DE2752984C2 - Process for the manufacture of a low-density detergent precursor - Google Patents

Description

The invention relates to a method for producing an in aqueous inorganic granular Low-density detergent precursor and a granular detergent composition with build-up substances low density.

More recently it has been found that ... with builders Granular synthetic inorganic detergents and cleaning agents based on non-ionic surfactants numerous advantages over the granular ones based on anion-active ingredients that were customary up to that point synthetic organic surfactants detergents and cleaning agents formed with builders for coarse, Have white and colored laundry. However, many problems still occurred in the production of the based on nonionic surfactants built up detergent compositions, if these according to the previously for the manufacture of such products using conventional methods, for example by spray drying the final composition from a mixer approach. The dust formation of the was particularly annoying non-ionic surfactants during the spray drying process. This resulted in the spray drying system escaping mist or smoke caused, and a loss of surfactant substance could not be avoided. Besides being undesirable in terms of environmental pollution, it renders the process more expensive and the particulate detergent composition prepared showed depending on the the conditions in the spray tower, there are great differences in terms of the active ingredient content (non-ionic Surfactant).

Attempts have been made to subsequently add most or all of the nonionic Surfactant to remedy this disadvantage. Commercial products have already been manufactured in this way, see US Pat 38 38 072, US-PS 38 49 327, US-PS 38 86 098 and US-PS 39 71 726 and DE-OS 25 14 677.

It can be done by the subsequent addition of the nonionic surfactant, usually by spraying a melt of the surfactant onto the surface of moving particles of a basic composition which is generally essentially inorganic in character and from the auxiliaries in the detergent composition or at least most of the parts These auxiliaries result in a readily usable product, but such a product generally has a higher bulk density than the compositions prepared earlier on the basis of anion-active surfactants (including soaps) present in the mixing set. In some cases the higher density particles are objectionable and even desirable, but there are many cases where it is desirable. To produce products with a low bulk density, for example those to which the consumer is already used, the bulk densities of which are generally in the range from 03 to 0.5 g / cm ^J.

It has been found that when a mixer batch consisting essentially of inorganic constituents is spray-dried, the spherical particles obtained in this way, after the addition of the nonionic surfactant, often have a higher density than is desired, so that density values in the range from 035 to 0, often result. 75 g / cm ³ are present. When nonionic surfactant is post-sprayed or otherwise applied to the particles of the base composition as a topcoat, the densities of these particles increase somewhat or sometimes remain the same. In order to create a commercial detergent and cleaning agent based on nonionic surfactant for coarse, white and colored laundry with the usual density and built up with structural substance, attempts have therefore been made to increase the bulk density of the spray-dried spherical particles of the basic composition and to make granular detergent from such base particles manufacture low density.

It was found that by using soap or other anionic surfactants in small amounts as constituents of an "essentially inorganic mixer batch, the bulk density of the dried particles resulting therefrom during spray drying. Such effects are in the US-PS 39 71 726 and in the aforementioned DE-OS 25 14 677 described. However, by using such detergent products, even if they are added in only small proportions, the Foaming ability promoted, and this is often undesirable for granular detergent compositions. In addition, when processing small amounts of anionic surfactants, as described in DE-OS 25 14 677, certain special process conditions in the spray tower be respected. In some cases only very specific compositions can be used with the one you want low bulk density. The invention is based on the object of a method for the production of detergent precursors low density to create such undesirable Properties of the products and the limitation to certain compositions as well as special Ie Working methods can be avoided and with which practically any compositions can be obtained in a simple manner can be processed into end products with the desired low bulk density.

It has now been found that to solve this problem, a substantially inorganic granular Detergent precursor can go out, in which before the spray drying in a mixer approach (Crutchcr mixture) a small proportionate amount of an or-

ganic hydrotropic salt is incorporated, and that subsequently nonionic surfactant is applied as a coating. Due to the presence of the hydrotropic The base particles and also the particles of the finished detergent composition can be combined in the mixer approach produce in significantly lower density.

Accordingly, the object is achieved according to the invention by a method for producing a substantially inorganic granular detergent precursor of low density, in which one accordingly the characterizing part of claim 1 precedes This intermediate can be by adding a nonionic surfactant according to the method according to claim 6 in a built-up with builders convert synthetic organic detergent composition.

