EP0663005A1

EP0663005A1 - Process for producing granulated surfactants

Info

Publication number: EP0663005A1
Application number: EP93920800A
Authority: EP
Inventors: Volker Bauer; Ditmar Kischkel; Andreas Syldath; Joachim Peters; Peter Kraeplin; Jochen Jacobs
Original assignee: Henkel AG and Co KGaA
Current assignee: Cognis IP Management GmbH
Priority date: 1992-09-30
Filing date: 1993-09-22
Publication date: 1995-07-19
Anticipated expiration: 2013-09-22
Also published as: ES2140467T3; DE59309891D1; CN1087945A; WO1994007990A1; ATE187200T1; DE4232874A1; EP0663005B1

Abstract

Detergent anionic surfactant granules of high anionic surfactant content can be produced by neutralization of anionic surfactants in their acid form using a powdered neutralizer, with simultaneous granulation and, as needed, simultaneous drying. Preferably this involves the neutralization of fatty alcohol sulfonic acids, alkyl benzene-sulfonic acids and/or (alpha)-alkylsulfonic acid methyl ester acids with an excess of sodium carbonate, and the simultaneous granulation with other liquid components, in particular with anionic surfactant pastes, aqueous hydrogen peroxide solution and/or a zeolite suspension. This production can be effected in any apparatus in which neutralization can be carried out simultaneously with granulation and drying. Preferably this preparation takes place in a continuous fluidized bed system.

Description

"Process for the Production of Surfactant Granules"

The invention relates to a process for converting anionic surfactants in their acid form into washable and cleaning-active surfactant compounds and storage-stable and dust-free granules with preferably increased bulk density.

The economic synthesis of light-colored surfactant powders, in particular anionic surfactants based on fatty alkyl sulfates (FAS) and alkyl benzene sulfonates (ABS), is now a state of the art. The corresponding surfactant salts are obtained in aqueous preparation forms, water contents being adjustable in the range from about 20 to 80% by weight and in particular from about 35 to 60% by weight. Products of this type have a paste-like to cutable quality at room temperature, the flowability and pumpability of such pastes at room temperature being restricted or lost in the range of about 50% by weight of active substance, so that such pastes, in particular, are further processed Considerable problems arise when they are incorporated into solid mixtures, for example in solid washing and cleaning agents. Accordingly, it is an old need to provide detergent surfactants in a dry, in particular free-flowing form. In fact, it is also possible to obtain free-flowing surfactant powders, for example free-flowing FAS powders, using conventional drying technology, especially in the spray tower. Here, however, there are serious restrictions which in particular jeopardize the economic efficiency of the industrial use of the powders obtained in this way, in particular such FAS powders. FAS powder dried over the tower, for example, has a very low bulk density, so that unprofitable conditions occur in the packaging and distribution of these powders or these powders have to be compacted into heavier granules by granulation. But even in the manufacture of the tower powders, safety-related concerns can make such a highly restrictive manner of tower drying necessary that practical difficulties arise here. Safety-related studies on tower powder based on FAS with 20% by weight or higher active substance contents show that the atomization technique of such formulations is only possible to a very limited extent and for example, tower inlet temperatures below 200 ° C are required. Another disadvantage of spray drying technology is that caking can occur in the tower, which leads to brown discoloration of the powder.

Comparable or other difficulties arise in the conversion of aqueous, in particular pasty, preparation forms of numerous other detergent-active and detergent-active compounds to storage-stable solids. Further examples of anionic oleochemical surfactant compounds are the known sulfofatty acid ethyl esters (fatty acid methyl ester sulfonates, ES), which by α-sulfonation of the methyl esters of fatty acids of vegetable or animal origin with predominantly 10 to 20 carbon atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono salts, in particular the corresponding alkali salts. The ester cleavage gives rise to the corresponding sulfo fatty acids or their disalts, which, like mixtures of disalts and sulfo fatty acid methyl ester mono salts, have important washing and cleaning properties. However, comparable problems also occur in other surfactant classes when trying to display the corresponding surfactant raw materials in dry form. Reference is made here to washing and cleaning-active alkyl glycoside compounds. In order to obtain light-colored reaction products, a final bleaching, for example with aqueous hydrogen peroxide, is generally required in their synthesis, so that here, too, today's technology leads to aqueous paste form. Such aqueous alkyl glycoside pastes (APG pastes) are more at risk from hydrolysis or microbial contamination, for example, than corresponding dry products. Here, too, simple drying according to the technologies customary to date presents considerable difficulties. Finally, drying an aqueous paste of the alkali salts of detergent soaps and / or ABS pastes can also cause considerable problems.

