DE2655578A1 - METHOD OF RECYCLING DETERGENT POWDER - Google Patents

Description

UEXKÜLL & STOLBHRG PATEIJTANWALTE

= ?. J.-D. FRHR. from UE

2 HAMBURG 52

BESELERSTRASSE 4

_t DR. J.-D. FRHR. by UEXKÜLL · ·

DR. ULRICH GRAF STOLBERG DIPL.-ING. JÜRGEN SUCHANTKE

Colgate-Palmolive Company (priority: December 15, 1975

300 Park Avenue ^{US 64} ° ⁷⁹² " ¹³⁵⁷⁴ >

New York, N.Y. 10022 / V.St.A.

Hamburg, December 6th, 1976

Process for recycling detergent powders

The invention relates to the reprocessing of poorly pourable or caking detergent powders and in particular a method of treating such powders with a non-phosphate compound which is the Powder converted into a non-caking, easily pourable form without affecting its washing properties will.

In the manufacture of synthetic detergent powders, builder and filler salts (filier) are commonly used. However, these often tend to absorb water. Comes So free moisture in contact with the ingredients of the detergent mixture can cause hydration lead such builder salts. The hydrates, in turn, can dartti act as binders that hold the particles together and either worsen the pourability of the product.

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tern or, in the worst case, lead to caking. Such properties are of course undesirable for one Product that should be in powder form and pourable from a storage container. Various attempts have therefore been made have been to produce detergent mixtures that contain so little moisture that hydration and caking is not a problem. Alternatively, try for any moisture present have been made to consume these by hydrating the salts present prior to packaging. aside from that are preferably spherical, by spray drying, in order to maintain the pourability of the detergent mixtures produced powder particles have been used. In addition, certain builder salts have been found to be primarily the polyphosphates, such as pentasodium tripolyphosphate, have the ability to absorb significant amounts of moisture without losing their pourability, and that such builder salts, incorporated in detergent mixtures, also preserve their pourability.

In spite of changes in the composition and in spite of the use of particle shapes which promote pourability, detergent mixtures are exposed to changing humidity and temperatures during storage, and this often leads to Dehydration of previously hydrated salts. These are then re-hydrated and bake together, so that a caked or poorly pourable product is created. In addition, the content of detergents

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Mixtures of polyphosphates are legally limited to prevent the pollution of lakes and rivers with phosphates to prevent, as these supposedly have a eutrophic effect. Due to the removal of polyphosphates from detergent mixtures or at least reducing the content of these, other builders such as silicates are stronger tend to cause caking of the particulate materials with which they are associated in order to maintain the high builder detergency. aside from that The commonly used non-ionic detergents tend to be oily liquids or waxy solids are, to worsen the pourability of detergent powders. With regard to various changes, which have been proposed to improve the cleaning power of detergent mixtures, especially in Related to phosphate-free products, and many of which have been used in the manufacture of laundry detergents and due to uncontrolled storage conditions, either the finished sales package or before packaging, some detergent mixes are as manufactured in terms of their bulk and caking properties not satisfactory. In the past, such products were reprocessed in detergent manufacturing but only in small quantities so that the end product does not have poor pourability. Alternatively, detergent products that do not meet the requirements are returned to the soap kettle.

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den in order to at least partially use their organic To achieve constituents. In the worst case, such products had to be discarded.

It is often difficult to find those that do not meet the requirements To process detergent products again, since at the point in time at which these deficiencies are discovered, the Manufacture of the special product can already be finished and it would therefore have to be canceled until such a product is restored, or it would have to be mixed with another product, but with the desired properties this product can be affected. In contrast, the method according to the invention now allows an economical one and effective reprocessing or recycling of a detergent mixture that does not meet the requirements, that is sticky, difficult to pour or caked up. Such a mixture can be sufficiently effective be reprocessed so that they can be packaged and sold and after storage even under unfavorable conditions atmospheric storage conditions having.