Accordingly, the detergent precursor, which is sometimes also referred to as the carrier composition or base composition, consists essentially of inorganic materials, primarily one or more inorganic builders and preferably additionally one or more inorganic fillers. It can also contain other desired ingredients of the finished detergent composition, with the exception of nonionic surfactants, provided that these are sufficiently heat-resistant and remain stable to a drying treatment, for example conventional spray drying. Usually, a redeposition of detached dirt preventing agents, such as sodium carboxymethyl cellulose, and the 15%, preferably 10% excess amounts of sodium silicate, based on the basic composition, are added afterwards, before, after or with the nonionic surfactant, advantageously in the form of solid single particles. If desired, commercially available clays which improve the flow properties can also be added subsequently, but the use of such substances is normally not necessary for the production of a sufficiently free-flowing, non-sticky and non-baking product. Colorants, perfumes, optical brighteners, fungicides, herbicides and other adjuvants can also be added subsequently, and if they are sufficiently soluble, they can be dispersed or dissolved in the nonionic surfactant and applied together with them to the base particles, for example sprayed on. The builder components of the compositions according to the invention are preferably water-soluble polyphosphates, carbonates, silicates, borates, bicarbonates and phosphates, usually in the form of the sodium or potassium salts, for example pentasodium tripolyphosphate, tetrapotassium pyrophosphate. Sodium carbonate, potassium carbonate, sodium silicate (Na ₂ O: SiO ₂ = 1: 2.35), borax and disodium hydrogen phosphate, but it goes without saying that organic builder salts can also be used; they can at least partially replace the inorganic builder substances. For this purpose, one can also use water-insoluble builder substances, such as sodium aluminosilicates, preferably crystalline or amorphous zeolites of type A or X; Numerous examples of this are described in US Pat. No. 2,882,243, BE-PS 8 13 581 and BE-PS 8 35 351, DE-OS 24 12 837 and DE-OS 24 12 839 and in Austrian patent applications A 4,484 / 73, A 4 642/73, A 4 666/73, A 4 717/73. A 4 750/73, A 4 767/73, A 4 787/73, A 4 788/73. A 4 816/73 and A 4 888/73. Such insoluble builders are further described in the treatise "Zeolite Molecular Sieves" by Donald W. Breck, published in 1974 by John Wiley & Sons, specifically listed there in Table 9.6 on pages 747-49. Normally at least 50% of the builder substances used are present in the form of water-soluble inorganic builder salts, their proportionate amount is preferably less than

ίο at least 80%, especially at least 90% and especially preferred at 100%. It is not necessarily true required to incorporate a filler salt into the base particles or into the finished detergent composition, however, the presence of such materials often produces desirable results. Best proven as Filler has more commonly sodium sulfate, which is usually present alone as a filler material makes up more than 50% and advantageously more than 90% of the filler content. It can be used to determine the particle strength, Stability and flowability, influence favorably and the cost factor can be reduced. It can, however other water-soluble and non-deliquescent inorganic salts that are heat-stable are also used such as sodium chloride, which sometimes pis an impurity in one of the product ingredients occurs. Potassium sulfate, sodium bisulfate and potassium chloride.

As a hydrotropic salt that according to the invention in the Production of the carrier particles with low density is also used, one can use any compound use which has the ability to improve the water solubility of poorly soluble substances. One such hydrotropic compound contributes to the formation of carrier material and end product particles with lower Density especially when the mixer approaches a base composition at elevated temperatures be spray dried. Preference is given to using water-soluble salts νοΛ substituted as such compounds or unsubstituted benzenesulfonic acids, such as their alkali salts, in particular the sodium salts, a. Although alkali benzenesulfonates such as sodium benzenesulfonate are useful hydrotropes Are compounds that can be used in the method according to the invention, but it is advantageous if in the compound used one or more hydrogen atoms on the benzene ring, for example by an alkyl group with 1 to 4 carbon atoms, preferably with 1 to 2 carbon atoms and in particular with 1 carbon atom (Methyl), are substituted. Examples of these are sodium toluene sulfonate, sodium xylene sulfonate, and potassium sulfonate and corresponding salts of cumene, mesitylene, ethylbenzene and pseudocumene. Usually If the sulfonates are mixtures of isomers in which normally and preferably the para and ortho configurations dominate. Examples for this are sodium p-methylbenzenesulfonate, sodium o.o-dimethylbenzenesulfonate and sodium o, p-dimethylbenzo'julfonate. Mixtures of different hydrotropic compounds can also be used, for example sodium toluene sulfonate and sodium xylene sulfonate or the corresponding chewing salts.

As already stated, the invention also extends to a method for producing one with builders degraded granular detergent and cleaning agent low density, which is characterized is that a mixer batch of 20 to 50% water, 10 to 50% of one or more water-soluble inorganic framework salts, 5 to 50% of one or

several water-soluble inorganic filler salts and about 0.2 to 5% of one or more water-soluble organic hydrotropic salts based on a substituted or unsubstituted benzenesulfonic acid are used and spray-dried and that then on the surfaces of the particles consisting of the dried mixture, an amount ensuring the washing effect is applied to nonionic surfactant. The density of the product obtained is noticeably reduced to 0.25 or 03 to 0.45 or 0.5 g / cm ^J (corresponding to 0.25 to 0.45 g / cm ³ in the particles of the basic composition). An effective detergent amount, usually 5 to 17%, preferably 7 to 15%, of nonionic surfactant is applied by spraying onto the surfaces of the particles of the dried mixture.