Granulation is an alternative to spray drying of surfactant pastes. For example, European patent application EP 403 148 describes a process for producing FAS granules which can be dispersed in cold water. A highly concentrated aqueous FAS paste is used contains less than 14% by weight of water and less than 20% by weight of further additives, mechanically processed at temperatures between 10 and 45 ° C. until granules form. In this way, FAS granules are obtained which are already dispersed at washing temperatures between 4 and 30 ° C; however, the process temperature to be observed and the relatively low maximum water content of the surfactant paste represent critical process parameters. In addition, it is not disclosed what bulk densities the granules produced by this process have.

A process for the production of FAS and / or ABS granules is known from European patent application EP 402112, the neutralization of the anionic surfactants in acid form to give a paste with a maximum of 12% by weight of 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 is carried out in a tendon-running mixer. Again, the amount of water to be maintained represents a critical process parameter. In addition, it is not disclosed what bulk densities the surfactant granules obtained by this process have.

From European patent application EP 402111 a process for the production of detergent-active and granular surfactants with a bulk density between 500 and 1200 g / l is known, a surfactant preparation containing water as a liquid component and additionally organic polymers and May contain builder substances, mixed with a finely divided solid and granulated in a high-speed mixer. Here, too, the water content of the surfactant paste is a critical process parameter. If the water content of the surfactant paste is too high, the solid is dispersed so that it can no longer act as a deagglomeration agent. On the other hand, if the solids content exceeds a certain value, the mass does not have the consistency necessary for the granulation.

European patent application 353 976 discloses an anhydrous production process for surfactant granules, anionic surfactants in their acid form on granular or powdery carriers such as phosphate, arbonate, Bicarbonate or silicate are adsorbed and then agglomerated in a fluidized bed.

The object of the invention was to provide a process for the production of concentrated surfactant granules, in which the content of a non-surfactant liquid component, in particular water, is not a critical process parameter.

The invention accordingly relates to a process for the preparation of washable and cleaning-active anionic surfactant granules by neutralizing anionic surfactants in their acid form, characterized in that the anionic surfactants are neutralized in their acidic form with a powdery neutralizing agent, at the same time being granulated and the resulting granules if desired, be dried simultaneously.

Suitable anionic surfactants in their acid form are either an anionic surfactant in its acid form or a surfactant from the group of the anionic surfactants in their acid form, preferably in combination with anionic, nonionic, amphoteric and / or cationic surfactants. Preferred anionic surfactants in their acid form are C8-C22-alkylsulfonic acids, Cg-Ci ^ -alkylbenzenesulfonic acids, usually called dodecylbenzenesulfonic acid, and α-sulfofatty acid methyl esters in their acid form. Particularly preferred alkylsulfonic acids are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, in particular from fatty alcohols, for example from coconut oil alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, pal ityl or stearyl alcohol, or the Cιo-C20 ~ O ^χoa alcohols and those secondary alcohols of this chain length. The sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 moles of ethylene oxide, are also suitable. In particular, according to the process according to the invention, esters of α-sulfofatty acids (ester sulfonic acids) which, for example, the α-sulfonated by α-sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin with 10 to 20 C atoms in the fatty acid molecule Methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, and the α-sulfofatty acids (diacids) obtainable by ester cleavage. Also the use of mixtures of mono acids and Diacids with other anionic surfactants in their acid form, for example with alkylbenzenesulfonic acids and / or fatty alkylsulfonic acids, are preferred.

Also suitable are alkanesulfonic acids, which are obtainable from Ci2-Ci8-alkanes by sulfochlorination or sulfoxidation.

The content of neutralized anionic surfactants in the finished granules is generally 0.5 to 60% by weight, preferably 0.5 to 30% by weight and in particular 1 to 10% by weight.

