of whether the pure anionic surfactant acid is a mixture of anionic surfactant acid and other washing and cleaning agent ingredients, the pure aqueous alkali solution or an aqueous alkali solution containing, for example, nonionic surfactant is foamed for foam generation from the anionic surfactant in its acid form and the highly concentrated aqueous alkaline component the gaseous medium each in amounts of at least 20 vol .-%, based on the amount of liquid to be foamed.

For example, if you want to foam one liter of a highly concentrated ABS acid, are preferably at least 200 ml of gaseous medium for foaming used. In preferred processes, the amount of gaseous medium is clear above this value, so that processes are preferred in which those used for foaming Gas quantity one to three hundred times. preferably five to two hundred times and in particular ten to one hundred times the volume of the foam to be foamed Amount of liquid. As mentioned earlier, is called gaseous Medium is preferably air. But it is also possible to use other gases or Use gas mixtures for foaming. For example, it may be preferred to clean Oxygen or the air to be used for foaming via an ozonizer lead before the gas is used for foaming. In this way you can mix gases produce that contain, for example, 0.1 to 4 wt .-% ozone. The ozone content of the foaming gas then leads to the oxidative destruction of undesirable components in the liquids to be foamed. Especially with partially discolored anionic surfactant acids a clear brightening can be achieved by adding ozone.

Preferred for foaming the liter of ABS acid cited above by way of example 1 to 300 liters, preferably 5 to 200 liters and in particular 10 to 100 liters of air used.

The liquids to be foamed in the sub-steps can be prepared before foaming Have room temperature, but the foaming can also at elevated temperature be performed. Preferred processes are characterized in that the ones to be foamed Liquid components before foaming temperatures from 20 to 100 ° C, preferably from 30 to 90 ° C and in particular from 50 to 75 ° C.

The two foams produced in the partial steps are then combined. This forms a stable neutralizate foam with partial release of the previously trapped gas when the gas flow is much larger than the liquid flow is selected (continuous process control), this excess gas supports the transport of the foam, the dissipation of the heat of reaction and the Discharge of excess water from raw materials and the neutralization reaction comes. Excessively high temperatures lead to an undesirable brown color of the neutralized foam that should be avoided. In preferred variants of the invention The process therefore has the neutralized foam at temperatures below of 115 ° C, preferably between 50 and 95 ° C and in particular between 70 and 90 ° C, on.

The resulting neutralizate 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 neutralized foam has a density of at most 0.80 gem ^-3 , preferably from 0.10 to 0.60 gcm ^-3 and in particular from 0.30 to 0.55 gcm ^-3 . It is further preferred that the neutralized foam has average pore sizes below 10 mm, preferably below 5 mm and in particular below 2 mm. The average pore size is calculated from the sum of all pore sizes (pore diameter) divided by the number of pores and can be determined, for example, by photographic methods.

The specified physical parameters of temperature, density and average pore size characterize the neutralized foam at the time of its creation. Preferably the procedure is chosen so that the neutralized foam the criteria mentioned are also met 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 it has formed, the neutralized foam is placed in a mixer Given solid bed and serves as a granulation aid. This stage of the process can be carried out in a wide variety of mixing and granulating devices. In a suitable mixing and granulating device, for example in a corresponding one Plants of the type of an Eirich mixer, a Lödige mixer, for example one Ploughshare mixer from Lödige, or a mixer from Schugi, is used by Circumferential speeds of the mixing elements, preferably between 2 and 7 m / s (ploughshare mixer) or 3 to 50 m / s (Eirich, Schugi), in particular between 5 and 20 m / s submitted a solid bed and then with the addition of the neutralized foam granulated. At the same time, a predetermined grain size can be achieved in a manner known per se of the granulate can be adjusted. The granulation and mixing process only needs a very short period of time, for example about 0.5 to 10 minutes, in particular about 0.5 to 5 minutes (Eirich mixer, Lödige mixer) for homogenizing the mixture with formation of the free-flowing granules. In the Schugi mixer, however, is usually enough a dwell time of 0.5 to 10 seconds to give a free-flowing granulate receive. Mixers suitable for carrying out this method step are, for example Eirich® mixers of the R or RV series (trademark of the machine factory Gustav Eirich, Hardheim), the Schugi® Flexomix, the Fukae® FS-G mixer (trademark the Fukae Powtech, Kogyo Co., Japan), 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).