As nonionic surfactants, polyoxcthyücrte are preferably higher? Fettallcnhole used, such as the water-soluble condensation products of 3 to 15 moles, preferably 7 to 11 moles, of ethylene oxide and fatty alcohols having 10 to 18 carbon atoms, preferably 12 to 15 carbon atoms. Such non-ionic Surfactants have such melting and softening properties that they are at a temperature below 45 "C in droplet form. For this purpose, commercially available Products that are condensation products of a mixture of 12 to 15 carbon atoms Fatty alcohols are about 7 moles of ethylene oxide per mole of fatty alcohol. More commercially available nonionic condensation products of this type, which can also be used for the purposes of the present invention suitable, contain an average of 10 to 11 moles of ethylene oxide per mole of oxyethylated alkenols with 16 to 18 carbon atoms.

In addition to the preferred polyoxethylated higher fatty alcohols and similar alkanols, various other nonionic surfactants can be used at least partially, for example up to 25 or 50%, as described in detail by McCutcheon's in "Detergents and Emulsifiers", 1973, and in Surface Active Agents ”, Volume II, by Schwartz, Perry and Berch (Interscience Publishers, 1958). Nonionic surfactants of this type are usually ^{pasty or waxy solvents at room temperature (20 0} C) and they either have sufficient water solubility that they quickly dissolve in water, especially in the presence of the hydrotropic compound, or they melt quickly at the temperature that the wax water has, for example if its temperature is above 40 or 50 ⁰ C, and distribute in it. It should expediently only normally non-fluid surfactants be used at room temperature, because otherwise there is the risk that they agglomerate the granular finished detergent into a sticky structure, so that it is poorly free-flowing and can clump or solidify when stored. Examples of nonionic surfactants which can be used according to the invention and which impart sufficient detergency at the concentrations in which detergent compositions according to the invention are used, for example 0.1 to 0.2% of detergent composition in the washing water, are the polyalkenoxy derivatives, which are customarily obtained by condensation of low levels Alkyienoxide (containing 2 to 4 carbon atoms), for example ethylene oxide. Propylene oxide (with sufficient ethylene oxide to make the product water soluble) with a compound having a hydrophobic, e.g. hydrocarbon, chain containing one or more active hydrogen atoms. such as, for example, higher alkylphenols, higher fatty acids, higher fatty mercaptans, higher fatty amines, higher fatty polyols and the aforementioned higher fatty alcohols. In general, such compounds are oxyalkylated with an average of about 3 to 30, preferably 3 to 15 and in particular 7 to 11 alkylene oxide units. Particularly useful are nonionic ίο surfactants of the formula RO (C ₂ H ₄ O) _n H, where R is a radical of a linear saturated primary alcohol (an alkyl) with 12 to 15 carbon atoms and η is an integer from 7 to 11 means.

In addition to the adjuvants mentioned above, which are advantageously added to the spray-dried base particles are added, small amounts of anion-active in the base spherical particles and amphoteric compounds may be present or added to them subsequently. Such accessories are for the preparation of the detergent particles according to the invention is not absolutely necessary and when used they are normally only present in small proportions, for example 0.5 to 2%. Examples of substances of this type are the alkali metal sulfonates, preferably sodium alkylbenzenesulfonates 12 to 15 carbon atoms in the alkyl group, which is preferably linear, higher fatty alcohol sulfates, higher alkyl sulfonates, higher olefin sulfonates and polyoxethylated higher fatty alcohol sulfates. In all cases the contain higher alkyl or alkene groups usually 1 to 20 or 12 to 18 carbon atoms and are up to a content of 3 polyoxethylated to 30 or 3 to 15 alkylene oxides per mole. Instead of the specified synthetic anion-active Organic surfactants can be used for all or part of the usual fatty acid soaps use, usually sodium soaps of mixed fatty acids with 8 to 18 carbon atoms such as the soaps obtained from tall oil and coconut oil, and mixtures of the anion-active Use surfactants, the total amount being provided within the percentage range given above is. Instead of the anion-active surfactants, amphoteric surfactants can also be used. It deals are usually higher fatty carboxylates, phosphates, sulfates or sulfonates, which are a cationic Substituents such as an amino group containing, for example, lower alkyl groups Can be quaternized, or their chains on the amino group, for example by condensation with such a lower alkylene oxide, for example Ethy'.inoxid, can be extended. Such water-soluble amphoteric organic surfactants are commercially available. It may sometimes be desirable to use small amounts of cationic organic surfactants, for example as an antistatic agent or plasticizer to be used with. These products are z. B. to ethylene oxide condensates of N-tall oil trimethyldiamines or polyoxethylated quaternary ammonium chlorides which are sold commercially. Different other synthetic surfactants and surface active agents that are useful in the present invention Use purposes are in the McCutcheon and Schwartz publications cited above and employees.