The invention accordingly relates to a method for reprocessing poorly pourable or caked detergent powder containing a synthetic organic surfactant contain inorganic salt and moisture, with a small proportion of the latter containing the salt to form a caking,

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poorly pourable form hydrated, which is characterized is that such a detergent powder is mixed with 0.5 to 10 wt.% of a molecular sieve zeolite which at least Based on its weight, can absorb a further 10% by weight of moisture. In a preferred embodiment of the method, the reprocessing takes place at about Room temperature by mixing the poorly pourable or caked detergent powder with the prescribed Amount of an anhydrous molecular sieve zeolite of type 4A in finely divided powder form from 30 seconds to 10 minutes treated for a long time in a rotating tubular container with the axis of rotation more horizontal than vertical, The preferred detergent mixtures treated according to the invention are phosphate-free spray-dried detergent powders that contain a certain percentage of sodium dodecylbenzenesulfonate, Sodium Silicate, Sodium Sulphate, Nonionic Surfactant, Sodium Soap of Higher Fatty Acids, Sodium Carboxymethyl Cellulose and contain moisture.

The molecular sieve zeolites for the treatment of poorly pourable or caking detergent mixtures are water-insoluble, crystalline aluminum silicate zeolites of natural or synthetic origin that are marked are characterized by a network of equally large, very small pores, e.g. from about 3 to 10 A, the size of which is determined by the unit structure of the zeolite crystal. Zeolites with two or several network structures with different pore sizes

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can also be used. Amorphous zeolites can also be used, but crystalline zeolites with pores of even size are more suitable.

The molecular sieve zeolite used is also preferably a univalent cation exchange zeolite, i.e., it should be an aluminosilicate containing a univalent cation such as sodium, potassium, lithium (if practicable), ammonium or contains hydrogen. The zeolite should preferably be an alkali metal, namely potassium or, in particular, sodium, contain.

Crystalline zeolites which are suitable as molecular sieves for the purposes of the invention are at least in part zeolites of the following crystal structure groups: A, X, Y, L, mordenite and erionite. Also mixtures of such molecular sieve zeolites are suitable, especially if they contain zeolite A, e.g. zeolite 4A. These preferred crystalline Types of zeolites are generally known and are described in more detail in "Zeolite Molecular Sieves" by Donald W. Breck, published 1974 with John Wiley & Sons. Typical commercially available zeolites of the structure types mentioned are shown in the table 9.6 listed on pages 747 to 749 of the cited reference.

According to the invention, zeolite is preferably used as the molecular sieve a synthetic molecular sieve zeolite is used. This

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should preferably be of type A. Such type A zeolites are described on page 133 of the cited literature reference. Particularly good results are achieved according to the invention when a molecular sieve zeolite of type 4A is used, the contains sodium as a cation and its pore size is about 4 Å. The particularly preferred molecular sieve zeolites are described under the name Zeolite A in US Pat. No. 2,882,243.

The molecular sieve zeolites can either be dehydrated or calcined form with a water content of less than 1.5 up to 3% or in hydrated or with water loaded form are produced, which, depending on the type of zeolite used, additionally adsorbed water in an amount of up to about 20 to 30%, based on the total weight of the zeolite. Preferably they are anhydrous or partially hydrated Molecular sieve zeolites used for the process according to the invention. These should preferably be at least 10%, based on their weight, can adsorb moisture, the moisture from the poorly pourable detergent mixture is removed and taken up by the crystal structure of the molecular sieve zeolite. It is particularly preferred the anhydrous or substantially anhydrous form of the zeolite used, which usually has a moisture content less than 5%, preferably less than 3%, and most preferably less than about 2% or even less. The production of such crystals is well known. at

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For example, in the manufacture of zeolite A, the partially hydrated or completely hydrated zeolite crystals, which in the crystallization medium (such as an aqueous amorphous sodium aluminosilicate gel) are formed, a high-temperature dehydration (calcination to a water content of 3% or less), as is customary in the manufacture of such crystals for use as catalysts, e.g. cracking catalysts, happens. In some cases, however, the high-temperature dehydration can occur before the complete Dehydration can be canceled or the temperature for dehydration can be lower, so that a partial hydrated zeolite is obtained which has a desired moisture content, e.g., 8%, and yet at least can absorb a further 10% (anhydrous basis) of moisture.

Usually, the molecular sieve zeolite should be in finely divided form exist, e.g. in crystals (amorphous or poorly crystalline particles can also be used to a certain extent) with mean particle diameters of about 0.5 to 12 µm, preferably 5 to 9 µm and especially about 5.9 to 8.3 µm, e.g. 6.4 to 8.3 µm.