Powdered alkali metal hydroxide or alkali metal carbonate is preferably used as the powdered neutralizing agent, the use of the sodium salts and potassium salts, in particular sodium carbonate and potassium carbonate, being preferred. The neutralizing agent is advantageously used at least in stoichiometric amounts, for example in molar ratios of neutralizing agent to anionic surfactant in acid form from 0.5: 1 to 120: 1, preferably from at least 10: 1 and in particular from 20: 1 to 110: 1. If further solids are used, molar ratios of the neutralizing agent to anionic surfactant in acid form from 0.5: 1 to 10: 1 and in particular from 1: 1 to 5: 1 may also be preferred. It is even possible to use the neutralizing agent in a substoichiometric amount. This can even be advantageous from a procedural point of view. The non-neutralized portions of the liquid anionic surfactants in their acid form then remain liquid in the fluidized bed, do not agglomerate themselves, but can be a valuable auxiliary as a binder in the granulation and become solid when they emerge from the fluidized bed.

In a preferred embodiment of the invention, the anionic surfactants are used in their acid form in combination with anionic, nonionic, amphoteric and / or cationic surfactants. In particular, the alkylbenzenesulfonates, fatty alkyl sulfates and methyl α-sulfofatty acid esters already described are preferred as anionic surfactants. It is particularly preferred to mix mixtures of tallow fatty sulfonic acids and / or alkylbenzenesulfonic acids in combination with tallow fatty alkyl sulfate and / or alkylbenzenesulfonate or α-sulfofatty acid esters in their acid form in combination with oc-sulfofatty acid ester mono salts and / or alkylbenzenesulfonates in the

To bring proceedings. Other suitable anionic surfactants include, for example, alkanesulfonates and the salts of sulfosuccinic acid or soaps made from natural or synthetic, preferably saturated or ethylenically unsaturated, fatty acids. Soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids, are particularly suitable. Preferred in this context are those which are 50 to 100% saturated Ci2-CI8 fatty acid soaps ^un - ^z - - soaps are composed to 50% of oleic acid.

The anionic surfactants can be used in the form of their sodium, potassium, calcium and ammonium salts and as water-soluble salts of organic bases, such as mono-, di- or triethanolamine.

Preferred nonionic surfactants are derived from liquid ethoxylated, in particular primary alcohols with preferably 9 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide per mole of alcohol, in which the alcohol radical can be linear or methyl-branched in the 2-position, or li¬ may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, linear residues of alcohols of native origin with 12 to 18 carbon atoms, such as, for example, coconut oil, tallow fat or oleyl alcohol, are preferred. The degrees of ethoxylation given represent statistical mean values which can be an integer or a fractional number for a special product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow ranks ethoxylates, nre). In particular, alcohol ethoxylates are preferred which have an average of 2 to 8 ethylene oxide groups. The preferred ethoxylated alcohols include, for example, Cg-Cu oxo alcohol with 7 E0, Ci3-Ci5-0xo alcohol with 3 E0, 5 E0 or 7 E0 and in particular Ci2-Ci4 alcohol with 3 E0 or 4 E0, Ci2-Ci8- Alcohols with 3 E0, 5 E0 or 7 E0 and mixtures of these, such as mixtures of Ci2-Ci4 alcohol with 3 E0 and Ci2 ~ Ci8 alcohol with 5 E0. As nonionic surfactants, alkyl glycosides of the general formula R-0- (G) _x , in which R is a primary straight-chain or aliphatic radical which is methyl-branched in the 2-position and has 8 to 22, preferably 12 to 18, carbon atoms, G is furthermore a symbol , which stands for a glycose unit with 5 or 6 carbon atoms, and the oligomer Degree of fixation x is between 1 and 10, preferably between 1 and 2 and in particular is significantly less than 1.4.

The anionic surfactants in their acid form, which are in liquid form, can be introduced into the process either separately or in a mixture with these other surfactants. In a preferred embodiment of the invention, however, in addition to the liquid phase of the anionic surfactants, at least one further liquid component, which is present in liquid to pasty form under normal pressure at temperatures between 20 and 70 ° C., is simultaneously introduced in its acid form. It is preferred that one of these additional liquid components contains anionic and / or nonionic surfactants, but especially anionic surfactants that are present as a water-containing paste. Anion surfactant pastes in the form of about 30 to 60% by weight aqueous preparations in which the anionic surfactants are obtained by neutralizing the corresponding acids when they are not prepared according to the invention are particularly preferred.