The solid bed placed in the mixer can all be used in detergents and cleaning agents contain substances used. In this way, with the invention Process finished detergents and cleaning agents are produced. Usually if certain ingredients of washing and cleaning agents are not granulated, to prevent undesirable reactions of these components among themselves under the mechanical Avoid exposure to the pelletizing tools. Ingredients that arise Surfactant granules usually only subsequently, i.e. following a granulation are added, for example, bleaching agents, bleach activators and enzymes.

It is preferred that the surfactant granules produced according to the invention in addition to the surfactant Contain substances that are later used as active substances in detergents and cleaning agents act. In preferred processes, the solid bed placed in the mixer therefore contains one or more substances from the group builders, in particular the alkali metal carbonates, sulfates and silicates, the zeolites and the polymers.

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 can usually be used Builders 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, 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 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 in dissolving 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, compacting / 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 as meaning that the products have microcrystalline areas 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 conventional water glasses, are described, for example, in German patent application DE-A-44 00 024 . Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

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 ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula Na ₂ ^O. (1-n) K ₂ O ^· Al ₂ O ₃ ^· (2 to 2.5) SiO ₂ ^· (3.5 to 5.5) H ₂ O can be described. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 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 builder substances possible if such use is not avoided for ecological reasons should be. The sodium salts of orthophosphates, pyrophosphates, are particularly suitable and especially the tripolyphosphates.

Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if 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 from these.

By adding the neutralized foam and under the influence of the mixer tools a surfactant granulate is formed. Methods according to the invention are preferred where the neutralized foam in the weight ratio foam: solid from 1: 100 to 9: 1, preferably from 1:20 to 10: 1 and in particular from 1:10 to 1: 1, to that in the mixer submitted solid bed is given. With the preferred amounts of granulation aid (Neutralized foam) optimal granulation results are achieved.

The method according to the invention is with regard to the selection of the ingredients to be used and their concentration can be varied over a wide range. Regardless it is preferred if surfactant granules are produced according to the invention, the 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 densities 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 surfactant granules produced by the process according to the invention can subsequently with other ingredients from detergents and cleaning agents to the finished product be mixed. If necessary, these ingredients can also be on the solid bed or incorporated directly into the surfactant granules via the neutralized foam and are described below:

In addition to the ingredients mentioned, surfactant and builders are particularly common in laundry and Detergents usual ingredients from the group of bleaching agents, bleach activators, Enzymes, pH adjusting agents, 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.

Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. 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 alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoxyacidoxy (PAP), )], o-Carboxybenzamidoperoxycapronsäure, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, Diperocysebacinsäure, diperoxybrassylic acid, diperoxyphthalic acids, the 2-decyldiperoxybutane-1, 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 improve when washing or cleaning at temperatures of 60 ° C and below To achieve 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 C atoms, in particular 2 to 4 C 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 triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated Glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially 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 diacetate 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 around bleach-enhancing transition metal salts or transition metal complexes such as, 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 in particular are preferred Proteases obtained from Bacillus lentus are used. Here are enzyme mixtures, for example from protease and amylase or protease and lipase or Protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, but especially mixtures containing cellulase of special interest. Peroxidases or oxidases have also been found in some Cases proved to be suitable. The enzymes can be adsorbed on carriers and / or be embedded in coating substances to protect them against premature decomposition.

In addition, components can also be used that allow oil and fat to be washed out 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, the 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 hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups from 1 to 15% by weight, based in each case 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 ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives of these. Of these, the sulfonated ones are particularly preferred Derivatives of phthalic acid and terephthalic acid polymers.

The detergents and cleaning agents can be derivatives of diaminostilbenedisulfonic acid as optical brighteners or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar built-up compounds that instead of the morpholino group a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group wear. Brighteners of the substituted diphenylstyryl type may also be present be, e.g. 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 Improve impression of the products and the consumer in addition to the softness performance a visually and sensory "typical and unmistakable" product to deliver. As perfume oils or fragrances, individual fragrance compounds, e.g. synthetic products of the ester, ether, aldehyde, ketone, alcohol type and hydrocarbons are used. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, Dimethylbenzyl-carbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, Ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g. the Jonone, ∝-isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, citronellol, Eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons mainly include the terpenes like limes and pinene. 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, as they are accessible from plant sources, e.g. Pine, citrus, jasmine, patchouly, Rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile 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 can also be advantageous to apply the fragrances to the carrier, which increase the liability of the perfume on the laundry and by a slower fragrance release for long-lasting fragrance of the textiles. Such carrier materials have, for example Cyclodextrins have proven themselves, with the cyclodextrin-perfume complexes additionally can be coated with other auxiliaries.