The synthetic organic surfactants, which are components of the detergent powder to be reprocessed, can be anionic or be non-ionic. Although ampholytic and cationic surfactants can sometimes also be suitable,

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these are usually used for the mixtures according to the invention not used. The anionic surfactants used usually have 8 to 26 and preferably 12 to 22 carbon atoms per molecule and usually have an alkyl or aliphatic chain of about 8 to 18 carbon atoms and preferably 10 to 16 carbon atoms in a straight chain Alkyl group. Most preferred of these surfactants are alkali metal compounds of higher alkyl benzene sulfonates like the sodium and potassium salts in which the higher alkyl groups 10 to 18 carbon atoms and preferably 12 to 14 carbon atoms and preferably straight chain are. Other such anionic surfactants are cL-olefin sulfonates, Paraffin sulfonates, ethoxylated alcohol sulfates, alkyl sulfates and sulfated higher alkylphenyl polyoxyethylene ethanols, all preferably in the form of their alkali metal salts such as the sodium salts. A list of such surfactants can be found in US Pat. No. 3,637,339. Anionic surfactants also include the higher fatty acid soaps, the sodium salts of fatty acids having 12 to 18 carbon atoms.

Together with the anionic surfactants or as a partial or complete replacement of these, non-ionic surfactants can be used Surfactants are used. These are usually lower alkylene oxide condensation products such as polyethylene oxides, which sometimes contain polypropylene oxide, but only to such an extent that the product is still water-soluble. Preferred examples of such materials are the higher ones

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Fatty alcohol-polyethylene oxide condensates in which the higher fatty alcohols have 10 to 18 and preferably 12 to 15 carbon atoms and the ethylene oxide component is a chain of 6 to 30, preferably 7 to 15 and particularly preferably 10 to 15 ethylene oxide units. Similar ethylene oxide condensates of 0, -C ₁ "-alkylphenols, such as nonylphenol or isooctylphenol, are also suitable. However, these are not preferred.

The inorganic builder and filler salts are usually water soluble Salts of suitable inorganic acids. The builder salts are accordingly salts of silicic acids, boric acid, carbonic acids and polyphosphoric acids, while the filler salts are salts of sulfuric acids and hydrochloric acid. Of course, others can too inorganic acids can be used. Preferably the salts are alkali metal salts and of these in turn are the sodium salts are preferred, although both sodium and potassium salts can be used. The most preferred Builder salts are sodium silicates and the most preferred filler salt is sodium sulfate. Good as well suitable builder salts are sodium carbonate, pentasodium tripolyphosphate and borax. The salts act as carriers for the synthetic organic surfactants and can also be used to adjust the pH of the detergent solution. The silicates and phosphates have the effect of water softeners or sequestering agents, limiting the formation of insoluble and gelatinous soaps

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and other calcium and magnesium compounds such as calcium and magnesium salts of surfactant acids that are undesirable or less active than the sodium salts in the wash water can be, to a minimum. The sequestering agents are also special suitable to prevent iron staining or staining on the items to be washed Materials to prevent. Various organic builders such as sodium gluconate, tetrasodium ethylenediamine tetraacetate, Trisodium nitrilotriacetate and sodium citrate can also be used.

In addition to surfactants, builders, filler salts and moisture, which is also present in the detergent mixtures to be treated according to the invention, the detergent mixture can contain various generally known auxiliaries for such products contain. Most important of these are the anti-dirt redeposition agents, the redeposition Prevent dirt particles on the laundry during washing. In the present case, such materials are special important because they help to keep the molecular sieve zeolite in solution, which would otherwise be deposited on dark-colored laundry and could significantly change such dark or strong colors (e.g. a color change towards pastel tones). Examples of agents against redeposition of dirt are sodium carboxymethyl cellulose (CMC), polyvinylpyrrolidone, Polyvinyl alcohol, hydroxypropylmethyl cellulose, hydroxyethyl ethyl cellulose and various other cellulose and starch derivatives and, as is well known, suitable for this purpose

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nice rubber. Of the substances mentioned, CMC is preferred.

