DE10123622A1 - Preparing granules of high anionic surfactant content, useful for preparing washing and cleaning compositions, by fluidized bed processing of neutralization foam - Google Patents

Abstract

Granules (A) with a high content of anionic surfactant (I) are prepared by (i) making a 'neutralization foam' (B) from a concentrate containing at least one (I) in acid form and a concentrated aqueous solution of alkali and (ii) introducing (B), optionally combined with other ingredients of washing and cleaning compositions, into a fluidized bed apparatus for simultaneous drying and granulation.

Description

The present invention relates to a method for producing surfactant granules. she relates in particular to a method which allows surfactant granules with high Surfactant content largely avoiding additional drying steps manufacture. It also relates to a process for the production of washing or Detergents with these surfactant granules.

Granular detergent and cleaning agent compositions are largely made by spray drying. When spray drying, the ingredients are like Surfactants, builders, etc. with about 35 to 50 wt .-% water to an aqueous Slurry, the so-called slurry, mixed and in spray towers in one Hot gas stream atomizes, whereby the detergent and cleaning agent particles form.

Surfactant granules can, for example, by conventional drying technology from Solutions and pastes containing surfactants, especially in the spray tower. So is used, for example, in European patent EP-B-0 319 819 (Henkel KGaA) Process for the production of surfactant granules by spray drying disclosed, wherein a sulfonic acid and a highly concentrated aqueous sodium hydroxide solution separated with a gaseous medium, then in stoichiometric amounts merged, neutralized in a multi-component nozzle and at a high Propellant gas pressure is sprayed in the drying tower. The products obtained are solid these products are mostly relatively dusty, a relatively high one Have water content and a low bulk density.  

Both the facilities for this process and the implementation of the process are costly because most of the slurry water must be evaporated to Particles with residual water content to get the 5 to 10 wt .-%. They also have Granules produced by spray drying are usually excellent Solubility, but have only low bulk weights, which leads to higher Packaging volumes as well as transport and storage capacities. Also the Flowability of spray-dried granules is due to their irregular Surface structure is not optimal, which also affects its visual appearance effect. Spray drying processes have a number of disadvantages that there was no lack of attempts, the production of detergents and cleaning agents to be carried out completely without spray drying or at least the smallest possible proportion of To have spray drying products in the finished product.

W. Hermann de Groot, I. Adami, G. F. Moretti describes "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 Detergents and cleaning agents. These processes have in common that premixed solids with the addition of the liquid ingredients granulated and be dried if necessary.

With other granulation processes there is again a certain water content and one maintain certain process temperature. For example, that describes European patent EP-B-0 403 148 (Procter & Gamble) a process for the production of fatty alcohol sulfate granules that are dispersible in cold water. Doing so a highly concentrated aqueous fatty alcohol sulfate paste that is less than 14% by weight Water and less than 20 wt .-% contains other additives at temperatures between Machined at 10 and 45 ° C until granules are formed. In this way Although fatty alcohol sulfate granules are obtained that are already at washing temperatures be dispersed between 4 and 30 ° C; the process temperature to be observed and however, the relatively low maximum water content of the surfactant paste is critical driving parameters. It is also not disclosed which bulk weights the after have granules produced by this process.

From the European patent EP-B-0 402 112 (Procter & Gamble) is a method for Production of fatty alcohol sulfate and / or alkylbenzenesulfonate granules known the neutralization of the anionic surfactants in acid form to form a paste with a maximum of 12% by weight  Water with the addition of auxiliaries such as polyethylene glycols, ethoxylated Alcohols or alkylphenols, which have a melting point above 48 ° C, and the granulation takes place in a high-speed mixer. Again, the amount of water to be observed is a critical process parameter does not disclose the bulk densities of the surfactant obtained by this process have granules.

From the European patent EP-B-0 402 111 (Procter & Gamble) is a method for Production of detergent-active granules with a bulk density that are active in washing or cleaning between 500 and 1200 g / l, a surfactant formulation known as Liquid component contains water and also organic polymers and May contain builder substances, mixed with a finely divided solid and in one High speed mixer is granulated. Here too the water content of the Surfactant paste is a critical process parameter. If the water content of the If the surfactant paste is too high, the solid is dispersed so that it is no more than Deagglomeration agent can act. On the other hand, the solids content exceeds a certain value, the mass does not have the necessary for the granulation Consistency.

In the European patent EP-A-0 603 207 (Henkel KGaA) a method for Production of detergent-active granules with a bulk density that are active in washing or cleaning above 500 g / l by granulation of a surfactant preparation form, which is a non- Has surfactant liquid component, described, a surfactant preparation form that under normal pressure at temperatures between 20 and 40 ° C in liquid to pasty form is present, if desired with the addition of an inorganic or organic solid is granulated and dried at the same time. This granulation and simultaneous drying preferably takes place in a fluidized bed (Fluidized bed granulation) instead. The surfactant preparation used contains, besides the surfactants also include a non-surfactant liquid component, which is preferably Represents water or an aqueous solution. In this process, in contrast to State of the art, the content of a non-surfactant liquid component not a critical process parameter. On the contrary, containing anionic surfactants Formulations are usually neutralized by the anionic surfactants in their Acid form made with concentrated aqueous alkaline solutions. So that one such a form of preparation, however, is in liquid to pasty form at 20 to 40 ° C., the mixture must generally be diluted with water. Here is the high one  However, the energy consumption required to remove the water is disadvantageous to watch.

This problem is addressed in the European patent EP-B-0 663 005 (Henkel KGaA) tackled by instead of a concentrated aqueous alkaline solution powdered neutralizing agent is used. According to the teaching of this patent Granules containing high anionic surfactants can be neutralized by anionic surfactants in its acid form with a powdered neutralizing agent and at the same time Produce granulation and, if necessary, simultaneous drying. It is preferred the neutralization of fatty alcohol sulfonic acids, alkylbenzenesulfonic acids and / or α- Sulfofatty acid methyl ester acids with an excess of sodium carbonate and the simultaneous granulation with other liquid components, especially with Anionic surfactant pastes, aqueous hydrogen peroxide solution and / or a zeolite Suspension. The production is in a continuous fluidized bed system prefers. The process has the advantage that it is dried and granulated at the same time the temperature load remains low.

Another problem arises when the surfactant granules to be produced are high are surfactant. Anionic surfactant granules with a surfactant content of 50% by weight and more are z. T. very hygroscopic and thus tend to stickiness and bad Flowability. The international provides a proposal to solve this problem Patent application WO-A-00/27961 (Henkel KGaA). After teaching this registration soluble, free-flowing and non-sticky surfactant granules with 55 to 95 wt. % Anionic surfactant, if this 5 to 30 wt .-% zeolite of the faujasite type contain. In the manufacture, an aqueous paste of a surfactant or a Pre-surfactant, preferably an anionic surfactant acid, and a faujasite zeolite granulated together and preferably dried at the same time, preferably in a fluidized bed. Neutralization, granulation and drying can be done simultaneously occur. So that the energy released during the neutralization directly at the Drying of the granules A disadvantage of this method, however, is that this method does not achieve 100 percent neutralization. Will the Subsequent surfactant granules with acid-sensitive substances such as. B. Perfumes treated, there is a risk that non-neutralized surfactant residues decompose act on these substances and so z. B. worsen the fragrance impression.  