The content of the finished granules in additionally used surfactants, in particular in anionic surfactants, which are introduced into the process in aqueous, pasty form or as powder, is preferably 10 to about 99.5% by weight, in particular 30 to 80% by weight. and advantageously 40 to 70% by weight, so that the finished granules contain a total of preferably 10 to 100% by weight, in particular 30 to 80% by weight and advantageously 40 to 70% by weight of surfactants, in particular anionic surfactants .

The liquid component or the liquid components can also contain further ingredients of detergents and cleaning agents. For example, it is preferred that a liquid component contains silicates, for example crystalline sheet silicates of the general formula NaMSi _x 02χ + i ^φ H20, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, or contains amorphous alkali silicates with a molar ratio M2θ: Siθ2 of 1: 1 to 1: 4, preferably from 1: 2 to 1: 3.3, or aluminosilicates in detergent quality. In particular, the use of aqueous zeolite suspensions, for example an aqueous suspension of zeolite NaA and of mixtures of NaA and NaX, is preferred. The suspension can make small additions of nonionic surfactants contain as stabilizers, for example 1 to 3% by weight, based on

Zeolite, on ethoxylated Ci2-Ci8 fatty alcohols with 2 to 5 ethylene oxide groups.

In a further preferred embodiment of the invention, a non-surfactant liquid component is introduced into the process which contains constituents of organic and / or inorganic nature and preferably under normal pressure below 250 ° C., advantageously below 200 ° C. and in particular between 60 and 180 ° C is boiling. Mono- and / or polyfunctional alcohols, for example methanol, ethanol, propanol, isopropanol, butanol, secondary and tertiary butanol, pentanol, ethylene glycol, 1,2-, are preferably used as the optional organic constituent of the non-surfactant liquid component. Propanediol, glycerin and mixtures of these are used. In particular, it is preferred to use water as the inorganic constituent, preferably together with ethanol, 1,2-propanediol or glycerol.

In addition to the powdery neutralizing agent, further solids, which are preferably the usual ingredients of detergents and cleaners, can be introduced into the process. The crystalline sheet silicates already mentioned above, sheet silicates such as smectite or bentonite, amorphous silicates and above all zeolite, in particular zeolite NaA, should be mentioned in particular. The zeolite can also be used as a spray-dried powder. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 20 to 22% by weight of bound water. The content of zeolite and / or layered silicates and / or amorphous silicates in the finished granules is preferably 15 to 70% by weight and in particular 20 to 60% by weight, in each case calculated as water-containing substance.

In a further preferred embodiment of the invention, bleaching agents, chlorine bleaching agents, but preferably peroxy bleaching agents, are introduced into the process. Of the compounds which serve as bleaching agents and which supply H2O2 in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching itte! are, for example, peroxy carbonate, peroxypyrophosphates, citrate perhydrates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid. However, it is particularly preferred to use hydrogen peroxide as the bleaching agent in one of the liquid components. The content of peroxy bleaching agents, in particular hydrogen peroxide, in the finished granules is preferably 0.5 to 10% by weight and in particular 1 to 5% by weight.

If desired, bleach activators can also be incorporated into the granules. Examples of these are N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N.N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. The bleach activators contain bleach activators in the usual range, preferably between 1 and 8% by weight and in particular between 2 and 5% by weight. Particularly preferred bleach activators are N, N, N '.N'-tetraacetylethylene diamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.

Additives, for example neutral salts, in particular alkali sulfates, salts of polycarboxylic acids, in particular salts of citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid or mixtures of these, dyes, foam inhibitors and / or the other, can be used as further liquid, pasty or solid constituents Solubility-improving ingredients are introduced into the process.

Suitable foam inhibitors are, for example, soaps of natural and synthetic origin, which have a high proportion of Ci8 ~ C24 fatty acids. Suitable non-surfactant-like foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of different foam inhibitors are also advantageously used, for example those made from silicone and paraffins or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. The foam inhibitor content of the surfactant preparation form is preferably 0.01 to 0.5% by weight. Components that improve solubility include liquid, pasty and solid compounds. Polyethylene glycols with a relative molecular weight between 200 and 20,000 and highly ethoxylated fatty alcohols with 14 to 80 ethylene oxide groups per mole of alcohol, in particular Ci2-Ci8 fatty alcohols with 20 to 60 ethylene oxide groups, for example tallow fatty alcohol with 30 E0 or 40 E0, are preferred as solubility-improving constituents used. The use of polyethylene glycols with a relative molecular weight between 200 and 600 is particularly preferred. These polyethylene glycols are advantageously used as part of one of the additional liquid components. However, solid polyethylene glycols with a relative molecular weight greater than or equal to 2000, in particular between 4000 and 20,000, can also be used. The content of the finished granules in these constituents improving the solubility of the finished granules is preferably 0.5 to 15% by weight and in particular 1 to 10% by weight, for example between 2 and 7% by weight.