The detergent mixtures to be treated according to the invention may contain other auxiliaries, such as brighteners, Colorants and perfumes and, in many cases, agents which improve the pourability, such as clays, which are used in however, the materials to be treated according to the invention have no effect. Fluorescent brighteners include the various cotton brighteners, polyamide brighteners and Polyester brighteners, the reaction products of cyanuric chloride and the disodium salt of diaminostilbene disulfonic acid can, benzoxdinsulfondisulfonsauren, aminocoumarins, diphenylpyrazoline derivatives or naphthotriazolylstilbenes, for example under the names Calcofluor, Tinopals RBS and 5BM and Phorwite BHC are commercially available. Such materials are described in the article "Optical Brighteners and Their Evaluation "by Per S. Stensby in" Soap and Chemical Specialties ", April, May, July, August and September 1967, described in particular on pages 3 to 5.

Together with the listed ingredients it can sometimes be desirable to have per-compounds in the detergent mixtures and activators for these are included. Suitable per compounds include sodium perborate, usually as Tetrahydrate, sodium carbonate peroxide and sodium percarbonate. Activators for the per compounds are well known and promote the development of oxygen from them

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Improvement of the bleaching effect. These activators include both triazine and acyl type compounds such as 2- / bis (2-hydroxyethyl) -amino7-4,6-dichloro-s-triazine (BHADT), 2,4-dimethoxy-6-chloro-s-triazine (DCT), diacetyldimethylglyoxime (DDG), and tetraacetylglycoluril (TAG), all of which are described in the US patent application with serial no. 640 791 or in the

parallel German patent application with the file number

are listed. However, as stated in the cited patent application, some detergent mixtures are the one Per compound, such as sodium perborate tetrahydrate, so strongly hydrated that caking by the inventive Proceedings cannot be prevented. Accordingly, the content of per compound and in particular of sodium perborate tetrahydrate should be in the mixtures to be treated according to the invention not more than 20 and preferably not more than 10% otherwise the detergent mixtures will stick together may be irreversible (albeit the presence of the surfactant, the CMC, and various other organic materials can help prevent hydration irreversibility).

The different, according to the method according to the invention Detergent mixtures to be treated can be prepared by mixing powdered compounds together, reducing the Particle size, drum drying, spray cooling or, preferably, spray drying can be produced. Such components, which are unstable to such treatment

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preferably added afterwards. For example, when using spray drying, any per compounds and Perfumes and any clays to improve pourability after spray drying and usually after addition other ingredients to be added subsequently.

Spray drying is usually accomplished by placing the various ingredients in an aqueous medium, usually mixed at a solids content of 40 to 70% and preferably 50 to 70% and this mixture then in drier Air at a temperature of about 250 ° C, spray-dried. Spray drying takes place in a countercurrent or cocurrent spray drying tower. The product consisting of spherical particles can then be sieved or classified in order to maintain a certain particle size range. Usually the particle range is such that over 95% and preferably 100% pass through a U.S. Standard No. 8 sieve and less than 10%, preferably less than 5% and am at best 0% pass a US standard No. 140 sieve. A particle size range between the US Standard Sieves No. 10 and No. 100. The spray-dried product particles have various shapes, but are mostly round and almost spherical, so that the contact surfaces and thus the risk of caking on one Minimum are limited. (In some cases, the molecular sieve zeolites described above can be used in the spray-dried Product particles, but often the zeo-

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lithen then partially or fully hydrated by mixing in an aqueous medium, making them less effective regarding moisture absorption and caking prevention).

Based on the detergent powder to be treated, 0.5 to 10%, preferably about 1 to 5% and in particular about 2% molecular sieve zeolite used. The amount of zeolite to be used is generally determined by the amount of excess or free moisture in the product and according to the amount of moisture caused by crystallization or otherwise contained in the product ingredients, usually in the hydratable, inorganic ones Salts, and the particles containing them stick together or soften other product components. In general, the moisture level in the synthetic detergent mixture is the caking and the poor pouring properties causes only a part and often only a very small part of the total present Humidity. So the moisture content of the detergent particles is up to 15%, usually 5 to 15% and often 5 to 10%, e.g. 7%, then the amount of moisture causing caking can be 0.05 to 2% and often Make up 0.1 to 1%. The molecular sieve zeolite used should therefore be able to completely absorb this moisture to record. For example, if there is 2% of this free moisture in the product and the molecular sieve zeolite used a total capacity of 22% moisture