For the production of the granular, synthetic organic built up with builders according to the invention Low density detergent compositions and the corresponding particulate base ingredients

low density compositions, which are usually essentially inorganic material acts, as far as .man focuses on the normally solid constituents of the mixture, an aqueous solution dispersion prepared, which is commonly referred to as a mixer approach (crutcher mix), and which contains the various heat-resistant components of the final product, except the non-ionic surfactant and other appropriate materials to be added subsequently. The mixer approach should be used to save energy and to increase the throughput of the drying device as high a solids content as possible, for example about 50 to 80%. The rest, about 20 to 50%, is Water. A higher proportion of water can be provided, but then the energy requirement and the throughput increase of the spray tower becomes lower, the resulting product may be stickier and poorer flow properties have, and it may happen that the granular base composition and finished Detergent compositions cannot be obtained with the desired low density. When the moisture content of the mixer approach makes up about 20 to 50%, the proportions are water-soluble inorganic Builder salts at about 10 to 50%, the proportions of inorganic filler salts at about 5 to 50% and the content of water-soluble organic hydrotropic salts is about 0.2 to 5%. When inorganic filler salt does not exist, the content of inorganic Builder salt which, in addition to the water content and the content of hydrotropic compounds (as well as other any heat-stable adjuvants present) make up any residual amount of the composition. Preferred builder salts are sodium tripolyphosphate, normally used as pentasodium tripolyphosphate is introduced and typically makes up at least half of the builder salts in the crutcher. Sodium sulfate is used as the preferred filler salt, and this generally makes at least half of the total filler salts present in the mixer batch. The water content in the mixer batch must be provided in such a way that the other components present are adequately dissolved or dispersed.

Spray drying is used and the mixer batch is sprayed under increased pressure, usually at 3 to 50 bar, preferably 20 to 40 bar, through a spray nozzle into a spray tower through which drying air is passed in such a way that the resulting droplets of the mixer batch are free-flowing, round-grained Particles with low density arise. Instead of the spray nozzles, atomizers or other devices can be used. The spray tower is preferably designed as a countercurrent system, its height is usually 5 to 25 m. The inlet temperature for the hot air, which is usually gaseous combustion products from oil or gas, is set to a temperature range of 200 to 400 ^° C. is withdrawn while the air at the outlet usually at a temperature in the range of 50 to 90 ⁰ C. Synchronous spray tower systems can also be used in which inlet air and outlet air are approximately the same temperature. In DE-OS 25 14 677 it is stated that spherical particles with a low density can be manufactured better if instead of countercurrent drying, cocurrent spray drying is used; With the method according to the invention, however, the desired products with low density can be produced with both spray marks. Countercurrent drying is preferred because the drying process takes place with greater efficiency because the heat gradient for the extraction of moisture from the partially dried product in the vicinity of the tower outlet is greater.

The dimensions of the spray nozzle to produce droplets of the mixer approach in the desired Dimension is chosen so that the base particles have sizes in the range from 336 to 0.094 mm clear mesh size attack. The product is preferably completely lying when it is removed from the spray tower in the form of particles of this size range, but one can fall out of this size range Particles, which can be present in a weight proportion of 2 to 10%, either sieve off or on Shred the desired size range or add it to this or a later mixing batch. For some uses the product can be found with particles ranging from 336 to 0.094 mm Sieve the clear mesh size in such a way that a narrower size range, for example between 2.38 to 0.149 mm clear mesh size. One can also, in order to obtain such a product by means of spray drying, so that you can dispense with further sieving or crushing, the spraying conditions accordingly modify.

After it has been completely dried and the particles are in the desired size, the nonionic surfactant applied to the surface of these particles, preferably molten surfactant, which can be present as a concentrated aqueous solution, but is preferably anhydrous, on the surface of the Sprayed on base particles circulated in an inclined drum: the particles are thereby released from a higher insertion part to the removal outlet end moved forward. Instead of an inclined drum, fluid beds of different types can also be used Arrangement or other commercially available mixing devices, for example the Schugi mixer, use. The proportion of nonionic surfactant, preferably a polyoxethylated higher fatty alcohol, is advantageously up to 4 to 15%, and the spherical Particles onto which the surfactant is sprayed contain about 3 to 16%, preferably 5.6 to 13.3% and in particular 5.6 to 11.1% moisture, so that in the End product a water content of about 2.5 to 15%, advantageously 5 to 12% and preferably 5 to 10% is. The moisture content of the base particles can also be set higher, if afterwards moisture-free ingredients are to be added.

The proportions of adjuvants are generally less than 15%, preferably less than 10% and in particular less than 5%. based on the total product, and the proportions of individual special adjuvants are in most cases less than 5% each, preferably less than 2% each and in particular less than 1%. The total content of adjuvants can be in the range from about 0 or 1 to 15%, preferably 1 to 5%, and the concentrations of the individual components can be 0 or 0.1 to 5%. preferably from 02 to 1%. If a bleaching agent, such as for example Nairium perborate, usually as teirahydrate and activated, is to be incorporated into the detergent and cleaning agent, larger percentages thereof, for example 5 to

40%, preferably 10 to 30%, be present. As a result Sodium perborate is not one of the aforementioned common adjuvants in this regard. It should, if it is used, it can be added afterwards.