The anionic surfactants in their acid form are simultaneously neutralized, granulated and the resulting granules are dried. "Drying" is understood to mean the partial or complete removal of the non-surfactant liquid components. The process according to the invention has the advantage that the heat generated during neutralization can be used simultaneously for drying the resulting granules. If desired, residual values of free, that is to say unbound water and / or mono- and / or polyfunctional alcohols can be present as long as the finished granules are free-flowing and non-sticky. However, a free water content of 10% by weight and in particular 0.1 to 2% by weight, based in each case on the finished granules, is preferably not exceeded.

According to the invention, the granules can be produced in all devices in which neutralization with simultaneous granulation and with simultaneous drying can be carried out. Examples of this are heatable mixers and granulators, in particular granulators of the Turbo dryer ( ^R ) type (device from Vomm, Italy). In a preferred embodiment, the invention provides that the combination of these process steps in a batch or continuous the current fluidized bed is carried out. It is particularly preferred to carry out the process continuously in the fluidized bed. The liquid anionic surfactants in their acid form or the various liquid components can be introduced into the fluidized bed simultaneously or in succession via one, for example via a nozzle with several openings, or via several nozzles. The nozzle or the nozzles and the direction of spraying of the products to be sprayed can be arranged as desired. The solid carriers, which are the neutralizing agent and, if appropriate, further solids, can be dusted in via one or more lines simultaneously (continuous process) or in succession (batch process), preferably pneumatically via blowing lines, the neutralizing agent in batch process is dusted as the first solid.

Fluidized bed apparatuses which are preferably used have base plates with dimensions of at least 0.4 m. In particular, fluidized bed apparatuses are preferred which have a base plate with a diameter between 0.4 and 5 m, for example 1.2 m or 2.5 m. However, fluidized bed apparatuses are also suitable which have a base plate with a diameter greater than 5 m. A perforated floor plate or a Conidur plate (commercial product from Hein & Leh¬mann, Federal Republic of Germany) is preferably used as the base plate. The method according to the invention is preferably carried out at fluidizing air speeds between 1 and 8 m / s and in particular between 1.5 and 5.5 m / s, for example up to 3.5 m / s. The granules are discharged from the fluidized bed advantageously by means of a size classification of the granules. This classification can be carried out, for example, by means of a sieve device or by an opposed air flow (classifier air) which is regulated in such a way that only particles of a certain particle size are removed from the fluidized bed and smaller particles are retained in the fluidized bed. In a preferred embodiment, the inflowing air is composed of the heated or unheated classifier air and the heated soil air. The soil air temperature is preferably between 80 and 400 ° C, in particular between 90 and 350 ° C. Temperatures between 200 and 300 ° C. are particularly advantageous. The fluidizing air is generally cooled by heat losses and possibly by the evaporation heat the components of the non-surfactant liquid component. This

However, heat loss can at least partially be compensated for by the heat of neutralization, as stated above. It is even possible that the air outlet temperature exceeds the temperature of the vortex air about 5 cm above the base plate. In a particularly preferred embodiment, the temperature of the fluidizing air is approximately 5 cm above the base plate 60 to 120 ° C., preferably 65 to 100 ° C. and in particular 70 to 90 ° C. The air outlet temperature is preferably between 60 and 120 ° C, in particular below 100 ° C and particularly advantageously between 70 and 90 ° C. In the process which is preferably carried out in the fluidized bed, it is necessary that a starting mass is present at the start of the process, which serves as the initial carrier for the sprayed-in anionic side in its acid form. Ingredients of detergents and cleaning agents are particularly suitable as starting mass, in particular those which can also be used as solids in the process according to the invention and which have a particle size distribution which corresponds approximately to the particle size distribution of the finished granules. In particular, however, it is preferred to use surfactant granules as starting mass which have already been obtained in a previous process.