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absorption and if the zeolite when mixed with the detergent mixture and before the absorption of any moisture already contains 2% moisture, 10% molecular sieve zeolites will be used to remove all harmful moisture to absorb in the detergent mixture. In general, it is desirable to have some excess dehydrating capacity of the zeolite. Therefore, the zeolite should be able to contain at least another 10% its weight to be able to absorb moisture and preferably this should have additional water absorption capacity be at least 15% and in some cases 20% or more. For example, 2% anhydrous zeolite 4A which can be easily hydrated to a moisture content of 22% Absorb 0.4% of the moisture of the added detergent mixture.

The water uptake by the molecular sieve zeolite is by its small particle size and large surface area and also facilitated by the fact that the very fine particles can penetrate into the small cavities between and in the crystal structures to extract the moisture and thus destroy the bond between the particles and make the product more pourable. The small molecular sieve particles tend to stick to the surface of the product and thereby prevent despite their small size dust and at the same time remain in a position in which they prevent the particles from sticking together, even if

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During storage, water is released due to the decomposition of the hydrates or if storage takes place in a moist environment.

Although spray-dried detergent products are preferred according to the invention be treated, granulated and other finely divided detergent mixtures can also be used to prevent this the caking are treated according to the invention. In these cases the particles can range in size from 325 or 400 up to 8 mesh but usually in the range 140 to 250 or 325 mesh.

The proportions of the various ingredients described in the detergent mixtures to be treated are customary about 10 to 30% synthetic organic surfactant, 30 to 75% or 85% inorganic salt, with 5 to 30% being preferred Sodium silicate and 25 to 60%, preferably sodium sulfate, and 5 to 10% moisture. The content of synthetic organic anionic surfactant is generally 10 to 28% and preferably 15 to 25%, and the The content of the nonionic surfactant is 1 to 20, and preferably 1 to 5%. If next to the silicates and the sulfate if further inorganic salts or builders are present, their total proportion is usually 2 to 20 and preferably 5 to 15%, which is at the expense of the sodium sulfate content. An exception is pentasodium tripolyphosphate, of which up to 35% can be present if desired, usually at the expense of the sodium sulfate content. Loading

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preferred levels of soap, agents to prevent redeposition of dirt and other auxiliary materials (including fluorescent brighteners, clays, coloring agents and perfumes) are usually in the range of 0.5 to 5%, 0.3 to 3% or 0.5 to 10% and preferably in the range from 0.5 to 2%, 0.5 to 2% and 0.5 to 5%, respectively. The proportion of aluminum ilicate or clay to improve pourability (before treatment according to the invention) is usually 0.5 to 3% and preferably about 1%.

When a detergent mixture is found to be caking (preferably only slightly caked) or difficult to pour or tends to become sticky when stored them in a minor amount, e.g., 0.5% of the anhydrous or partially hydrated and additionally hydratable Molecular sieve zeolites treated and thus reprocessed in order to improve the pourability, another To prevent caking during storage and to make the product salable and usable again. After addition such an amount of molecular sieve zeolite and after only about 1 minute of mixing in a normal inclined mixing drum, which is preferably more to the horizontal than to the vertical and in particular at an angle of 3 to 15 ° to the horizontal is inclined, a sample is taken and examined for its pourability and tendency to cake. If this examination, a visual comparison test described below, is positive, the treated washing agent can

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medium mix are packaged, delivered and sold. However, if the pourability is still poor, a further 0.5% of the molecular sieve zeolite can be added. If the exact amount of zeolite required is determined in this way, further batches of the same detergent can be used treated with the same amount of zeolite without having to examine the pourability each time. Usually an addition of about 1 to 5% and preferably 1 to 3% of zeolite proves to be sufficient, in particular when an anhydrous zeolite is used. The mixing time for adequate mixing and anti-caking is usually 30 seconds to 10 minutes, and preferably 1 to 5 minutes. Mixing in the Zeolites are preferably carried out at about room temperature, 20 to 30 ° C, but can very generally be carried out at 10 to 45 ° C. Products that are very caked together can break up the larger lumps before the zeolite is added mechanically treated so that the caking particles are more accessible to the zeolite.