A European patent that covers the direct use of the neutralization of Uses anionic surfactant-free energy to dry the granules, is EP-B-0 683 814 (Henkel KGaA). Here is a manufacturing process granules containing anionic surfactants with a bulk density above 500 g / l Granulation of a surfactant preparation form that is a non-surfactant liquid Has component described, in which the water requirement and thus the Energy required to evaporate the water can be reduced, when the anionic surfactant is in its acid form or a mixture containing one or more Contains anionic surfactants in their acid form, and separately an aqueous alkaline solution charged with a gaseous medium, then in almost stoichiometric Quantities separated or combined at a high propellant pressure in the Granulating and drying room, preferably a fluidized bed, sprayed and the subsequent granulation, if desired with the addition of a or several inorganic or organic solids and under simultaneous Drying is carried out. This method also suffers from the disadvantage that does not achieve 100 percent neutralization.

All previously mentioned property rights have in common that at least one of the Components that are introduced into the granulation and / or drying room, in a liquid, aqueous preparation form is present.

In the international patent application WO-A-00/18872 (Henkel KGaA) against it specified a granulation process in which the components to be granulated in Form of a neutralized foam are fed to the granulating room. It will be a Process for the preparation of surfactant granules disclosed, in which an anionic surfactant in its acid form and a highly concentrated, aqueous alkaline component separated be charged (foamed) with a gaseous medium and then brought together and neutralized to form a neutralizate foam. This Neutralisate foam is subsequently placed on a solid bed placed in a mixer given where it acts as a granulation aid for solids. The use of a Fluidized bed apparatus is not disclosed. The granulation with a foam as Granulation aid is called "foam granulation" for short. The process has several Advantages on. Among other things is not an adjustment of the viscosity of the components to be granulated necessary so that the energy-consuming water evaporation is largely avoided can be. Complete neutralization can also be achieved. A disadvantage of However, this method is the broad grain size distribution of the resulting granules  with a relatively large amount of oversize and undersize and their very limited upper limit Surfactant. However, a high surfactant content is in the sense of freedom Formulation of detergents or cleaning agents desirable.

The present invention was based on the object of a method for the production to provide high surfactant-containing anionic surfactant granules.

The problem is solved with a mixing and granulating process in which foamed preparations containing anionic surfactants and alkali solutions into one Neutralisate foam are combined, which is then used as a granulation aid in a fluidized bed granulation step is used. The subject of the invention is thus a process for the production of surfactant granules with a high anionic surfactant content in which (a) consists of a concentrated surfactant component which has at least one anionic surfactant contains in its acid form, and a concentrated aqueous alkaline component a neutralized foam is produced and (b) this neutralized foam alone or together with other detergent or cleaning agent ingredients in one Fluid bed apparatus is introduced and granulated and dried there at the same time.

That a neutralized foam can be used successfully in a fluidized bed process can be surprising, since it would actually be expected that the relatively dry Neutralisate foam completely, except for one, when it enters the fluidized bed apparatus very low water content, is dried, losing its binder properties and is therefore no longer available as a granulation aid. Would be expected moreover, that the neutralizate foam entering the fluidized bed apparatus immediately increases a fine tenside dust is dried, which increases the risk of explosion in the fluidized bed apparatus increased dramatically, especially given the blown hot air and the high surfactant content of the neutralized foam.

However, the present invention just discloses a fluidized bed process in which neutralized foam is used and which does not have the disadvantages described above, but which also has several advantages:

• - The neutralizate foam entering the fluidized bed apparatus has one relatively low water content. This is compared to surfactant pastes or even aqueous solutions that otherwise i. a. are used in fluidized bed processes, significantly reduced. This has a positive effect on the economy of the process  Form of a reduced energy requirement, i.e. H. in the form of reduced water evaporation costs.
• - In addition, granulation and drying take place simultaneously, so that for the Drying no additional, cost-increasing process step can be carried out got to.
• - Another contribution to the superior economy of the process is made by short residence time of the granulate particles in the fluidized bed apparatus. this makes possible increased throughput and therefore lower running production costs.
• - The granulate particles produced by the process according to the invention have in addition, despite its high surfactant content, good pourability. High Granules containing anionic surfactants are generally very hygroscopic and tend to stick and clump at high moisture contents. The after Process according to the invention produced granules containing high levels of anionic surfactants on the other hand have a very low water content, even with air exposure remains stable over a relatively long period. The good flowability enables the advantageous transport of the granulate particles in big bags.
• - The water of the neutralized foam entering the fluidized bed apparatus is as already mentioned above, relatively quickly in the method according to the invention dried off. Via the parameters nozzle pressure (pressure under which the foam enters the Fluidized bed apparatus occurs), fluidized bed temperature, supply air volume and residence time the speed of drying can be set precisely and via the amount of water to dry away the dwell time. Associated with this is the advantageous one Possibility to adjust the extent of agglomerate formation precisely.
• - Another advantage of the method according to the invention is the narrow and good adjustable grain size distribution of the resulting surfactant granules. This enables the easy incorporation of these granules into modern granules Detergent or cleaning agent and reduces the sedimentation problem.
• - Furthermore, the inventive method has the advantage that Foam neutralization step ensures complete neutralization and thereby treating the resulting granules with pH-sensitive Substances such as B. perfumes is made possible. The result of the changing Odor particularly noticeable acid-related decomposition of perfumes or perfume Ingredients on anionic surfactant granules of the prior art can z. B. be prevented.

The term "foam" used in the context of the present invention denotes Formations from gas-filled, spherical or polyhedral cells (pores), which through liquid, semi-liquid 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 surfaces reducing effect of the interfacial tension spherical. Above the limit In the densest spherical packing, the bubbles are deformed into polyhedral which are limited by approximately 4-600 nm thin cuticles. The cell webs, connected via so-called nodes form a coherent framework. Between Cell slats span the foam lamellae (closed-cell foam). Will the Foam lamellae destroy or flow into the cell webs at the end of foam formation back, you get an open-cell foam. Foams are thermodynamically unstable, because surface energy can be obtained by reducing the surface. The Stability and thus the existence of those generated by the method according to the invention Foams therefore depend on the extent to which they can self-destruct prevent.

To generate the foams (foaming), a gaseous medium is placed in each anionic surfactant component and the aqueous alkaline component blown in, or the foaming is achieved by violent beating, shaking, Spray or stir the liquid in the gas atmosphere in question. by virtue of the easier and more controllable and feasible foaming is in the frame the present invention, the foam generation by blowing the gaseous Medium ("fumigation") clearly preferred over the other variants. The Fumigation takes place continuously or depending on the desired process variant discontinuous. A fumigation process has proven to be suitable in which the gaseous medium under pressure, preferably at about 6 bar, through a nozzle in the liquid to be foamed is blown in. The influence of the occurring Shear forces lead to foam formation, the size of the shear forces being the size of the Co-determined foam bubbles. Another suitable fumigation process will the gaseous medium through a perforated screen or a perforated plate released from the liquid be wetted, bubbled into the liquid. The perforated screen is with a shower head comparable. In a third suitable gassing process, the gaseous Medium and the liquid to be foamed in a static mixer (e.g. inline Mixer from Sulzer or Kenics) mixed. Furthermore, with one  other suitable fumigation processes, the liquid to be foamed through a Baffle plate to be pressed in a tube. In the presence of the gaseous medium the high shear forces that occur cause foaming. As Baffle plates have sintered discs, filter fabric discs or perforated plates proven a pore diameter of 50 to 2500 microns. The free cross section of the The baffle plate should be less than 10% of the total area of the baffle plate. In addition, fumigation processes are possible in which the gaseous medium via sintered disks, homogenizers or other common systems for foaming is placed in a liquid.