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 Insensitivity 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 neutralized foam produced in the process according to the invention and its use So far, granulation aids have not been described in the prior art. Another The present invention therefore provides a neutralized foam by combining an anionic surfactant foamed with a gaseous medium in its acid form and a highly concentrated, foamed with a gaseous medium aqueous alkaline component, which is characterized in that the Foam medium pore sizes below 10 mm, preferably below 5 mm and in particular below 2 mm.

As already emphasized in the description of the method according to the invention, is preference is given to a neutralized foam in which the gaseous medium has at least 20% by volume, based on the amount of liquid foamed. With a particularly preferred one Neutralisate foam makes the gaseous medium one to three hundred times. preferably five to two hundred times and in particular ten to one hundred times of the volume of the foamed liquid quantity.

Regarding the ingredients of the foams produced in separate steps, is also to the description of preferred embodiments of the method according to the invention directed. Preferred neutralized foams are made by combining one Foam from an anionic surfactant in its acid form, which is optionally further, preferably contains acid, ingredients of detergents and cleaning agents and one Foam from an aqueous alkali metal hydroxide, preferably sodium hydroxide solution, the possibly further ingredients of washing and cleaning agents, in particular contains nonionic surfactants. It is preferred that the neutralized foam by combining an anionic surfactant foam and a nonionic surfactant Sodium hydroxide foam was obtained, the sodium hydroxide foam being 5 to 80% by weight, preferably 10 to 75% by weight and in particular 25 to 70% by weight of nonionic surfactant, each based on the weight of the sodium hydroxide foam. Another preferred Neutralisate foam is made by combining a foam from an anionic surfactant its acid form, the nonionic surfactants in amounts of 0.1 to 10 wt .-%, preferably from 0.5 to 7.5% by weight and in particular from 1 to 5% by weight, in each case based on the weight of the anionic surfactant foam, and a foam from an aqueous Alkali metal hydroxide, preferably sodium hydroxide solution, the further optionally Contains ingredients of washing and cleaning agents, in particular non-ionic surfactants, receive.

The neutralizate foam according to the invention is preferably high in surfactant. Neutralisatschäume, the surfactant contents from 20 to 99% by weight, preferably from 60 to 95% by weight and in particular from 70 to 90% by weight, in each case based on the weight of the foam, have are preferred.

Another object of the present invention is the use of the invention Neutralisate foams as a granulation liquid in the manufacture of surfactant granules. With regard to the quantitative relationships between granulation aids (neutralized foam) and solid bed, the mixers to be used and those which can be used in the solid bed Ingredients are referred to the above explanations.

Examples: a) continuous seduction:

The following mass flows were fed in through two separate pipe sections equipped with non-return valves: Liquid component I 103.7 kg / h C _9-13 alkylbenzenesulfonic acid 10.6 kg / h C _12-18 fatty acid 4.2 kg / h Hydroxyethane-1,1-diphosphonic Liquid component II 61.7 kg / h C _12-18 fatty alcohol with 7 EO 33.9 kg / h Sodium hydroxide solution, 50%

Before the foaming, the liquid component I had a temperature of 74 ° C. and the liquid component II a temperature of 61 ° C. The mass flows were foamed over sintered disks with 8 m ³ / h of air each and the foams formed were combined in a static mixer. The two foams were completely mixed to form the neutralized foam in a dynamic mixer with an internal volume of 5 liters (type RM 3-30 / 65, company GTA, D-31699 Beckedorf), so that the residence time was in the range of seconds. The resulting stable neutralizate foam had the following physical parameters at the outlet of the dynamic mixer: temperature 80 ° C density 0.45 gcm ^-3 pore size <2 mm

The 80 ° C warm neutralizate foam was fed into a ploughshare mixer via a 20 mm pipe dosed with 2 knife heads (type KM300-D, Gebrüder Lödige, Paderborn), the foam in the area of the first cutter head onto the moving solid bed onto surface.