The most preferred detergent mixtures for the treatment according to the invention are phosphate-free detergent mixtures, the anionic surfactant, sodium silicate, CMC and sodium sulfate and in many cases also non-ionic Contains surfactant. All of these materials (except possibly Sodium sulfate) play a part in the detergent's tendency to become sticky and cake together.

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Nevertheless, the mixtures described often have to be prepared in order to produce detergents with satisfactory cleaning properties that are comparable to those which are phosphate detergent. The manufacture of such products is particularly important where there are phosphates in detergent mixtures are not permitted.

The method according to the invention therefore improves the physical properties of the preferred phosphate-free detergents sufficient so that they can be marketed, which is a significant technical advance represents. Moreover, this improvement is achieved without the addition of very large amounts of an ingredient which the properties of the detergent are significantly impaired. Rather, the molecular sieve zeolites have only a small amount Effect on detergents, in fact, is just another builder ingredient and is one in this regard Improvement. The molecular sieve zeolites do not lead to environmental pollution, do not affect the need for biological Oxygen in the wastewater of the washing process and settle in the small amounts used, especially in Ge in the presence of an agent to prevent the redeposition of dirt on the laundry to be washed.

In the following examples, all percentages are given in % By weight and all temperature data in C.

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example 1 Component percent

Sodium dodecylbenzenesulfonate (linear alkyl radical) 23

Sodium silicate (Na ₂ O: SiO = 1: 2.4) 25

Sodium sulfate 40

High fatty acid sodium soap (hydrogenated sebum:

hydrogenated coconut oil = 4: 1) 1

non-ionic surfactant (Neodol 45-11) 1

Sodium carboxymethyl cellulose 0.5

Aluminum silicate (pourability improvement

medium) 1

Auxiliary materials (fluorescent brighteners, perfume,

Stabilizers, coloring agents) 1

Humidity 7

The above product was made by spray drying an aqueous mixture having a solids content of 60% containing all ingredients in addition to the perfume and aluminum silicate, in a countercurrent spray drying tower with drying air of about 250 C. The resulting product was cooled to room temperature, sprayed with perfume, mixed with a pourability-improving agent and sieved so that it is rounded, essentially spherical particles that passed through a U.S. Standard No. 8 sieve and not through a U.S. Standard No. walk. More than 90% of the particles, i.e. essentially all, also passed through a US standard sieve No. and did not pass through a U.S. Standard No. 100 sieve.

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Due to the presence of excess free moisture that will soften some detergent mix ingredients and leads to hydration of the silicate, whereby some of the particles stick together with other particles caking and poor pourability of the detergent mixture after a few hours of storage in a container observed. On a rating scale from 0 to 10, where 0 is optimal pourability and 10 is complete caking means, the product thus produced was rated by various observers with 8, 9 and 10, i.e. it was unacceptable for packaging and sales in this condition.

The caked product turned into smaller pieces with mostly broken to a diameter of less than 1 cm and in a continuously operating drum mixer, the was inclined to the horizontal at an angle of 8 ° and rotated at a speed of 40 rpm, with 2% of a substantially anhydrous (2% hydrated) molecular sieve zeolite 4A from Henkel & Cie (HAB-100) with a particle size in the range of 6.5 to 8.3 µm. A sample was taken after mixing for 5 minutes and was observed to be significantly better looked more pourable and less prone to caking. The pourability was between 1 and 4 judged. This product and a control sample, which had previously been treated in the same way, were then

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but without the addition of molecular sieve zeolite were compared and it was found that the control sample was comparatively difficult to pour and many of them caked together Contained lumps. Samples of the test product and the control product were placed in sealed vessels and stored there for 7 days. Then they were examined again. The test product was still pourable, accordingly Bulk ability ratings from 1 to 3, and the control product was severely caked and scored a 10 judged.

In a modification of the experiment described, 4% of a molecular sieve zeolite was used, the initial one Moisture content of 10%. Were accordingly other anhydrous molecular sieve zeolites, all with a moisture content of less than 5%, in lieu of that described Molecular sieve zeolites 4A used. For example, a 4A zeolite manufactured by Union Carbide Corporation, other molecular sieve zeolites of type A and those of types X, Y and L and mixtures thereof. The pourability the detergent products could be improved considerably in all cases.