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. For reasons of cost, the invention Process preferably carried out with air as the gaseous medium. If the components to be foamed are stable to oxidation, the gaseous medium also consist entirely or partially of ozone, which can be oxidatively destroyed Contamination or discoloration in the surfactant-containing foam to be foamed eliminates flowable components or prevents germ contamination of these components can be.

The foaming of the anionic surfactant component and the aqueous one alkaline component is preferably designed so that the two resulting Foams have approximately the same volume. For example, this is about the amount of Gaseous medium controllable and / or foam via the targeted addition stabilizing agents such. B. Nonionic surfactants. For example, foaming of a liter of alkylbenzenesulfonic acid 1 to 300 l, preferably 5 to 200 l and in particular 10 to 100 l of air are used. The foaming can both Room temperature as well as at an elevated temperature. preferred Processes are characterized in that the liquid to be foamed components before foaming temperatures of 20 to 100 ° C, preferably from 30 to 90 ° C and in particular from 50 to 75 ° C, have.

As mentioned, the two foams are mixed in a mixer after foaming a neutralized foam, which then either alone or together with  further detergent or cleaning agent ingredients in a fluidized bed apparatus introduced and granulated and dried there at the same time.

The neutralization of the foams in the mixer is in preferred variants of the The inventive method carried out so that the neutralized foam Temperatures below 115 ° C, preferably between 50 and 95 ° C and in particular between 70 and 90 ° C. This will make an unwanted one Avoid brown coloring of the neutralized foam.

It is further preferred if the resulting neutralized foam has a density of at most 0.80 g.cm ^-3, preferably from 0.10 to 0.60 g.cm ^-3 and in particular from 0.30 to 0.55 g.cm ^-3 having. 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 neutralized foam produced by the process according to the invention is preferably high surfactant. Neutralisate foams, the surfactant contents from 40 to 99% by weight, preferably have from 50 to 90% by weight, based in each case on the Weight of the foam are preferred.

The specified physical parameters of temperature, density and mean Pore size characterize the neutralized foam at the time of its creation. Preferably, however, the procedure is chosen so that the Neutralisate foam also meets the criteria mentioned when it is introduced into the Fluid bed apparatus fulfilled.

The residence time of the foam in the mixer is that of the foam used Pressure determined. On the one hand, this must be high enough to be continuous Transport of the foam to the fluidized bed apparatus, d. H. a non-halting or tearing off foam flow, to ensure. On the other hand, the pressure must not be so high be that the residence time is too short for complete neutralization. He comes Foam flow stalls or even tears off, the nozzle can clog and the Production process is disturbed, which leads to poor granulate formation.  

In principle, for the introduction of the neutralized foam into the fluidized bed apparatus preferred two methods. In one, the foam is injected directly into the Fluid bed apparatus introduced, while in the other the foam indirectly a template, one or more pumps and one or more nozzles are introduced.

In the preferred direct method, the neutralized foam is piped with the help of the one at the outlet of the mixer in which the neutralization takes place Pressure is transported to the fluidized bed apparatus and introduced via a nozzle. at Fluidized bed apparatuses that are equipped with several nozzles have this method the disadvantage that in front of each nozzle that is to be operated, a separate mixer must be switched, which is associated with considerable investment costs. she has on the other hand the advantage that foams with very low water contents are transported and can be introduced, which leads to comparatively lower production costs. Compared to methods of the prior art, in which surfactant pastes in the Fluidized bed apparatus can be introduced can be inventively with this preferred method to reduce production costs by up to 65%.

In the also preferred indirect method, the neutralized foam is first in transported a template. Put simply, this is a Collecting container for neutralized foam. One or more pumps are attached to this template connected, which convey the neutralized foam to one nozzle each. at Fluidized bed apparatuses that are equipped with several nozzles have this method the advantage that only one pump has to be switched in front of each nozzle and not yet one Mixer, so that lower investment costs are incurred for this method. The disadvantage is however, that with this method only foams with comparatively higher Water contents can be promoted, making this method too comparative leads to higher production costs. Compared to prior art methods, at which surfactant pastes are introduced into the fluidized bed apparatus can also be used this preferred method according to the invention still reduces the production costs cut up to 20%.

In the context of the present invention, the direct method is impressive because of the low production costs over the indirect method particularly preferred.

The neutralized foam is introduced into the fluidized bed apparatus preferably via a two-component or multi-component nozzle equipped with an annular channel,  through which an atomizing gas is blown into the fluidized bed apparatus. The Solid, further detergent or cleaning agent ingredients are introduced preferably pneumatically via one or more pipes at one or more points of the fluidized bed apparatus. Liquid, further detergent or cleaning agent ingredients are introduced in a similar way to the neutralized foam via nozzles which are in or above the Fluidized bed are arranged. The introduction advantageously takes place in such a way that Caking and blockages are excluded.

The construction of a two-fluid nozzle with an annular channel can be simplified as a tube in the Introduce the tube, the neutralized foam being transported in the inner tube while through the outer tube, which completes the inner tube along the longitudinal axis encloses, the atomizing gas is pressed. In the case of multi-component nozzles, the arrangement shows accordingly several inner tubes or other concentric openings. The pipes are tapered at the outlet opening. Nozzles suitable for the present invention can e.g. B. from the companies Düsen-Schlick GmbH, Lechler GmbH u. Co KG or Spraying Systems Co. The advantage of two- or multi-component nozzles is that the neutralized foam to be atomized is not under pressure at the outlet end of the nozzle needs to stand. Two- or multi-component nozzles can be on at least one channel be operated almost without pressure. This has the positive effect that the structure of the Foam is not damaged or even destroyed by unfavorably high pressure.

About the pressure of the atomizing gas in the ring channel (outer tube) can be Control the relative speed in relation to the neutralized foam in the exit direction. This relative speed determines the atomizing effect. The atomization Effect is that the neutralized foam emerging from the nozzle in Direction of exit is accelerated, and thus in the direction of the fluidized bed apparatus Primary granules present, provided the nozzle is on the primary granules is directed. If the relative speed of the atomizing gas exceeds one certain threshold value, the emerging neutralisate foam is torn to shreds, in other words, atomized to shreds. The trajectories of the foam scraps form a cone that has the exit direction as an axis and its opening angle (Angle between the cone shell and the cone axis) with increasing pressure of the Atomizing gas, or increases with its increasing relative speed.

It is preferred according to the invention if the atomizing gas is compared to the Neutralizate foam has a relative speed in the exit direction that  is sufficient to atomize the neutralisate foam in rags. Is further preferred it when the atomizing gas in relation to the neutralized foam in the exit direction has a relative speed. It is also preferred if the Scraps of neutralized foam under the effect of the atomizing gas in the direction of the Primary granules are accelerated.