The components of the non-surfactant liquid component evaporate partially or completely in the fluidized bed. Dried to dried germs are formed, which are coated with further amounts of introduced anionic surfactants in their acid form and, if appropriate, additionally introduced anionic surfactant pastes, optionally neutralized with neutralizing agent, granulated and again dried at the same time.

A particularly important embodiment provides that the anionic surfactants are granulated in their acid form with the addition of an inorganic and optionally an organic solid, at least one of which has neutralizing properties, and the resulting granules are dried simultaneously, if necessary. Suitable organic solids are, for example, surfactants or surfactant mixtures which have been produced by granulation, by spray drying or by the process according to the invention and which are recycled after grinding in order to increase the surfactant concentration in the finished granulate. In particular, the use of spray-dried and / or surfactant granules obtained by the process according to the invention is preferred. Highly ethoxylated fatty alcohols with, for example, 20 to 80 EO, preferably 20 to 60 E0 and in particular tallow fatty alcohol with 30 or 40 E0, can also advantageously be used as solids.

The solids are preferably used as finely divided materials, which can either be produced directly in this state, are commercially available, or are converted into this finely divided state by conventional comminution methods, for example by grinding with conventional mills. Preferred solids have, for example, no more than 5% by weight of particles with a diameter above 2 mm and preferably no more than 5% by weight of particles with a diameter above 1.6 mm. In particular, solids are preferred which consist of at least 90% by weight of particles with a diameter below 1.0 mm, in particular below 0.6 mm. Solids are particularly preferred which consist of at least 40% of particles with a diameter below 0.1 mm. Examples of this are alkali carbonates with more than 90 parts by weight of particles with a diameter of less than or equal to 0.5 mm and zeolite NaA powder in detergent quality, which contains at least 90 parts by weight with a diameter below 0.03 mm contains.

In a further embodiment, the surfactant granules which can be produced by the process according to the invention are claimed. Preferred surfactant granules have a surfactant content of 10 to 100% by weight, in particular 30 to 80% by weight and with particular advantage between 40 and 70% by weight, based in each case on the finished granules. Pure surfactant granules are obtained when sodium carbonate is used as the neutralizing agent in stoichiometric amounts, the neutralization has passed 100%, the non-surfactant liquid component of the anionic surfactant paste optionally used is completely evaporated and the granules are thus completely dried and the any added solids consist of a pure surfactant material. In this case, surfactant granules which have been produced by the process according to the invention and now serve as a solid in the process according to the invention are optionally comminuted to the desired particle size distribution and recycled. The content of surfactants in the granules can be set to any of the desired values. In addition to the surfactants, preferred granules contain 20 to 70% by weight, in particular 40 to 60% by weight, sodium and / or potassium carbonate.

In a further embodiment of the invention, granular washing and cleaning agents are claimed which can be produced by the process according to the invention. Preferred granular washing and cleaning agents contain 30 to 80% by weight of surfactants, 20 to 60% by weight of zeolite and / or crystalline layered silicates, smectite, bentonite or mixtures of zeolite, crystalline layered silicates and / or smectite and / or bentonite and / or amorphous silicates, and 0.5 to 10% by weight of peroxy bleach and, if appropriate, further ingredients of washing and cleaning agents. Granular detergents and cleaning agents are particularly preferred which additionally contain 0.5 to 10% by weight, preferably 1 to 8% by weight, sodium and / or potassium carbonate.

The surfactant granules or granular detergents and cleaning agents obtained by the process according to the invention generally have a bulk density of 350 to 1000 g / 1, preferably between 450 and 850 g / 1 and in particular between 500 and 800 g / 1 dust-free, ie in particular they do not contain any particles with a particle size below 50 μm. Otherwise the particle size distribution of the granules corresponds to the usual particle size distribution of a heavy detergent of the prior art. In particular, the granules have a particle size distribution in which a maximum of 5% by weight, particularly advantageously a maximum of 3% by weight, of the particles have a diameter below 0.1 mm, in particular below 0.2 mm. The particle size distribution can be influenced by the nozzle positioning in the fluidized bed system. The granules are characterized by their light color and their flowability. A further measure to prevent the granules produced according to the invention from sticking together is not necessary. If desired, however, a process step can be followed, the granules being powdered in a known manner with finely divided materials, for example with zeolite NaA, sodium carbonate, silica or calcium stearate, in order to further increase the bulk density. This powdering can for example during a rounding step. However, preferred granules already have such a regular, in particular approximately spherical, structure that a rounding step is generally not necessary and is therefore not preferred.