The following mass flows were processed as a solid bed: 288.6 kg / h Zeolite A (Wessalith® P, Degussa) 256.2 kg / h sodium sulphate 169.6 kg / h sodium 85.9 kg / h Sokalan® CP 5, 50%

The granulate continuously discharged from the mixer has the following physical parameters: bulk weight 840 g / l Sieve analysis: > 1.6 mm 3 Wt .-% > 1.2 mm 9 Wt .-% > 0.8 mm 26 Wt .-% > 0.4 mm 41 Wt .-% <0.4 mm 22 Wt .-% colour pure white

For comparison, the inventive method described above was not in accordance with the invention varies in that the liquids do not mix before mixing were foamed (no air feed). In this comparative example, rose the temperature in the dynamic mixer exceeded 110 ° C and the neutralized paste discolored turn brown. The feed into the mixer provided a sticky granulate with high Oversize.

b) Batchwise procedure:

With the help of a glass frit, the liquid components I and II heated to 70 ° C., the composition of which is given below (data based on the entire batch), were foamed to twice the volume with air as the gaseous medium. Liquid component I 10.37 Wt .-% C _9-13 alkylbenzenesulfonic acid 1.06 Wt .-% C _12-18 fatty acid 6.71 Wt .-% C _12-18 fatty alcohol with 7 EO 0.42 Wt .-% Hydroxyethane-1,1-diphosphonic Liquid component II 2.53 Wt .-% Sodium hydroxide solution, 65%

The foamed liquid components I and II were mixed with a laboratory stirrer and the neutralized foam is foamed again to twice the volume. Subsequently the neutralized foam was opened in a 50L Lödige mixer with a chopper the solid bed placed in the mixer (composition: see below), where a batch of 10 kg was processed.

Solid bed: 30.88 Wt .-% Zeolite A (Wessalith® P, Degussa) 32.93 Wt .-% sodium sulphate 6.51 Wt .-% sodium 8.59 Wt .-% Sokalan® CP5, 50%

The granulate discharged from the mixer has the following physical parameters: bulk weight 835 g / l Sieve analysis: > 1.6 mm 13 Wt .-% > 0.8 mm 22 Wt .-% > 0.4 mm 33 Wt .-% > 0.2 mm 24 Wt .-% > 0.1 mm 7 Wt .-% <0.1 mm 1 Wt .-% colour pure white

Further experiments on a production scale were carried out with liquid components of the composition given in Table 1. For this purpose, the liquid components I and II were each metered into a pipe section equipped with a check valve at a temperature of 50 ° C. and foamed over sintered disks with 50 times the volume of compressed air. The resulting foams were combined in a static mixer and homogeneously mixed in a dynamic mixer to form a neutralizate foam [density: 0.5 gcm ^-3 , pore size <1 mm, temperature: approx. 80 ° C. (by neutralization reaction)].

The neutralized foam was metered into a ploughshare mixer with 2 cutter heads (type KM300-D, Gebrüder Lödige, Paderborn), the foam in the area of the first cutter head striking the moving solid bed (composition see table 2) and the mixer tools at peripheral speeds of 3 m / s were moved. The continuous granulation was carried out with a mass discharge of 1 to 1.4 t / h. Pure white, free-flowing surfactant granules were again formed, the composition of which is given in Table 3 and the physical properties of which are summarized in Table 4. The surfactant granulate E2 was fed to a 2-screw extruder from Lihotzky and extruded under a pressure of 25 bar at a temperature of 54 ° C. through perforated die plates with hole diameters of 1.8 mm. After the extrusion, the resulting strand sections were rounded off in a commercially available rounding device, 3.5% by weight of zeolite A being used as the powdering agent. The information in Table 4 relates to the crude extrudate for example E2. Example E2 also shows that so-called small components (here: optical brightener) can be easily incorporated into the products via the foams. Composition of the flowable surfactant components [% by weight] E1 E2 E3 E4 E5 a) Liquid component I C _9-13 alkylbenzenesulfonic acid 87.5 87.7 87.5 87.5 87.5 C _12-18 fatty acid 9.0 4.8 9.0 9.0 9.0 Hydroxyethane-1,1-diphosphonic 3.5 7.5 3.5 3.5 3.5 b) Liquid component II Sodium hydroxide solution 50% 33.5 47.0 33.5 99.5 - Potash lye, 50% - - - - 41.5 carboxymethylcellulose - - - 0.5 - C _12-18 fatty alcohol with 7 EO 66.5 25.8 66.5 - 58.5 Polyethylene glycol 400 - 25.8 - - - optical brightener - 1.4 - - - Solid bed composition [% by weight] E1 E2 E3 E4 E5 Zeolite A (Wessalith® P, Degussa) 34.5 5.1 37.0 34.5 - Zeolite X (Wessalith® XD, Degussa) - 56.1 - - 36.5 sodium sulphate 32.8 - 28.0 33.0 44.0 sodium 21.5 - 23.5 29.0 8.5 sodium citrate - 6.2 - - - Polyethylene glycol 4000 - 3.1 - - - polymer compound 11.2 17.1 11.5 3.5 11.0 Fatty alcohol sulfate compound - 12.4 - - - Composition of the surfactant granules [% by weight] E1 E2 E3 E4 E5 Liquid component I (Table 1 a) 11.85 18.55 11.85 23.17 11.85 Liquid component II (Table 1 b) 10.10 12.27 10.10 6.65 11.47 = Neutralized foam (Table 1) 21.95 30.82 21.95 29.82 23.32 Solids (Table 2) 78.05 69.18 78.05 70.18 76.68 Physical data of the surfactant granules E1 E2 E3 E4 E5 Bulk density [g / I] 850 750 916 828 980 Sieve analysis [% by weight]: > 1.6 mm 7 90 2 2 0 > 1.2 mm 13 9 4 4 1 > 0.8 mm 23 1 14 15 5 > 0.4 mm 26 - 52 27 26 <0.4 mm 31 - 28 44 68 colour pure white brilliant white pure white pure white pure white