During their flight through the fluidized bed apparatus, the neutralized foam can scraps under the drying effect completely release their water content. According to the invention, however, it is preferred if the flight duration is relative speed of the atomizing gas is controlled so that the neutralized foam shred over a certain amount when hitting the primary granulate particles Have water content. According to the invention, this is preferably just so high that the Spread scraps of foam onto the primary granulate particle and connect to it, whereby the particle grows. The drying can be controlled so that the torn pieces of foam on average before a collision between two primary granules are completely dry, d. H. no binder or Have more adhesive effect, or a certain residual water content have and thereby still have a binder or adhesive effect. In this case the drawn-up scraps of neutralized foam act like a granulation aid and it agglomeration between the primary granulate particles can occur. Without one There is no binding or adhesive effect of the neutralized foam scraps Agglomeration between the primary granules, because of the collision two primary granulate particles in the fluidized bed are sufficient to fuse the colliding particles. Should agglomeration between the primary granules, it is preferred if the Neutralisate foam contains film-forming, water-containing substances. By a suitable one The degree of agglomeration can thus be adjusted to the drying effect check. It is preferred according to the invention if there is no agglomeration between the Primary granules occur.

The fluidized bed apparatus can be operated continuously and with a classifying one Discharge. A device is placed under a sifting discharge understood, which makes a selection of the granulate particles based on their weight. In preferred process variants, the bottom of the Fluidized bed apparatus a pipe through which, in addition to the fluidized air, at about 1.5-4 m / s is blown in, so-called classifier air is blown in at about 3-8 m / s.  

The granulate particles moving in the fluidized bed can make up the fluidized bed Leave apparatus through this classifier only if they have a certain minimum weight have reached and their weight is greater than the opposite on them acting force through the classifier air. This increases the weight of the Granulate particles leaving the fluidized bed apparatus in the direction of low values limited. On the other hand, the particle weight is also limited in the direction of high values, because heavy particles leave the fluidized bed relatively quickly via the classifier and as a result, no more mass can be gained. The average length of stay of the In the process according to the invention, surfactant granules in the fluidized bed apparatus are of Water content of the neutralized foam and dry substances introduced, or whose water binding capacity is determined. In a preferred embodiment of the According to the inventive method, the residence time is about 15 minutes.

In a further preferred embodiment of the method according to the invention are the surfactant contents of the anionic surfactant leaving the fluidized bed apparatus Granules above 50 wt .-%, preferably above 60 wt .-%, each based on the granules. In particularly preferred cases, the surfactant content can even be up to amount to approximately 100% by weight if namely as granule nuclei surfactants and otherwise no further detergent or cleaning agent ingredients are used.

In variants preferred according to the invention of the method according to the invention the anionic surfactant granules leaving the fluidized bed apparatus as a result Drying effect on such a low water content that an additional Drying step can be omitted. The contents are preferably present residual, free water of those produced by the process according to the invention Surfactant granules at less than 10% by weight, preferably at less than 7.5% by weight and particularly preferably less than 5% by weight, in each case based on the granules.

The anionic surfactant granules produced by the process according to the invention have preferably, despite their high surfactant content, good flowability, which is a Storage in big bag or silo enabled.

As indicated above, the weight and size of the surfactant granules increase during the time they remain in the fluidized bed apparatus. The weight of the surfactant granulate particles and the classifier air velocity determine the time of exit from the fluidized bed apparatus. Since, on the one hand, the growth of the surfactant granulate particles stops abruptly when it emerges from the fluidized bed apparatus, but on the other hand the surfactant granulate particles can only leave the fluidized bed apparatus if they have a relatively precisely defined size, the process according to the invention enables the production of surfactant granules with very narrow particle sizes. In preferred process variants according to the invention, the surfactant granules produced have a particle size distribution in which

• Less than 10% by weight, preferably less than 7.5% by weight and particularly preferred less than 5% by weight of the particles have a particle size greater than 1.6 mm and
• Less than 2.5% by weight, preferably less than 1% by weight and particularly preferably less than 0.5% by weight of the particles a particle size smaller than 0.4 mm

exhibit.

It is further preferred according to the invention if the surfactant granules produced Bulk weights above 500 g / l, preferably above 600 g / l and particularly preferably above 700 g / l, based in each case on the granules.

As already indicated, further washing or Detergent ingredients are added. This can basically be all substances that can be used in detergents or cleaning agents. The admixture Certain detergent or cleaning agent ingredients can already before Foaming done. However, they can also be presented in the fluidized bed apparatus or during or after the introduction of the neutralized foam into the fluidized bed apparatus can be added. However, the admixture can also be applied to several or all of the mentioned places.

To the other detergent or cleaning agent ingredients that already exist before Foaming can be admixed, preferably include acid-stable Substances. These are preferred for the anionic surfactant component admixed, preferably in amounts of 0.1 to 40% by weight, preferably of 1 up to 15 wt .-% and particularly preferably from 2 to 10 wt .-%, each based on the Weight of the mixture to be foamed. Furthermore, this preferably includes base stable substances. These are preferred to the aqueous alkaline component admixed, preferably in amounts of 0.1 to 80% by weight, preferably 10 up to 75% by weight and in particular from 25 to 70% by weight, in each case based on the weight the mixture to be foamed.  

The acid-stable substances preferably include further anionic surfactant acids, Nonionic surfactants, carboxylic acids, especially fatty acids, precursors of organic cobuilders such as Phosphonic acids, polymer acids or partially neutralized polymer acids and - where none There are concerns about their use - including phosphoric acids. Continue to offer 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. Of course, come too Mixtures of the substances mentioned above, also with their already whole or only partially neutralized forms in question. Among these substances are mainly those preferred, which are liquid at the corresponding process temperature.

The base-stable substances preferably include water-soluble alkalis, Swelling agents such. B. synthetic and natural polymers and foam stabilizing Means such as B. Nonionic surfactants. Among these substances, preference is also given to those which the corresponding process temperature are liquid.

To the other detergent or cleaning agent ingredients, which are preferably in Fluidized bed apparatus are submitted include. B. builders and carriers such. B. Aluminosilicates, silicates, carbonates, inorganic salts, polymers or mixtures it. Among these substances, however, those are preferred which are used in the corresponding process temperature are fixed. These ingredients are the germs for the surfactant granules. These germs grow during the introduction of the Neutralisatschaumes and the other detergent or cleaning agent ingredients Primary granules until the growth when the finished surfactant granules emerge particles abruptly ceases from the fluidized bed apparatus.

To the other detergent or cleaning agent ingredients that appear during or after Introducing the neutralized foam into the fluidized bed apparatus can include z. B. substances that are able to bind water and / or as Carrier for e.g. B. nonionic surfactants are suitable. It is particularly preferred if at least a part of these further detergent or cleaning agent ingredients for powdering the Anionic surfactant granules is suitable, since this ensures good flowability of the resulting Surfactant granules contributes. Builders such as are preferred according to the invention Aluminosilicates, especially zeolites, especially zeolites X and P; carbonates, in particular calcined and / or ground soda, sulfates, cumene sulfonate,  Toluene sulfonate, starch and / or starch derivatives and polymers are preferred. It can too Mixtures of the above substances are used.

About the ingredients that the anionic surfactant component preferred added to the foaming process are primarily anionic surfactants or their acidic ones Precursors. One or more substances are preferably used as anionic surfactants in acid form the group of carboxylic acids, sulfuric acid half-esters and sulfonic acids, preferably from the group of fatty acids, fatty alkyl sulfuric acids and Alkylarylsulfonic acids used. To have sufficient surface active properties to have, the compounds mentioned should have longer-chain Hydrocarbon radicals have at least 6 carbon atoms in the alkyl or alkenyl radical exhibit. The C chain distributions of the anionic surfactants are usually in the range from 6 to 40, preferably 8 to 30 and in particular 12 to 22 carbon atoms.