In a particularly preferred embodiment of the invention, the granules have an improved dissolving behavior. This is due to the fact that when alkali carbonate is used as the neutralizing agent, carbon dioxide is produced in the neutralization reaction, which escapes during the granulation and drying process, whereby granules with a pronounced pore structure can be obtained under certain circumstances.

Examples

Examples 1 and 2 used alkylbenzenesulfonic acid (Marlon (R) AS3, a commercial product from Huls AG, Federal Republic of Germany) and a tallow alcohol sulfate paste containing 54% by weight tallow alcohol sulfate and 41% water (sulfopone ( ^R. ) T55, commercial product of the applicant) through a 3-component nozzle into a plant for granulation drying (AGT; Glatt, Federal Republic of Germany). At the same time, sodium carbonate (bulk density approx. 550 g / l; commercial product from Matthes & Weber, Federal Republic of Germany) was introduced into the fluidized bed via a blow line. A surfactant granulate was used as the starting mass, which had been produced in a previous batch (under the same process conditions) and had approximately the same composition as the finished granules of Examples 1 and 2. The process conditions can be found in Table 1. Through simultaneous drying neutralization, granulation and drying, dust-free, non-sticky granules with high surfactant contents were produced (see Table 2).

Table 1: Process parameters

fluidized bed

- diameter in mm

- area in ^2nd

Vortex air velocity in m / s (under operating conditions)

Temperatures in ° C

- soil air

- classifier air

- Vortex air approx. 5 cm above the base plate

- Air leakage

Air flow in m ³ / h 9500 9400

(under operating conditions)

Throughput of anionic surfactant acid (ABS acid) in kg / h

Throughput of anionic surfactant paste (TAS) in kg / h

Sodium carbonate in kg / h

Starting mass in kg Table 2: Characteristics of the products

Examples 1 2

Alkylbenzenesulfonate in% by weight 6.5 1.6

Tallow alcohol sulfate in% by weight 31.0 42.2

Sodium carbonate in% by weight 58.1 51.0

Water (according to Fischer) in% by weight 0.8 1.2 unsulphated components, inorganic salts in% by weight 3.6 4.0 in g / 1 550 510 in% by weight

In a repeat experiment of Example 1, the position of the granules with a grain size above 2.5 mm was reduced to a value below 5% by weight by another positioning of the nozzle for the liquid components.

Claims

1. A process for the preparation of washable and cleaning-active anionic surfactant granules by neutralizing anionic surfactants in their acid form, characterized in that the anionic surfactants are neutralized in their acidic form with a powdery neutralizing agent, granulated at the same time and, if desired, the resulting granules are simultaneously dried become.

2. The method according to claim 1, characterized in that an anionic surfactant in its acid form or a surfactant mixture from the group of anionic surfactants in their acid form, preferably C.8-C22-alkyl sulfonic acids, especially fatty alkyl sulfonic acids, Cg-Ci3-alkylbenzenesul- fonic acids and sulfofatty acid ethyl esters in their acid form, in combination with anionic, nonionic, amphoteric and / or cationic surfactants, in particular anionic surfactants and / or liquid ethoxylated fatty alcohols with 2 to 8 ethylene oxide groups per mole of alcohol, are used.

3. The method according to claim 1 or 2, characterized in that pulverized alkali metal hydroxide or alkali metal carbonate is used as the neutralizing agent, the use of the sodium salts and potassium salts, in particular sodium carbonate and potassium carbonate, being preferred and the neutralizing agent at least in stoichiometric amounts, for example in a molar ratio of neutralizing agent to anionic surfactant in acid form from 0.5: 1 to 120: 1, preferably from at least 10: 1 and in particular from 20: 1 to 110: 1, in the presence of further solids, preferably from 0.5: 1 to 10: 1 and in particular from 1: 1 to 5: 1, is used.

4. The method according to any one of claims 1 to 3, characterized in that a liquid component, which is present under normal pressure at temperatures between 20 and 70 ° C in liquid to pasty form, at the same time with and in addition to the liquid phase of the anionic surfactants in their Acid form is entered.