Claims (28)

1. A process for the production of surfactant granules in which an anionic surfactant in its add form and a highly concentrated aqueous alkaline component are separately exposed to a gaseous medium, subsequently combined and then neutralized, characterized in that both the anionic surfactant in its acid form and the highly concentrated aqueous alkaline component are foamed by the gaseous medium and the acidic and alkaline foams formed are combined to form a neutralizate foam which is subsequently applied to a bed of solids accommodated in a mixer.
2. A process as claimed in claim 1, characterized in that one or more substances from the group of carboxylic acids, sulfuric acid semiesters and sulfonic acids, preferably from the group of fatty acids, fatty alkyl sulfuric acids and alkylaryl sulfonic acids, islare used as the anionic surfactant in acid form.
3. A process as claimed in claim 1 or 2, characterized in that C_8-16, preferably C_9-13 alkyl benzenesulfonic acids are used as the anionic surfactant in acid form.
4. A process as claimed in any of claims 1 to 3, characterized in that other, preferably acidic, detergent ingredients in quantities of 0.1 to 40% by weight, preferably 1 to 15% by weight and more preferably 2 to 10% by weight, based on the weight of the mixture to be foamed, are added to the anionic surfactant in add form before foaming.
5. A process as claimed in any of claims 1 to 4, characterized in that nonionic surfactants in quantities of 0.1 to 40% by weight, preferably 1 to 15% by weight and more preferably 2 to 10% by weight, based on the weight of the mixture to be foamed, are added to the anionic surfactant in acid form before foaming.
6. A process as claimed in any of claims 1 to 5, characterized in that alkali metal hydroxide solutions, preferably sodium hydroxide solutions with concentrations of at least 40% by weight NaOH, preferably at least 50% by weight NaOH and more preferably at least 65% by weight NaOH, based on the aqueous alkaline component to be foamed, are used as the aqueous alkaline component.
7. A process as claimed in any of claims 1 to 6, characterized in that other detergent ingredients in quantities of 0.1 to 80% by weight, preferably 10 to 75% by weight and more preferably 25 to 70% by weight, based on the weight of the mixture to be foamed, are added to the aqueous alkaline component before foaming.
8. A process as claimed in claim 7, characterized in that surfactants, preferably anionic and/or nonionic surfactants, more particularly ethoxylated alcohols and/or soap, are added to the aqueous alkaline component before foaming.
9. A process as claimed in any of claims 1 to 8, characterized in that, for generating foam from the anionic surfactant in its acid form and the highly concentrated aqueous alkaline component, the gaseous medium is used in quantities of at least 20% by volume, based on the quantity of liquid to be foamed.
10. A process as claimed in claim 9, characterized in that the volume of gas used for foaming makes up one to three hundred times, preferably five to two hundred times and more preferably ten to one hundred times the volume of liquid to be foamed.
11. A process as claimed in any of claims 1 to 10, characterized in that air is used as the gaseous medium.
12. A process as claimed in any of claims 1 to 11, characterized in that the liquid components to be foamed have temperatures before foaming of 20 to 100°C, preferably in the range from 30 to 90°C and more preferably in the range from 50 to 75°C.
13. A process as claimed in any of claims 1 to 12, characterized in that the neutralizate foam has temperatures below 115°C. preferably between 50 and 95°C and more preferably between 65 and 90°C.
14. A process as claimed in any of claims 1 to 13, characterized in that the neutralizate foam has a density of at most 0.80 gcm^-3, preferably in the range from 0.10 to 0.6 gcm^-3 and more preferably in the range from 0.3 to 0.55 gcm^-3.