Carboxylic acids in the form of their alkali metal salts as soaps in washing and Technically, detergents are mainly made from native fats and oils obtained by hydrolysis. During the past century carried out alkaline saponification directly to the alkali salts (soaps) is today On an industrial scale, only water is used to split the fats into glycerin and the free fatty acids splits. Large-scale processes are, for example, those Splitting in an autoclave or continuous high pressure splitting. As part of the Carboxylic acids which can be used as the anionic surfactant in 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 use of fatty acids is preferred in the context of the present compound 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), hexacosanoic acid (Cerotic acid), triacotanoic acid (melissic acid) 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-octadecadienoic acid (linoleic acid), 9t, 12t-octadecadienoic acid (Linolaidic acid) and 9c, 12c, 15c-octadecatreic acid (linolenic acid). For cost reasons it is preferred not to use the pure species, but rather technical mixtures of the individual acids as they are accessible from fat cleavage. Such mixtures are  for example coscos oil fatty acid, hardened tallow fatty acid, technical oleic acid, technical palmitin / stearic acid and soybean oil fatty acid.

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 ester. 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 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 sensitivity to water hardness (solubility of the Ca Mark salts). Alkyl ether sulfuric acids are made like the alkyl sulfuric acids Synthesized fatty alcohols, which with ethylene oxide to the concerned Fatty alcohol ethoxylates are implemented. Instead of ethylene oxide, too Propylene oxide can be used. The subsequent sulfonation with gaseous Sulfur trioxide in short-term sulfonation reactors yields over 98% of the concerned 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 Sulphonic acid group bound terminally (primary alkanesulphonic acids) or along the C- Contain chain (secondary alkanesulfonic acids), only the secondary Alkanesulfonic acids are of commercial importance. These are through Sulfochlorination or sulfoxidation of linear hydrocarbons. Olefin sulfonates are made technically by reacting α-olefins with sulfur trioxide manufactured. Intermediate hermaphrodites are formed, which become so-called Sultons cyclize. Under suitable conditions (alkaline or acid hydrolysis) these sultones react to hydroxylalkanesulfonic acids or alkenesulfonic acids, which both can also be used as anionic surfactant acids.  

Other suitable anionic surfactants are linear alkylbenzenesulfonates (ABS or LAS). Here preferably come C ₉ -C ₁₃ alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C ₁₂ -C ₁₈ monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.

As mentioned, the surfactant-containing surfactant component can be prepared before foaming Phosphonic acids are added. These are in particular: Hydroxyalkanoic or aminoalkanephosphonic acids. Among the hydroxyalkane phosphon Acids, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) is of particular importance as a cobuilder. It is preferably used as a sodium salt in washing or cleaning agents used, the disodium salt neutral and the tetrasodium salt alkaline (pH 9) responding. Preferred aminoalkanephosphonic acids are ethylenediaminetetra methylenephosphonic acid (EDTMP), diethylene triamine pentamethylene phosphonic acid (DTPMP) and their higher homologues in question. They are in washing or Detergents preferably in the form of neutral sodium salts, e.g. B. as Hexasodium salt of EDTMP or as hepta and octasodium salt of DTPMP, used. As a builder, the class of the sodium salts of phosphonic acids preferably HEDP used. Have the sodium salts of aminoalkanephosphonic acids also a strong ability to bind heavy metals.

Polymeric acids, polymeric polycarboxylic acids, and polycarboxylic acids can also be used Surfactic acid must be added before foaming. Among polycarboxylic acids those carboxylic acids are understood that carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, Malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided that such use is not for ecological reasons objectionable, and mixtures of these. Preferred salts are among them Polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, sugar acids and mixtures of these.

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

Suitable polymers are in particular polyacrylic acids, which are preferably a Have molecular weight of 2000 to 20,000 g / mol. Because of their superior From this group, the short-chain polyacrylic acids can in turn solubility Molar masses from 2000 to 10,000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may be preferred.

Also suitable are copolymeric polycarboxylic acids, especially those of Acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid have proven to be particularly suitable, which contain 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative molecular weight, 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.

Other suitable copolymeric polycarboxylic acids include those of maleic acid Olefins. Copolymers of this type which have proven particularly suitable are those which the molar masses from 5000 to 12,000 g / mol, preferably from 7000 to 12,000 g / mol and have in particular from 9000 to 12,000 g / mol.

In washing or cleaning agents, the polymeric polyacrylic acids are preferably in Form of their (partially) neutralized metal salts, preferably the alkali metal salts and especially the sodium salts used. But ammonium salts are also conceivable. These (co) polymeric polycarboxylates can be either as a powder or as an aqueous one Solution are used. The content of (co-) detergents or cleaning agents polymeric polycarboxylates is preferably 0.5 to 20 wt .-%, in particular 3 to 10% by weight.

To improve water solubility, the polymers can also allylsulfonic acids, such as for example in EP-B-0 727 448 allyloxybenzenesulfonic acid and methallylsulfone acid, contained as a monomer.  

Biodegradable polymers of more than two are also particularly preferred various monomer units, for example those described in DE-A-43 00 772 as monomers salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomers salts of acrylic acid and the 2-alkylallylsulfonic acid and sugar derivatives.

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

Preference is given to the surfactant component containing anionic surfactant acid before foaming nonionic surfactants in amounts of 0.1 to 40% by weight, preferably 1 to 15% by weight and in particular from 2 to 10% by weight, in each case based on the weight of the mixture to be foamed, admixed. This addition can be physical Improve properties of the anionic surfactant foam and later incorporation nonionic surfactants in the surfactant granules or the entire washing or Make cleaning agents unnecessary.

The preferred nonionic surfactants include e.g. B. alkoxylated, advantageously ethoxylated, especially primary alcohols with 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 may be linear or preferably methyl-branched in the 2-position or linear and can contain methyl-branched radicals in the mixture, as are usually present in oxo alcohol 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 containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _{12- 14} alcohol with 3 EO and _C12-18 alcohol containing 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 either as sole nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the Alkyl chain, especially fatty acid methyl esters, such as those found in Japanese Patent application JP 58/217598 are described or preferably according to the in the international patent application WO-A-90/13533 become.

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 is 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. APG contents of the granules of more than 0.2% by weight, based on the total granules, are preferred. Particularly preferred surfactant granules contain APG in amounts of 0.2 to 10% by weight, preferably 0.2 to 5% by weight and in particular 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 alkanolamides can be suitable. The amount of these nonionic surfactants is 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 (II),

in which R ¹ CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands. 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 (III)

in which R ^{3 represents} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{4 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{5 represents} a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C _1-4 alkyl or phenyl radicals being preferred and [Z] representing 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 implementation with Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.  

Where there are no ecological concerns, the surfactant-containing anionic surfactant can Component preferably also added phosphoric acids before foaming become. In this case, orthophosphoric acid, in particular, is pyrophosphoric acid and particularly suitable for tripolyphosphoric acid.

Another preferred ingredient, the surfactant-containing anionic surfactant component Optical brighteners are preferably added before foaming. Examples of this are derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Ge 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 compounds of a similar structure which instead of the morpholino Group a diethanolamino group, a methylamino group, anilino group or carry a 2-methoxyethylamino group. Brighteners of the type of substituted Diphenylstyryle be present, e.g. B. the alkali salts of 4,4'-bis (2-sulfo styryl) diphenyls, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyls, or 4- (4-chlorostyryl) -4 '- (2- sulfostyryl) biphenyl. Mixtures of the aforementioned brighteners can also be used become.