The proportion of builder salts or filler salts can, me has been found particularly advantageous for products ranging from 3: 1 to 1: 2, in particular 2: 1 to 1: 1.5. The base spherical particles have a bulk density in the range from 0.2 to 0.45 g / cm / ³ and the spherical particles of the final product have a bulk density in the range from 0.3 to 0.5 g / cm ^J. These bulk density values are preferably 0.2 to 0.35 and 0.3 to 0.4, respectively. ^r > g / cm ^J.

The method according to the invention can be carried out particularly advantageously when the moisture content of the mixer batch is approximately 30 to 45% and the mixer batch has such a composition. The result is a spray-dried finished washing and cleaning product which, if it contains 7 to 13% of nonionic surfactant subsequently applied to the spray-dried spherical base particles in the form of a polyoxethylated higher fatty alcohol, 28 to 38% sodium tripolyphosphate, 3 to 8% sodium carbonate , 5 to 10% sodium nitrate with a Na ₂ O: SiO ₂ ratio of 1: 2 to 1: 2.4, 1.2 to 2% sodium toluene sulfonate (or sodium xylene sulfonate), 0.5 to 2% borax, 30 to 42 % Sodium sulfate and 5 to 10% moisture. A condensation product of a fatty alcohol having 12 to 15 carbon atoms with about 7 moles of ethylene oxide per mole of fatty alcohol, which is available as a commercial product, is advantageously present as a nonionic surfactant in such a product.

In this procedure, the mixer batch is preferably at a temperature of 80 to 105 ° C in the spray drying tower operated in countercurrent, in which the air with an air inlet temperature im Range of 200 to 400 ° C is initiated, sprayed, 3.3% sodium toluene sulfonate or sodium xylene sulfonate, 0 to 5.6% borax, 22 to 56% sodium sulfate and 5.6 to 13.3% water, with the corresponding particularly suitable ranges are as follows: 31.1 to 42.2%, 3.3 to 8.9%, 5.6 to 11.1% and 1.3 to 2.2% or 0.5 to 2.2% or 33 to 47% or 5.6 to 11.1%.

The particulate detergents and cleaning agents obtained by the process according to the invention for Coarse, white and colored laundry based on non-ionic surfactants have a desired low density show no stickiness, do not cake and are free-flowing. The method according to the invention is environmentally friendly, there are no undesirable vapors and from the spray towers used no smoke emitted. In addition, the tower throughput is increased and energy consumption is reduced. Despite the comparatively high proportions of non-ionic surfactant in the granular final composition the surfactant substance quickly and easily becomes from the spheroidal particles containing hydrotropes sorbed, and you can get by with comparatively short mixing times, for example 1 to 5 minutes. By the presence of the hydrotropic compound in the product, due to which the properties of the nonionic Surfactants are not affected in any way, improved solubility of some comparably insoluble Soiling substances that are often present on dirty laundry are improved, and it becomes about it In addition, the solubility of poorly soluble adjuvants that are present in the detergent and cleaning agent can be increased, thereby preventing undesired deposition of such substances on the laundry. For example, it can be prevented that dyes present in the detergent and cleaning agent be deposited on pieces of fabric from the laundry.

The main advantage of the present invention is that it is possible to use particulate products

and the spray conditions are adjusted to produce the desired low density. It is spray droplets form, dkr to a particle mixture with the method according to the invention, in which hydro-

dry from particle sizes essentially in the range of 336 to 0.094 mm clear mesh size. To the To obtain such particles, nozzles can be used whose nozzle outlet has a diameter of 0.2 up to 0.8 mm. During the subsequent spraying process, the non-ionic surfactant is applied to the surfaces of the sprayed on in an inclined rotating drum kept in motion particles of the basic composition The rotary drum can be inclined at an angle of 5 to 15 ° and with a Revolving speed of about 5 to 50 rpm, rotate. The non-ionic surfactant has when it comes to the circulated particles is sprayed on, a temperature of 35 to 50 ° C, and the particles are thereby on a temperature of 20 to 45 "C kept.

The process of manufacturing the spherical base or carrier particles is already in connection with the overall process for the production of the particulate detergent compositions have been described. However, there are when it is assumed that about 10% nonionic surfactant is added to the base spherical particles afterwards the preferred and particularly advantageous proportional amounts of the various ingredients of the spherical particles are somewhat different and are 22 to 44% sodium tripolyphosphate 33 to 16.7% Sodium carbonate 5.6 to 16.7% sodium silicate, 1.1 to tropical salts of the type described can also be used, even possible to manufacture products with a lower density than with soaps, mixtures of soaps and nonionic surfactants as well as anionic surfactants, used in equal amounts, are available.