Even with modified detergent compositions in which the linear sodium dodecylbenzenesulfonate is replaced by linear sodium tridecylbenzenesulfonate was replaced, the same results were obtained. Even if the proportion of the linear higher

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Alkylbenzenesulfonate reduced to 18%, the content of soap increased to 3%, 5% sodium carbonate added, the proportion of non-ionic, ethoxylated, alcoholic surfactant increased to 2 and 4%, with the non-ionic surfactant by half the mixing and before treatment with the perfume was sprayed, and the proportion of sodium carboxymethyl cellulose to 1% was increased, with the additional proportions of these materials at the expense of the sodium sulfate content and the moisture content was 8%, the addition of 4% of the above-mentioned anhydrous molecular sieve zeolite resulted in considerable Improvements in the pourability of the detergent. This is also the case when half the sodium higher alkylbenzenesulfonate by sodium paraffin sulfonate, sodium Od. -olefin sulfonate, sodium salt of higher fatty alcohol sulfates and higher sodium alkanesulfonates having 12 to 16 carbon atoms and mixtures thereof. the Desirable results are obtained even if the product does not contain any nonionic surfactant or soap.

In a further modification of the experiment, 8% was sodium sulfate replaced by 8% sodium perborate tetrahydrate with a particle size in the range from 140 to 250 mesh. That Sodium perborate tetrahydrate was added after mixing but before adding the perfume and the pourability enhancer By means of, admittedly. In such experiments, the use of 2 to 5% of the preferred 2% hydrated yielded Molecular sieve zeolites 4A significant improvements in pourability.

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10% - - 30%, and - in further modifications of the experiment, the levels of anionic surfactant, sodium silicate, sodium sulphate, other ingredients and of moisture in the detergent compositions and the amount of molecular sieve zeolites used for the treatment in order of 50% change, but remained in the areas previously specified in the description. If the detergent mixtures produced in this way were sticky and poorly pourable or caked together, the pourability could be considerably improved by adding molecular sieve zeolite in the manner described. The products, which were often stored for 1 day to 6 months, were superior to control products which did not contain post-added molecular sieve zeolite in all cases.

The various detergent mixtures produced, which contained the subsequently added molecular sieve zeolite, were pourable and non-caking detergents of good quality. When used in one concentration of 0.15% in cold or hot washing water with a hardness of 150 ppm (as calcium carbonate; 3: 2 = Ca: Mg hardness as calcium carbonate) at temperatures of 20 to 80 C and normally around 50 ° C all detergents cleaned satisfactorily, and there were no redepositions on both linen drying and drying in an automatic Laundry dryer detected. These washing tests were carried out in automatic laundry washing machines with a Volume of about 80 1 carried out. There were 4 kg each

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white and colored laundry, consisting of cotton, cotton-polyester blends and other fabrics.

Example 2 Component percent

linear sodium tridecylbenzenesulfonate 18

Sodium silicate (Na ₂ OrSiO ₂ = 1: 2.35) 15

Sodium carbonate 5

Sodium sulfate 50

Ethoxylated alcohol (Plurafac B-26) 1

Sodium tallow soap 1

Aluminum silicate clay 1

Auxiliary materials (Tinopal 5BM. Cone, fluorescent Brightener, dye mixture, stabilizer, 1.5 Pigment and perfume)

Humidity 7.5

The above product with essentially the same particle size as the products described in Example 1 showed according to the Production poor pourability and tended to Caking. The caked product was successively washed several times with 0.5% of the anhydrous described above Molecular sieve zeolites 4A added and treated in the manner described. After adding zeolite (3%) 6 times a product with a satisfactory pourability was obtained. This product proved to be the one described above Laundry test as a good laundry detergent, using a Gardner Color Difference Meter for evidence of improvements

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the washing properties was used. In terms of detergency, the product corresponded to an untreated control product, but was much more acceptable from a commercial point of view. Even after 1 month of storage it still had one very good pourability.