Another preferred group of ingredients according to the invention, the Anionic surfactant component containing surfactant acid is preferably added before foaming are dyes, especially water-soluble or water-dispersible Dyes. Dyes such as those used to improve the optical are preferred Product appearance in detergents and cleaning agents are usually used. The The choice of such dyes presents no problem for the person skilled in the art, especially since such conventional dyes have high storage stability and Insensitivity to the other ingredients of the wash-active preparations and against light and have no pronounced substantivity towards textile fibers, so as not to stain them. The dyes are those according to the invention Processed anionic surfactant granules preferably in amounts of less than 0.01% by weight % present.

The preferred ingredients of the aqueous alkaline component include all concentrated solutions of water-soluble alkalis in water. In principle, here are the various alkalis such as alkanolamines and metal hydroxides can be used for practical and economic reasons, however, as aqueous alkaline component alkali metal hydroxide solutions, preferably sodium hydroxide solutions with concentrations of at least 25% by weight NaOH, preferably  at least 50% by weight NaOH and in particular at least 65% by weight NaOH, each based on the aqueous alkaline component to be foamed. in this connection the concentration of sodium hydroxide in the solution can be increased if at the same time the temperature of the solution is increased.

By adding further ingredients of washing and cleaning agents to the Foamed alkaline component can increase its viscosity and the Viscosity of the anionic surfactant can be adjusted. For 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) before Foaming have similar, preferably even identical viscosity values. The Viscosities are measured in a manner known per se with the Ford Flow cup or spindle viscometer such as the Brookfield viscometer. The viscosity The alkaline component to be foamed can be used with commercially available Viscosity regulators can be set.

In addition to synthetic polymers such as polyacrylates, polyurethanes, etc. there are also natural or semi-synthetic products such as xanthans, Celluloses and cellulose derivatives, starch and starch derivatives, etc. These too Organic high molecular substances called liquids (liquids) soak up, swell and finally into viscous real or colloidal solutions pass over, come from the groups of natural polymers, the modified natural polymers and the fully synthetic polymers.

Natural polymers that are used as thickeners for example agar agar, carrageenan, tragacanth, gum arabic, alginates, pectins, Polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein. Modified natural products mainly come from the group of modified starches and celluloses, for example carboxymethyl cellulose and others Cellulose ether, hydroxyethyl and propyl cellulose as well as core meal ether called.

A large group of thickeners that are widely used in the Find a wide variety of applications, such as the fully synthetic polymers 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, Rohm & Haas), Dapral®-GT-282-S (alkyl polyglycol ether, Akzo), Deuterol®-Polymer-11 (dicarboxylic acid- Copolymer, Schönes GmbH), Deuteron®-XG (anionic heteropolysaccharide based from β-D-glucose, D-manose, D-glucuronic acid, Schönes GmbH), Deuteron®-XN (non-ionic polysaccharide, Schönes GmbH), Dicrylan®-Thickener-O (ethylene oxide- Adduct, 50% in water / isopropanol, Pfersse Chemie), 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, that of Xanthomonas campestris and some others Species is produced under aerobic conditions and has a molecular weight of 2 to 15 Million daltons. Xanthan is formed from a chain with β-1,4-bound glucose (Cellulose) formed with side chains. The structure of the subgroups consists of glucose, Mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units being the Viscosity of xanthan determined.

Carboxymethyl cellulose (CMC) has also proven particularly useful as a viscosity regulator. By using it, for example, it is possible to use sodium hydroxide solution without further additives foaming sufficiently stable.

Although it is possible in principle, the aqueous alkaline component without further Foam additives and this foam with the anionic surfactant foam into one To combine neutralisate foam is the addition of foam stabilizing agents aqueous alkali solution preferred before foaming. In preferred procedures the surfactant is added to the aqueous alkaline component before foaming, in particular anionic and / or nonionic surfactants, preferably ethoxylated Alcohols and / or soaps, mixed.  

Further detergent or cleaning agent ingredients can be used according to the invention preferred methods are also partially submitted to the fluidized bed apparatus before the neutralized foam is introduced, or they are added simultaneously or after the The neutralized foam is mixed into the fluidized bed apparatus. To the preferred ingredients include z. B. builders and carriers such. B. Aluminosilicates, in particular zeolites, silicates, carbonates, phosphates, inorganic Salts, polymers or mixtures thereof.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .yH 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 phyllosilicates of the formula given are those in which M is sodium and x is 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 Na ₂ O: SiO ₂ modulus from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.65, can also be used are delayed in dissolving and have secondary washing properties. The dissolution delay compared to conventional amorphous sodium silicates can be done in different ways, e.g. B. may have been caused by surface treatment, compounding, compacting / compression or 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 provide 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 are particularly preferred, compounded amorphous silicates and over-dried X-ray amorphous silicates.

All other sodium silicates, e.g. B. also non-delayed sodium silicates, provided they have builder properties. For example, B. sodium and / or potassium water glasses with a modulus (Na, K) ₂ O: SiO ₂ from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5 and in particular from 1: 2 to 1: 2.65. These can be of natural origin or have been produced synthetically. The latter can be used in the form of spray-dried, powdered water glasses or in the form of liquid water glasses. Suitable water glasses are e.g. B. Britesil C 20 (PQ Silica) and Pyramid P (Crosfield).

An optionally used finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P. Zeolite P-type is particularly preferred as zeolite MAP (e.g. commercial product: Doucil A24 from Crosfield). 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 (about 80% by weight of zeolite X) ), developed by CONDEA Augusta S. p. A. is sold under the brand name VEGOBOND AX® and through 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

n = 0.90 to 1.00
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.

Other substances used as builders are carbonates, bicarbonates, and Sesquicarbonates and their hydrates. Of these are the alkali carbonates and in particular Sodium carbonate preferred. These builders act as precipitation builders, by forming sparingly soluble precipitates with Ca and Mg ions, other than Alkalinity source and are mostly in combination with organic cobuilders or / and Silicates used.  

It goes without saying that the generally known phosphates are also used as Builder substances possible, provided that such use is not from ecological Reasons should be avoided. The sodium salts are particularly suitable Orthophosphate, the pyrophosphate and especially the tripolyphosphate.

Another object of the present invention is a method for producing Detergents or cleaning agents, according to the invention according to the above produced according to the method, high anionic surfactant containing anionic surfactant granules other detergent or cleaning agent ingredients are mixed. In preferred Embodiments of the method according to the invention make this anionic surfactant granules at least 60 wt .-%, preferably at least 75 wt .-% and in particular at least 90% by weight of the finished washing or cleaning agent turn off.

The other detergent or cleaning agent ingredients that are required for mixing the above-described high anionic surfactant granules come, preferably include sensitive detergent or cleaning agent ingredients, which under the conditions of neutralization and / or granulation and Damage to the drying step or could be lost. This includes for example enzymes, bleaches, bleach activators, perfumes, dyes and Mixtures of these.

Enzymes in particular come from the hydrolase class, such as Proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains, such as protein, greasy or starchy stains, and graying. Cellulases and others Glycosyl hydrolases can be removed by removing pilling and microfibrils Color preservation and increase the softness of the textile. For bleaching or Oxidoreductases can also be used to inhibit color transfer.

From bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens enzymatic agents. Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus are used. there are enzyme mixtures, for example of protease and amylase or protease and  Lipase or lipolytic enzymes or protease and cellulase or from Cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic acting enzymes and cellulase, but especially protease and / or lipase containing mixtures or mixtures with lipolytically active enzymes of particular Interest. Examples of such lipolytically active enzymes are the known ones Cutinases. Peroxidases or oxidases have also been found to be suitable in some cases proved. Suitable amylases include in particular α-amylases, iso-amylases, Pullulanases and pectinases. Cellobiohydrolases are preferably used as cellulases, Endoglucanases and β-glucosidases, which are also called cellobiases, or Mixtures of these are used. Because the different types of cellulase are characterized by their CMCase and Avicelase activities can be distinguished by targeted mixtures the desired activities are set for the cellulases.

The enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition. The proportion of enzymes, Enzymmi mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2% by weight.

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 which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Typical organic bleaches are the diacyl peroxides, such as. B. 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-phthalimoxy acid phthalimonic acid phthalimonic acid [ PAP)], o-carboxybenzamidoperoxy caproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacinic acid, diperoxybrodiacid, diperoxybryanoic acid -1,4-diacid, N, N-terephthaloyl-di- (6-amino percaproic 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, tribromo isocyanuric acid, dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations like potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhy danthoin are also suitable.

Should detergents or cleaning agents be produced that are more textile when washing Fabrics at temperatures of 60 ° C and below, and especially at the Pre-treatment of laundry can have an improved bleaching effect Bleach activators are added. Compounds which under perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted Perbenzoic acid result, are used. Substances that are O- and / or are suitable N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted Wear benzoyl groups. Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylene diamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl 2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially 1,3,4,6- Tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS), acylated hydroxycarboxylic acids, such as triethyl-O-acetyl citrate (TEOC), Carboxylic anhydrides, especially phthalic anhydride, isatoic anhydride and / or Succinic anhydride, carboxamides, such as N-methyldiacetamide, glycolide, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, isopropenylacetate, 2,5-diacetoxy-2,5-dihydrofuran and enol esters as well as acetylated sorbitol and mannitol or their mixtures (SORMAN), acylated sugar derivatives, in particular Pentaacetylglucose (PAG), Pentaacetylfructose, Tetraacetylxylose and Octaacetyllactose as well as acetylated, optionally N-alkylated glucamine or gluconolactone, triazole or triazole derivatives and / or particulate caprolactams and / or Caprolactam derivatives, preferably N-acylated lactams, for example N- Benzoylcaprolactam and N-acetylcaprolactam. Hydrophilically substituted acylacetals and Acyl lactams can also be used. Combinations of conventional ones Bleach activators can be used. Nitrile derivatives such as Cyanopyridines, nitrile quats, e.g. B. N-Alkyammoniumacetonitrile, and / or cyanamide derivatives  be used. Preferred bleach activators are sodium 4- (octanoyloxy) - benzenesulfonate, n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), Undecenoyloxybenzenesulfonate (UDOBS), sodium dodecanoyloxybenzenesulfonate (DOBS), Decanoyloxybenzoic acid (DOBA, OBC 10) and / or dodecanoyloxybenzenesulfonate (OBS 12) and N-methylmorpholinum acetonitrile (MMA). Such bleach activators are in the usual quantity range from 0.01 to 20% by weight, preferably in quantities from 0.1 to 15% by weight, in particular 1% by weight to 10% by weight, based on the total Composition.

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 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 as well as Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.

Fragrances and perfumes can be added to the aesthetic impression of the Improve products and consumers in addition to softness performance to provide sensory "typical and distinctive" product. As Perfume oils or fragrances can individual fragrance compounds, e.g. B. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and type Hydrocarbons are used. Fragrance compounds are of the ester type z. B. 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 z. B. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. B. the Jonone, ∝-isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, citronellol, Eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, among the Hydrocarbons mainly belong to the terpenes like limonene and pinene. However, mixtures of different odoriferous substances are preferably used create an appealing fragrance together. Such perfume oils can also contain natural fragrance mixtures as they are available from plant sources are, e.g. B. pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Likewise 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 fragrances can be incorporated directly, but it can also be advantageous Apply fragrances to carriers, which adhere the perfume to the laundry intensify and through a slower fragrance release for long-lasting fragrance Take care of textiles. Cyclodextrins, for example, have become such carrier materials proven, the cyclodextrin-perfume complexes additionally with others Auxiliaries can be coated.

However, the fragrances can also be bound in compounds which decompose easily under the action of water, light, acids, microorganisms or other environmental influences and thus control the fragrance and generally release it with a time delay. Silicic acid esters of the following formula have proven to be particularly suitable:

In this formula, R ¹ and R ^{4 are} independently selected from the group of straight-chain or branched, saturated or unsaturated, substituted or unsubstituted C _1-4 hydrocarbon radicals and the fragrance alcohol radicals, each R ² and R ³ is independently selected from the group the fragrance alcohol residues and n can take values between 2 and 20. Compounds of this type are described in international patent application WO-A-00/14091 and German patent application DE-A-100 12 949.

In addition to the detergent or cleaning agent ingredients described so far, the anionic surfactant granules produced by the process according to the invention, or the detergents or cleaning agents produced by the process according to the invention preferably still contain additives. These are also common, preferred detergent or cleaning agent ingredients such. B. UV absorbers, dyes, Foam inhibitors, anti-redeposition agents, graying inhibitors, color transfer inhibitors  and corrosion inhibitors. These substances are described in more detail below described.

The granules or agents produced by the processes according to the invention can as preferred additives contain UV absorbers on the treated textiles wind up and the lightfastness of the fibers and / or the lightfastness of the improve other recipe components. Under UV absorbers are organic To understand substances that are able to absorb ultraviolet rays and the absorbed energy in the form of longer-wave radiation, e.g. B. heat, again deliver (light protection filter). Compounds that have these desired properties have, for example, the effective by radiationless deactivation Compounds and derivatives of benzophenone with substituents in 2- and / or 4- Position. Substituted benzotriazoles are furthermore phenyl-substituted in the 3-position Acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes as well as natural substances such as umbelliferone and the body's own Urocanoic acid suitable. Biphenyl and above all have special meaning Stilbene derivatives as described for example in EP-A-0 728 749 and are commercially available as Tinosorb® FD or Tinosorb® FR ex Ciba. Further Suitable UV light protection filters are in the overview by P. Finkel in SÖFW-Journal 122, 543 (1996). The UV absorbers are usually used in amounts of 0.01 up to 5% by weight, preferably from 0.03 to 1% by weight.

Another group of additives preferred according to the invention are dyes, in particular water-soluble or water-dispersible dyes. Are preferred here Dyes, such as those used to improve the optical product appearance in washing and Cleaning agents are usually used. The selection of such dyes poses no difficulties for the person skilled in the art, in particular since such customary ones Dyes have a long shelf life and are insensitive to the rest Ingredients of the granules and Medium and against light as well as no pronounced substantivity towards textile fibers so as not to stain them. According to the invention, the dyes are in amounts of less than 0.01% by weight.