Theoretically, it has not yet been finally clarified.

to which these special effects that can be achieved with the method according to the invention can be attributed

so are.

It is surprising, however, that the small proportionate amounts of hydrotropic salt that are used are sufficiently effective that the properties of one see such a high percentage of inorganic Mixer approach containing salts or base spray drops can be modified significantly.

If you use the detergent compositions prepared according to the invention in the same way Used like commercial granular detergents for coarse, white and colored laundry, i.e. in usual Concentrations, for example 0.1 to 0.2% used in cold, warm or hot wash water, are achieved one very good cleaning of the individual pieces of the Vvaschgut. One can use the granular washing and Cleaning agent for treating very heavily soiled areas of the items to be washed, also with water process into a paste. The presence of the hydrotropic substance supports the detachment of such hard-

bare dirt, so there.!) this during the Washing preparations can be removed more easily.

The invention is further illustrated in the following examples; unless otherwise stated. all parts are to be understood as parts by weight and all temperature data in ° C.

Example t

Made from 23.9% sodium tripolyphosphate. A mixer formulation was prepared for 3.6% sodium carbonate, 5.1% sodium silicate, 1.1% sodium toluene sulfonate, 0.7% borax, 25.6% sodium sulfate, and 40% water. All ingredients except the sodium silicate and water were added as anhydrous powders. Sodium silicate was added as 10.2% of a 50% aqueous solution, and the NajO: SiO> ratio was t: 235. The aqueous composition was mixed for about 15 minutes in a conventional heated soap mixer (crusher) (polyphosphate was the last Component added) and by means of a high-performance pumping system (Triplex) with a pressure of 25 kg / cm ² at a temperature of 95 ° C on top of a 20 m high spray tower and pressed through a large number of nozzles having a diameter of 0.5 mm . This produced a spray stream of spray droplets with a size of essentially 336 to 0.094 mm clear mesh size, from which spherical particles of approximately the same size resulted. The drying air that has been introduced at the bottom of the spray tower had a temperature of about 300 ° C and left the tower top with a temperature of about 90 ⁰ C. The originating from the sprayed mixer approach spray droplets which pass fell through the tower, had a fact average dwell time of about 1 minute. The dwell times could be adjusted to vary between 30 seconds and 3 minutes, depending on the specific drying conditions. The spray-dried spherical particles, more than 95% of which consisted of particles of the desired size in the range from 6 to 160 mesh, were withdrawn from the tower at a temperature of about 45 ° C. at the bottom of the tower after they had been somewhat pre-cooled. At this temperature, the spherical particles were introduced into an inclined rotating drum and sprayed on the surface at a temperature of about 40 ° C. with a melt composed of a mixture of about 7 moles of ethylene oxide per mole of polyoxethylated C12 to Ci ₅ fatty alcohol. The drum was inclined at an angle of about 7 ° and the residence time of the particles therein was about 3 to 5 minutes. The spray nozzles were so large that the spray droplets had a mesh size of about 0.149 to 0.074 mm, and the spray jet was aimed at the surfaces of the circulating particles. During circulation, the product was cooled slightly, and after peeling off from the Umwälztrommel was again cooled to a temperature in the range 20-30 ⁰ C; then the product was ready for packaging.

The product thus produced was an excellent detergent and cleaning agent for coarse, white and colored laundry, which was particularly suitable for use in cold and warm water and in it many rose from about 0.29 g / cm ^J. The moisture content to which the mixer batch was dried in the formation of the base granule particles was 7.7%. The finished detergent composition gave the following analysis values: 33% nafium tripolyphosphate, 5% sodium carbonate, 7% sodium silicate, 1.5% sodium toluenesulfonate, 1% borax, 353% sodium sulfate, 10% nonionic surfactant and 7% water.

In a comparative experiment in which the same composition was used, but with the difference that nairium toluenesulfonate was not contained in the mixer batch, spray-dried base spherical particles were obtained which had a density of more than 0.5 g / cm ³ and the particles of the final detergent composition had a density of 0.59 g / cm ³ . For a commercial product which is to be brought onto the market as a replacement for the spray-dried detergent compositions customary up to now, such density values are unsatisfactorily high.

In a modified embodiment of the method according to the invention, the mixer batch was dried by drum drying and plate drying, and the resulting products were comminuted to a particle size of 336 to 0.094 mm clear mesh size and narrower areas. In this procedure, too, the desired reduction in the density of the product to density values in the range from 03 to 03 g / cm ^{3 was} achieved, whereas without the addition of hydrotropic salt, higher density values outside this range result. The bulk density can, if desired, be reduced even further by introducing air into the mixture in which the hydrotropic salt is present before drying. In this way, drum-dried and plate-dried products, as well as spray-dried products with reduced bulk density and in particle size ranges from 2.38 to 0.105 mm and 2.38 to 0.149 mm mesh size, as well as those outside these size ranges, can be obtained Particles are separated off and either reduced to the desired area or returned to the starting mixture to be treated with 2: u.