On the basis of the experiment described, other batches of the sticky and poorly pourable detergent mixture also treated with 3% of the molecular sieve zeolite and gave correspondingly improved products. Alternatively Different approaches were tested independently of one another, and all could be achieved by adding 2.5 to 3.5% of the anhydrous Molecular sieve zeolites a satisfactory improvement can be achieved.

Even when changing the mixing process, so that the temperatures of the detergent mixture fragments to be treated were at 15 ° C., 25 ° C. and 40 ° C., detergent mixtures resulted with good pourability properties. This was also the case when the relative humidity during the addition of the molecular xebe zeolite and during storage was varied in the range of 20 to 80%. Even with variation of the Mixing times from 1 minute to 10 minutes resulted in good products. Excessive mixing is undesirable because the spherical structure of the detergent particles can be destroyed. The method according to the invention is accordingly Particularly suitable as only very short mixing times are required for treating the product.

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Example 3

A powder detergent was prepared with a composition according to Example 1 with the difference that 25% of the sodium sulfate were replaced by pentasodium tripolyphosphate and the moisture content was increased from 7 to 9%. A product produced in this way cannot be poured sufficiently well, although the presence of pentasodium tripolyphosphate contributes to the fact that such a product has a satisfactory pourability at lower (7%) moisture contents owns. The detergent mixture thus produced was therefore in the manner described in Example 1 with 4% molecular sieve zeolite 4A treated. The result was a readily pourable and non-caking product.

Example 4

Products composed according to Examples 1 to 3 were in granulate form with a particle size in the range from 140 to 250 mesh made. Such products stuck together more strongly than the spray-dried products. But it was twice as much Molecular sieve zeolite added as described above, these products also had an improved pourability, and the tendency to cake was greatly reduced.

709824/0960

Claims (5)

patent claims 1. Process for reprocessing poorly pourable or caking detergent powder containing a synthetic organic surfactant, an inorganic salt and moisture, with a small part of the moisture turning the salt into a caking, poorly pourable form hydrated, characterized in that the detergent powder 0.5 to 10% by weight of a molecular sieve zeolite, which, based on its weight, is at least another 10% Can absorb moisture. 2. The method according to claim 1, characterized in that a detergent powder is treated as a synthetic organic surfactant, anionic surfactants, non-ionic surfactants, and mixtures thereof, as inorganic Salt sodium silicate, sodium sulfate, sodium carbonate and pentasodium tripolyphosphate and mixtures the same and 5 to 15% moisture, with caking and poor pourability from 0.1 to 1% of this moisture is effected, and that a molecular sieve zeolite is used which to is less than 5% hydrated. 709824/0960 3. The method according to claim 1 to 2, characterized in that a detergent powder is used which is essentially is free of phosphates and consists of spherical, spray-dried particles with a particle size of im Range from 8 to 140 mesh is a molecular sieve zeolite A is used, which is in finely divided powdery form with particle diameters in the range of about 0.5 to 12 .mu.m, and that the mixing of the poorly pourable or caking detergent powder with the molecular sieve zeolite in a rotating drum mixer whose axis of rotation is longer is inclined to the horizontal than to the vertical. 4. The method according to claim 1 to 3, characterized in that one uses a water-soluble, linear, higher alkylbenzenesulfonate with an alkyl group having 12 to 16 carbon atoms containing 10 to 30% synthetic organic surfactant, 5 to 30% sodium silicate with a Na ₂ O: SiO ₂ ratio in the range from 1: 2.0 to 1: 2.8, 25 to 60% sodium sulfate and 5 to 10% moisture, and that a molecular sieve zeolite 4A which is less than 3% hydrated with a Particle size in the range from 6.4 to 8.3 µm used and added to the detergent in an amount of 1 to 5%. 5. The method according to claim 1 to 4, characterized in that a detergent mixture is used which also contains 1 to 20% by weight of a condensation product of a ^c -i ₀ ~ ^C 18 "alkanol with 6 to 30 ethylene oxide units, as a water-soluble linear higher alkylbenzenesulfonate sodium dodecylbenzenesulfonate , Contains sodium silicate with a Na "0: SiO ₂ ratio of about 1: 2.4 and sodium sulfate, and that the mixing with the molecular sieve zeolite is carried out at a temperature of 10 to 45 ° C. for a period of 30 seconds to 10 minutes. ue: ka: bü