15. A process as claimed in any of claims 1 to 14, characterized in that the neutralizate foam has mean particle sizes below 10 mm, preferably below 5 mm and more preferably below 2 mm.
16. A process as claimed in any of claims 13 to 15, characterized in that the neutralizate foam satisfies the criteria mentioned at the time it is introduced into the mixer.
17. A process as claimed in any of claims 1 to 16, characterized in that the bed of solids initially introduced into the mixer contains one or more substances from the group of builders, more particularly alkali metal carbonates, sulfates and silicates, zeolites and polymers.
18. A process as claimed in any of claims 1 to 17, characterized in that the neutralizate foam is added to the bed of solids initially introduced into the mixer in a ratio by weight of foam to solids of 1:100 to 9:1, preferably 1:30 to 2:1 and more preferably 1:20 to 1:1.
19. A process as claimed in any of claims 1 to 18, characterized in that the surfactant granules have surfactant contents above 10% by weight, preferably above 15% by weight and more preferably above 20% by weight, based on the granules, and bulk densities above 600 g/l, preferably above 700 g/l and more preferably above 800 g/l.
20. A process as claimed in any of claims 1 to 19, characterized in that the surfactant granules have a particle size distribution where at least 50% by weight, preferably at least 60% by weight and more preferably at least 70% by weight of the particles are between 400 and 1600 µm in size.
21. A neutralizate foam obtainable by combining an anionic surfactant in its acid form foamed with a gaseous medium and a highly concentrated aqueous alkaline component foamed with a gaseous medium,
    characterized in that the foam has mean pore sizes below 10 mm, preferably below 5 mm and more preferably below 2 mm.
22. A neutralizate foam as claimed in claim 21, characterized in that the gaseous medium makes up at least 20% by volume, based on the foamed volume of liquid.
23. A neutralizate foam as claimed in claim 22, characterized in that the gaseous medium makes up from one to three hundred times, preferably five to two hundred times and more preferably ten to one hundred times the volume of foamed liquid.
24. A neutralizate foam as claimed in any of claims 21 to 23, characterized in that it is obtained by combining a foam of an anionic surfactant in its acid form, which optionally contains other, preferably acidic, detergent ingredients, and a foam of an aqueous alkali metal hydroxide, preferably sodium hydroxide, solution optionally containing other detergent ingredients, more particularly nonionic surfactants.
25. A neutralizate foam as claimed in any of claims 21 to 24, characterized in that it is obtained by combining a foam of an anionic surfactant in its acid form, which contains nonionic surfactants in quantities of 0.1 to 10% by weight, preferably 0.5 to 7.5% by weight and more preferably 1 to 5% by weight, based on the weight of the anionic surfactant foam, and a foam of an aqueous alkali metal hydroxide, preferably sodium hydroxide, solution optionally containing other detergent ingredients, more particularly nonionic surfactants.
26. A neutralizate foam as claimed in any of claims 21 to 25, characterized in that it is obtained by combining an anionic surfactant add foam and a sodium hydroxide foam containing nonionic surfactants, the sodium hydroxide foam containing 5 to 80% by weight, preferably 10 to 75% by weight and more preferably 25 to 70% by weight of nonionic surfactant, based on the weight of the sodium hydroxide foam.
27. A neutralizate foam as claimed in any of claims 21 to 26, characterized in that it has surfactant contents of 20 to 99% by weight, preferably 60 to 95% by weight and more preferably 70 to 90% by weight, based on the weight of the foam.
28. The use of the neutralizate foams claimed in any of claims 21 to 27 as a granulation liquid in the production of surfactant granules.