In the case of further changes to the procedure described, in which spray drying was carried out, the quantitative proportions of the various components in the mixer batch could be modified individually by ± 10, ± 20 and ± 30%, with the specified ranges being maintained and the proportionate amounts of the other components constant stayed. The working conditions could also be changed; the temperature of the Mischcransatzes to 85 ° C, 9O ⁰ C and 100 ⁰ C could be changed, the cross sectional area of the spray nozzle was increased by 10% or be decreased, and the EinlaOtemperatur for the drying air was introduced to various investigations to 250 ° C and Modify 350 ⁰ C. Instead of the inclined drum as indicated, the drum could be used with an inclination angle of up to 5 ° and 12 °, and in some cases the nonionic surfactant was applied by means of a Schugi device or in a fluidized bed of base particles

Detergents based on anionic detergent 65 led. The temperature of the base ball components was superior. The bulk density of the product was changed by + 5 ° C, as was that of the product before packaging, was 034 g / cm ¹ ; it was a nonionic surfactant sprayed on it the non-ionic

15 16

Tenskl (dissolved in it) 0.6% perfume added in all Advantageously usable products according to the invention were obtained from these tests which corresponded in their properties to those described above and were within the specified desired ranges. 5

Example 2

The procedure was as described in Example 1, however, instead of sodium toluenesulfonate, sodium was used Umxylenesulfonat used Essentially the same types of base composition and Final product obtained with low density. If instead of

whose sodium benzene sulfonate was used, can- § ■

if usable products are also produced, is §

but their effect was not quite as good as sg

that of the methyl-substituted benzenesulfonates | jj

containing products. If as a hydrotrope- M

part of the potassium salts were used, including ffj

of the chewing toluocolphonate, so essentially 20 i3

The same types of detergent compositions are used

make tongues. H

Equally good results were obtained if like | jj

previously described was worked with the sub-; N

it was decided that instead of a condensation product of 25 '-}

a C12 to Ci ₅ fatty alcohol with 7 moles of ethylene oxide! -J

per mole of fatty alcohol one from one Ck, - to ^: S

Qg fatty alcohol with an average of 10 to 11 moles of Et- | i '

ethylene oxide per Mo! Fatty alcohol was used. If ζί.

instead of pentasodium tripolyphosphate tetra χ \

sodium pyrophosphate used and if one for the _v ;

Production of phosphate-free detergent compositions

the sodium tripolyphosphate completely 0.

replaced by a mixture of two parts sodium car-; |

bonate and a part of sodium silicate are also pro 35 y

^{products with the cha- 1} J for the products according to the invention

characteristic properties and specifications .)

adjustable. This also applies if instead of sodium sulfate <;

Sodium chloride is used or the sodium sulphate is completely Λ!

constantly omitted and instead an increased men- 40 '

ge of sodium tripolyphosphate and sodium carbonate '

is used, and if one uses sodium silicate with a. ':] nem Na ₂ O: SiO ₂ ratio of 1: 2.0 and 1: 2.4.

45 ';

Claims (10)