5. The method according to claim 4, characterized in that this liquid component contains anionic and / or nonionic surfactants, preferably anionic surfactants, which are present as a water-containing paste.

6. The method according to claim 4 or 5, characterized in that the liquid component contains an aqueous zeolite suspension.

7. The method according to any one of claims 1 to 6, characterized in that as further powdery carrier solids, which are preferably usual ingredients of detergents and cleaning agents, in particular alkali sulfates, crystalline and amorphous alkali silicates and layer silicates and zeolite and salts of polycarboxylic acids, are introduced into the process.

8. The method according to any one of claims 1 to 7, characterized in that a non-surfactant liquid component, the constituents organic and / or inorganic nature and preferably under normal pressure below 250 ° C, advantageously below 200 ° C and in particular boiling between 60 and 180 ° C, is introduced into the process.

9. The method according to any one of claims 1 to 8, characterized in that a bleaching agent, preferably a peroxy bleaching agent, for example as perborate or percarbonate and in particular hydrogen peroxide, and optionally a bleach activator is introduced into the process.

10. The method according to any one of claims 1 to 9, characterized in that liquid, pasty or solid components which improve the solubility are introduced into the process.

11. The method according to any one of claims 1 to 10, characterized in that the heat of neutralization is used for drying.

12. The method according to any one of claims 1 to 11, characterized in that the neutralization and simultaneous granulation and the optionally, drying takes place simultaneously in a fluidized bed, batchwise or continuously, preferably continuously.

13. The method according to claim 12, characterized in that the Anionten¬ side in its acid form and the other liquid components are introduced simultaneously or in succession via one or more nozzles into the fluidized bed, while the solid carriers, wel¬ represent the neutralizing agent and optionally other solids, preferably pneumatically dusted in via one or more lines simultaneously or in succession, the neutralizing agent being dusted in as the first solid in a batch process.

14. The method according to claim 12 or 13, characterized in that the vortex air velocity between 1 and 8 m / s, preferably between 1.5 and 5.5 m / s, the soil air temperature between 80 and 400 ° C, preferably between 90 and 350 ° C, in particular between 200 and 300 ° C, the temperature of the vortex air about 5 cm above the base plate between 60 and 120 ° C, preferably between 65 and 100 ° C and in particular between 70 and 90 ° C, and the air outlet temperature is between 60 and 120 ° C, preferably below 100 ° C and in particular between 70 and 90 ° C.

15. The method according to any one of claims 12 to 14, characterized in that the granules are discharged from the fluidized bed via a size classification.

16. surfactant granules, produced according to one of claims 1 to 15, characterized in that it is 10 to 100 wt .-%, preferably 30 to 80 wt .-% and in particular 40 to 70 wt .-%, each based on the fer¬ term granules, on surfactants, in particular on anionic surfactants.

17. surfactant granules according to claim 16, characterized in that it contains 20 to 70 wt .-%, preferably 40 to 60 wt .-% sodium and / or potassium carbonate.

18 surfactant granules according to claim 16 or 17, characterized in that it has a bulk density of 350 to 1000 g / 1, preferably between 450 and 850 g / 1 and in particular between 500 and 800 g / 1.

19. Surfactant granules according to one of claims 16 to 18, characterized gekenn¬ characterized in that it contains no particles with a particle size below 50 microns.

20. Granular washing and cleaning agent, produced according to one of claims 1 to 15, characterized in that it contains 30 to 80% by weight of surfactants, 20 to 60% by weight of zeolite and / or crystalline layer silicates, smectite, bentonite or mixtures of zeolite, crystalline layered silicates and / or smectite and / or bentonite and / or amorphous silicates and 0.5 to 10% by weight of peroxy bleach and optionally further ingredients of detergents and cleaning agents.

21. Granular washing and cleaning agent according to claim 20, characterized ge indicates that it contains 0.5 to 10 wt .-%, preferably 1 to 8 wt .-% sodium and / or potassium carbonate.

22. Granular washing and cleaning agent according to claim 20 or 21, characterized in that it has a bulk density of 350 to 1000 g / 1, preferably between 450 and 850 g / 1 and in particular between 500 and 800 g / 1.

23. Granular washing and cleaning agent according to one of claims 20 to 22, characterized in that it contains no particles with a particle size below 50 microns.