When used in machine washing processes, it may be advantageous to add conventional foam inhibitors to the granules or compositions produced by the processes according to the invention. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C _18-24 fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bisstearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, for. B. from silicone, paraffins or waxes. The foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bisstearylethylenediamides are particularly preferred.

Other preferred additives can be those according to the process of the invention Granules and agents produced also anti-deposition agents, so-called soil Repellents included. These are polymers based on fibers or hard surfaces wind up and counteract re-soiling. This effect will Particularly clear if a textile is soiled that has already been used several times 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 hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30 wt .-% and Hydroxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic Cellulose ether, as well as the polymers known from the prior art Phthalic acid and / or terephthalic acid or their derivatives, in particular Polymers from ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid Polymers.

Another group of preferred polymers are graying inhibitors. This have the task of the hard surface and especially of the textile fiber to keep detached dirt suspended in the liquor, thereby re-opening prevent dirt and support the co-builder. For this are Suitable water-soluble colloids mostly organic, for example glue, gelatin, Salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or Salts of acidic sulfuric acid esters of cellulose or starch. Also water soluble Liche, acidic polyamides are suitable for this purpose, because of their  However, nitrogen content is less preferred. Furthermore, other than that Use the above starch products, e.g. B. degraded starch, aldehyde starches, etc. Polyvinyl pyrrolidone can also be used. Cellulose ethers such as Carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxyme ethyl cellulose and mixtures thereof, for example in amounts of 0.1 to 5% by weight, based on the granules or agents used. They are also oxidized starches suitable, as described in the international patent application WO-A-93/08251 become

Further in the granules or Color transfer inhibitors are preferred polymers. To include in particular polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as Poly (vinyl pyridine N-oxide) and copolymers of vinyl pyrrolidone with vinyl imidazole.

The granules or agents produced by the processes according to the invention can corrosion inhibitors are preferred to protect the wash ware or the machine contain, with silver protection in the field of automatic dishwashing have special meaning. In general, silver protection agents in particular can be selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes become. Benzotriazole and / or are particularly preferably to be used Alkylaminotriazole. You will also often find it in detergent formulations Agents containing active chlorine, which significantly reduce the corrosion of the silver surface can. Chlorine-free cleaners especially contain oxygen and nitrogen organic redox active compounds such as di- and trihydric phenols, for example Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds. Also salt and complex find inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce frequent use. Preferred are the transition metal salts that are selected are special from the group of manganese and / or cobalt salts and / or complexes preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the Cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and Manganese sulfate. Zinc compounds can also be used to prevent corrosion on Washware can be used.

Examples foaming

Arliconic acid (dodecylbenzenesulfonic acid, Trade name Maranil DBS, manufacturer Cognis) used as an alkali solution sodium hydroxide solution. These two liquid components were separated with air mixed and each by two separate and with check valves and baffle plates equipped pipe sections pressed. A sintered disc was used as a baffle plate used a pore diameter of 200 microns. The free cross-section of the baffle plate was less than 10% of the total area.

Neutralization

The two foams were made in a company's dynamic mixer GTA Maschinensysteme GmbH, Hamminkeln merged and homogenized. The Neutralisat foam emerges from the mixer as a foamy paste and is replaced by the applied air pressure of 6 bar directly to the fluidized bed apparatus.

granulation

For the granulation either an AGT 400 or an AGT 1800- Fluid bed apparatus from Glatt Ingenieurtechnik GmbH, Weimar, the one with was equipped with a sifting discharge. The neutralized foam was over a Introduced nozzle. Zeolite X was also introduced via a pneumatic system, or blown.

Table 1

Anionic surfactant acid: arliconic acid

Table 2

Alkaline solution: sodium hydroxide solution

Table 3

Foaming of both components and neutralization

Table 4

Fluidized bed apparatus

Table 5

Surfactant granules

The table clearly shows the high surfactant contents according to the invention Process produced surfactant granules and the narrow grain size distribution.

These granules 4 were used to assess the pourability after prolonged storage Stored in a big bag for months without air. Result: Good flowability.

Claims (15)

1. A process for the preparation of surfactant granules with a high anionic surfactant content, characterized in that

• a) a neutralized foam is produced from a concentrated surfactant component containing at least one anionic surfactant in its acid form and a concentrated aqueous alkaline component and
• b) this neutralized foam, alone or together with further detergent or cleaning agent ingredients, is introduced into a fluidized bed apparatus and is granulated and dried there at the same time.

2. The method according to claim 1, characterized in that the neutralized foam is either introduced directly into the fluidized bed apparatus via a nozzle or indirectly via a template, one or more pumps and one or more nozzles. 3. The method according to any one of claims 1 or 2, characterized in that the Neutralisate foam temperatures below 115 ° C, preferably between 50 and 95 ° C and in particular between 65 and 90 ° C. 4. The method according to any one of claims 1 to 3, characterized in that the neutralized foam has a density of at most 0.80 gcm ^-3 , preferably from 0.10 to 0.6 gcm ^-3 and in particular from 0.3 to 0.55 gcm ^-3 . 5. The method according to any one of claims 1 to 4, characterized in that the Neutralisate foam has a surfactant content of 40 to 99% by weight, preferably 50 to 90% by weight, each based on the weight of the foam. 6. The method according to claim 1 to 5, characterized in that the neutralizate foam is introduced directly into the fluidized bed apparatus via a nozzle, whereby for the transport and introduction of the neutralized foam the pressure at the exit of the Mixer is used in which the neutralization takes place. 7. The method according to any one of claims 1 to 6, characterized in that the Neutralisate foam into the fluidized bed apparatus via a two- or multi-component nozzle  is introduced, which is equipped with a ring channel through which a Atomizing gas is blown into the fluidized bed apparatus. 8. The method according to claim 7, characterized in that the atomizing gas a relative speed compared to the neutralized foam in the exit direction which is sufficient to atomize the neutralized foam in rags. 9. The method according to any one of claims 1 to 8, characterized in that the Surfactant granules surfactant contents above 50% by weight, preferably above 60% by weight, each based on the granules. 10. The method according to any one of claims 1 to 9, characterized in that the Surfactant granules residual free water contents of less than 10% by weight are preferred less than 7.5% by weight and particularly preferably less than 5% by weight, each based on the granules. 11. The method according to any one of claims 1 to 10, characterized in that the surfactant granules have a particle size distribution in which

• a) less than 10% by weight, preferably less than 7.5% by weight, particularly preferably less than 5% by weight of the particles, a particle size greater than 1.6 mm and
• b) less than 2.5% by weight, preferably less than 1% by weight, particularly preferably less than 0.5% by weight, of the particles have a particle size of less than 0.4 mm.

12. The method according to any one of claims 1 to 11, characterized in that the Surfactant granules bulk densities above 500 g / l, preferably above 600 g / l, particularly preferably above 700 g / l, based in each case on the granules, exhibit. 13. Process for the production of detergents or cleaning agents, thereby characterized in that anionic surfactant granules produced by the process according to one of claims 1 to 12, with further washing or cleaning agents ingredients are mixed.   14. The method according to claim 13, characterized in that the anionic surfactant granules at least 60% by weight, preferably at least 75% by weight and particularly preferably make up at least 90% by weight of the finished washing or cleaning agent. 15. The method according to claim 13 or 14, characterized in that the further Detergent or cleaning agent ingredients sensitive washing or cleaning agent ingredients are, preferably enzymes, bleaching agents, bleach activators, perfumes, Dyes and mixtures thereof.