Patent claims: 1. Process for the production of an essentially inorganic granular detergent prepro- low density duct, characterized in that a mixer approach is used that is made up of 20 to 50% water. 10 to 50% water-soluble inorganic framework salts. 5 to 50% water-soluble inorganic filler salts and about 0.2 to 5% of a water-soluble salt of a substituted or unsubstituted benzenesulfonic acid, and that this mixer approach is spray dried. A method according to claim 1, characterized in that at least half of the builder salt is used in the form of sodium tripolyphosphate, at least half of the filler salt in the form of sodium sulfate and, as the hydrotropic substance, a water-soluble salt of a lower alkyl substituted benzenesulfonic acid is used and that Performs spray drying in a countercurrent spray tower. 3. The method according to claim 2, characterized in that sodium tripolyphosphate, sodium silicate and sodium carbonate are used as the builder salt, sodium sulfate is used as the filler salt and a water-soluble salt of a mono- or dimethyl-substituted benzenesulfonic acid is used as the hydrotropic compound, the proportions of builder salt to filler salt in the range from 3: 1 to 1: 2 and spray-dry the mixer batch to a moisture content in the range from 3 to 16% and a bulk density of 0.2 to 0.45 g / cm ¹ 4. The method according to claim 3, characterized in that there is used as a spray-dried detergent precursor particles consisting of about 22 to 44% sodium tripolyphosphate. 33 to 16.7% sodium carbonate, 5.5 to 16.7% sodium silicate, 1.1 to 33% sodium toluene sulfonate or sodium xylene sulfonate, 0 to 5.6% borax, 22 to 56% sodium sulfate and from 5.6 to 133% water. 5. The method according to claim 4, characterized in that one uses the mixer approach with a «5 moisture content of about 30 to 45% and the composition of the mixer approach is selected so that it becomes a spray-dried granular detergent precursor, consisting of about 31.1 to 42.2% sodium tripolyphosphate, 33 to 8.9% sodium carbonate, 5.6 to 11.1% sodium silical with a NajO: SiOr ratio of 1: 2 to 1: 2.4, 13 to 2.2% sodium toluenesulfonate, 0.5 is made to 2.2% borax, 33 to 47% sodium sulfate and 6.5 to 1.11% water, is sprayed to the mixer approach with a temperature 80-105 ⁰ C in the spray-drying tower, while an inlet temperature for the introduced for drying in the spray tower air adjusts in the range of 200 to 400 ° C and sprayed the Mischcranatz in the spray tower to droplets of such a ω size that spray-dried particles of the mixture with a particle size in the range of essentially 336 to 0.094 mm clear mesh will. 6. A process for the production of a granular detergent and cleaning agent of low density built up with scaffolding, characterized in that that a mixer suction of 20 to 50% water, 10 to 50% of one or more water-soluble inorganic framework salts, 5 to 50% of one or several water-soluble inorganic filler salts and about 0.2 to 5% of one or more water-soluble organic hydrotropic salts based on a substituted or unsubstituted Benzenesulfonic acid is used and spray-dried and that is then applied to the surfaces of the consisting of the dried mixture particles an amount ensuring the detergency nonionic surfactant is applied. 7. The method according to claim 6, characterized in that at least half of the builder salt in the form of sodium tripolyphosphate, at least half of the filler salt in the form of sodium sulfate, a water-soluble salt of a benzenesulfonic acid substituted with a low alkytite and nonionic acid as the hydrotropic substance Surfactant uses a polyoxethylated higher fatty alcohol, the polyoxethylated higher fatty alcohol in a proportionate amount of 5 to 25% of the Product used and the spray drying is carried out in a countercurrent spray tower. 8. The method according to claim 7, characterized in that sodium tripolyphosphate, sodium silicate or sodium carbonate is used as the builder salt, only sodium sulfate is used as the filler salt and a water-soluble salt of a mono- or dimethyl-substituted benzenesulfonic acid is used as the hydrotropic substance, the ratio of builder salt to filler salt in the range from 3: 1 to 1: 2 is selected, the mixer batch is spray-dried to a moisture content in the range from 3 to 16% and a bulk density of 0.2 to 0.45 g / cm ³ , a condensation product of a polyoxethylated higher fatty alcohol 10 to 18 carbon atoms containing fatty alcohol and 3 to 15 moles of ethylene oxide per mole of fatty alcohol is used. 9. The method according to claim 8, characterized in that a mixture of 20 to 40% sodium tripolyphosphate, 3 to 15% sodium carbonate, 5 to 15% sodium silicate with a Na-iO : SiC »2 ratio in the range of 1: 1.6 to 1: 3.1 to 3% sodium toluene sulfonate or sodium xylene sulfonate, 0 to 5% borax, 20 to 50% sodium sulfate, 4 to 15% fatty alcohol-polyethylene oxide condensation product as a nonionic surfactant and 5 to 12% water and a such fatty alcohol ethylene oxide condensation product is used that melts or softens sufficiently low that it can be sprayed in droplets at a temperature below 45 ° C and the nonionic surfactant at a temperature below 45 ° C on the surfaces of the at a temperature below 55 ° C and above 10 ° C in motion spray-dried particles are sprayed on and melted thereon. 10. The method according to claim 9, characterized in that a mixer approach is used which has a moisture content of about 30 to 45% and has a composition such that after spray-drying a product contains which, if it is subsequently applied 7 to Contains 13% of polyoxethylated fatty alcohol as a nonionic surfactant, a spray-dried composition of 28 to 38% sodium tripoly- phosphate, 3 to 8% sodium carbonate, 5 to 10% sodium silicate with a Na20: SiOr ratio of 1: 2 to 1: 2.4, 1.2 to 2% of sodium toluenesulfonate, 0.5 to 2% borax, 30 to 42% Sodium sulfate and 5 to 10% moisture, the nonionic surfactant used being a condensation product of a fatty alcohol having 12 to 15 carbon atoms with about 7 moles of ethylene oxide per mole of fatty alcohol, the mixer batch being sprayed in the spray tower ^{at a temperature of 80 to 105 ° C. and} the inlet temperature for the drying air in the spray tower is set to a temperature in the range from 200 to 400 ⁰ C, the mixer batch in the spray tower is sprayed in the form of drops of such a size that the spray-dried particles of the mixture essentially have a particle size in the range A mesh size of 336 to 0.094 mm is present, and the subsequent spraying of the non-ionic surfactant onto the surface of these particles, which are thereby circulated, in an inclined position animal drum is carried out, wherein the non-ionic surfactant at a temperature of 35 to 50 ⁰ C and the circulated particles are used at a temperature of 20 to 45 ° C.