WO2000032739A1 - Granulation method - Google Patents

Abstract

The invention relates to a granulation method which permits omission of the step of drying the granulates without resulting in negative properties of the granulate. The inventive method also makes it possible to subject sensitive substances or mixtures of substances such as washing and cleaning compounds to wet granulation. The resulting products do not have further negative product properties such as poor solubility etc. To this end, the inventive method uses an oversaturated solution as granulation adjuvant.

Description

 'Granulation process'

The present invention relates to a granulation process for the production of granules from finely divided solids by adding a granulation aid ("granulation liquid"). In particular, the present invention relates to a method for producing detergent and cleaning agent granules.

The transfer of finely divided solids into a coarser form is desired in a wide variety of applications and a reliable state of the art. Depending on the type of "coarsening" solids, different methods are used. In addition to pure shaping processes, such as melting or sintering of the substances, press agglomeration and granulation processes in particular are of outstanding importance for "coarsening" the most diverse substances or mixtures of substances. Press agglomeration processes are characterized in that a premix is exposed to a high pressure and is plasticized and compacted in a shaping manner, possibly by the presence of binders contained in the mixtures. The most important and best known press agglomeration processes are extrusion, roller compaction, pelleting and tableting.

In addition to these processes, there is in particular the granulation of fine-particle substances in a wide variety of applications, such as in the production of fertilizers, animal feed, pill seeds, detergents and cleaning agents, pesticides and pesticides, pearl pitch, stone and mineral chippings, plastic granules, abrasive grains, cocoa sugar mixtures or pearl glue is widely used as an inexpensive and effective process.

In important granulation processes, a moving solid bed is granulated by the addition of granulation aids. The granulation aids, which are also known as granules tion liquids are referred to, form liquid bridges between the individual powder particles, which in this way are "glued" together to form larger aggregates - the granules. This process is made possible and supported by the action of shear forces caused by the movement of the mixing elements, a homogeneous addition and distribution of liquid being extremely important for the success of the granulation process. During the granulation process, the individual pulp particles are deformed and the intraparticulate spaces are filled with the granulation liquid, so that overall larger particles are formed, the bulk density of the mixture increasing and the particle porosity decreasing.

Depending on the material to be granulated, a wide variety of granulation aids are used, with water as a whole being of outstanding importance. In the detergent and cleaning agent industry, in addition to pure water, aqueous solutions of polymers or surfactants or the pure surfactants, in particular nonionic surfactants, or surfactant pastes are used as granulation liquids.

The use of water or aqueous solutions in many areas of application has the problem that the resulting granules are too moist and therefore have to be dried after the granulation in order to avoid product caking or stability problems. On the one hand, a sufficient amount of granulating liquid is required to ensure the granulation process, on the other hand, when using water or aqueous solutions, this amount can be too large for the finished product, so that drying is required. If temperature-sensitive substances are granulated, this drying is only possible with very low supply air temperatures, which increases the drying time and greatly reduces the throughputs that can be achieved.

The present invention was based on the object of providing a granulation process in which the drying of the granules can be dispensed with without resulting in negative granule properties. In particular, a method should be provided which enables sensitive substances or mixtures of substances such as washing and subjecting detergent compositions to wet granulation without resulting in further negative product properties such as poor solubility, etc.

It has been shown that the use of supersaturated solutions as granulation aids leads to a granulation process which fulfills the requirements mentioned. The present invention therefore relates to a granulation process in which a liquid granulation auxiliary is added to a moving solid bed, a supersaturated solution being used as the granulation auxiliary.

In the context of the present invention, supersaturation is the term for a metastable state in which more of a substance is present in a closed system than is required for saturation. A supersaturated solution obtained, for example, by hypothermia therefore contains more solute than it should contain in thermal equilibrium. The excess of dissolved substance can be brought to instantaneous crystallization by seeding with germs or dust particles or by shaking the system. In the context of the present invention, the term “oversaturated” always refers to a temperature of 20 ° C. If a substance dissolves x gram per liter in a certain solvent at a temperature of 20 ° C, the solution in the context of the present invention can be described as "supersaturated" if it contains (x + y) gram of the substance per liter , where y> 0 applies. In the context of the present invention, solutions which are added to the mixer at an elevated temperature at which there is more solute in the solution than are dissolved in the same amount of solvent at 20.degree. C. can also be referred to as "supersaturated" would.

The term “solubility” is understood by the present invention to mean the maximum amount of a substance that the solvent can absorb at a certain temperature, ie the proportion of the solute in a solution saturated at the temperature in question. If a solution contains more solute than it should contain in the thermodynamic equilibrium at a given temperature (e.g. under hypothermia), it is called supersaturated. By inoculating with germs it can be caused that the excess as the bottom body of the now only saturated solution fails. One in terms of a sub- Punched saturated solution can also dissolve other substances (e.g. you can still dissolve sugar in a saturated sodium chloride solution).

As described above, the state of supersaturation can be achieved by slow cooling or by subcooling a solution as long as the solute is more soluble in the solvent at higher temperatures. Other ways of achieving supersaturated solutions are, for example, combining two solutions, the ingredients of which react to form another substance that does not immediately fail (prevented or delayed precipitation reactions).

In principle, the state of supersaturation can be achieved with any type of solution, although the principle described in the present application is particularly preferably used in the production of detergents and cleaning agents. In addition to nonionic surfactants or common non-aqueous solvents, granulation processes are therefore particularly preferred in which a supersaturated aqueous solution is used as the granulation aid.

As already mentioned above, the state of supersaturation in the context of the present invention relates to the saturated solution at 20 ° C. The state of supersaturation can easily be reached by applying solutions as granulation aids which have a temperature above 20 ° C. Granulation processes in which the supersaturated solution used as granulation aid, when added to the moving solid bed, has a temperature between 35 and 120 ° C, preferably between 40 and 110 ° C, particularly preferably between 45 and 90 ° C and in particular between 50 and 80 ° C, has are preferred in the context of the present invention.

Since the granules produced are generally neither stored at elevated temperatures nor used later at these elevated temperatures, the cooling of the mixture leads to the precipitation of the proportion of solute from the supersaturated solution which exceeds the saturation limit at 20 ° C. in the solution was included. The supersaturated solution can cool down into a saturated solution and a soil split up. However, it is also possible that recrystallization and hydration phenomena cause the supersaturated solution to solidify upon cooling to a solid. This is the case, for example, when certain hydrated salts dissolve in their crystal water when heated. When cooling, supersaturated solutions are often formed here, which solidify through mechanical action or the addition of germs to a solid - the salt containing water of crystallization as the state that is thermodynamically stable at room temperature. This phenomenon is known, for example, of sodium thiosulfate pentahydrate and sodium acetate trihydrate, with the latter salt containing hydrate in the form of the supersaturated solution being particularly advantageously used in the process according to the invention. Special detergent and cleaning agent ingredients, such as phosphonates, also show this phenomenon and, in the form of solutions, are ideal as granulation aids.

Particularly preferred granulation processes are therefore characterized in that the supersaturated solution used as the granulation aid solidifies to a solid at room temperature. It is preferred here that the previously supersaturated solution, after solidification to a solid by heating to the temperature at which the supersaturated solution was formed, cannot be converted back into a supersaturated solution.

The supersaturated solution used as granulation aid can - as mentioned above - be obtained in several ways and then added to the moving solid bed. A simple way is, for example, that the supersaturated solution used as a granulation aid is prepared by dissolving the solute in heated solvent. If higher amounts of the dissolved substance are dissolved in this way in the heated solvent than would dissolve at 20 ° C., then a solution is supersaturated within the meaning of the present invention, which is either hot (see above) or cooled and in the metastable state in the Mixer can be given.

It is also possible to dehydrate salts containing hydrate water by "dry" heating and to dissolve them in your own water of crystallization (see above). This is also a method of producing supersaturated solutions that can be used in the context of the present invention. Another way is to add a gas or another liquid or solution to a non-supersaturated solution so that the solute reacts in the solution to a poorly soluble substance or dissolves poorly in the mixture of solvents. Combining two solutions, each containing two substances that react with each other to form a poorly soluble substance, is also a method for producing supersaturated solutions, as long as the poorly soluble substance does not immediately fail. Granulation processes which are likewise preferred in the context of the present invention are characterized in that the supersaturated solution used as granulation aid is prepared by combining two or more solutions. Examples of such ways to make supersaturated solutions are discussed in detail below.

The granulation is carried out by adding the granulation liquid (granulation aid) to a moving solid bed. The weight ratio between supersaturated solution and solid bed is preferably in the range from 5: 1 to 1: 100, preferably from 2: 1 to 1:50 and in particular from 1: 1 to 1:10.

As already mentioned above, the method according to the invention is particularly suitable for the production of detergents and cleaning agents. Granulation processes in which the moving solid bed contains ingredients of detergents and cleaning agents, in particular from the groups of surfactants, builders, bleaching agents, bleach activators and mixtures thereof, are therefore preferred according to the invention. The ingredients mentioned are described below.

The surface-active substances come from the group of anionic, nonionic, zwitterionic or cationic surfactants, anionic surfactants being clearly preferred for economic reasons and because of their range of services.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are C _9-13 - Alkyl benzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates, as they are ₁₂ _ ₁₈ -Monoolefmen with terminal or internal double bond, for example, from C by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products . Also suitable are alkanesulfonates, which are obtained from C ₁₂ _ ₁₈ alkanes, for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become. Preferred sulfated fatty acid glycerol esters are the sulfate products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half-esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C ₁₀ -C ₂₀ -Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical which is produced on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. In addition, 2,3-alkyl sulfates, which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants. The sulfuric acid monoesters of the straight-chain or branched C ₇ ethoxylated with 1 to 6 mol of ethylene oxide. ₂ , alcohols, such as 2-methyl-branched C ₉ . _n alcohols containing on average 3.5 mol ethylene oxide (EO) or C ₁₂ _ ₁₈ fatty alcohols with 1 to 4 EO, are also suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8.18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants, including the soaps, can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol Holrest may be linearly branched or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, such as are usually present in oxo alcohol residues. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. Preferred ethoxylated alcohols include, for example, C ₁₂ _ _ι4 alcohols with 3 EO or 4 EO, C ₉ "-. Alcohol with 7 EO, _{C13. 15} - alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ . _lg - alcohols with 3 EO, 5 EO or 7 EO and mixtures _thereof , such as mixtures of C _12.14 - alcohol with 3 EO and C ₁₂ _ _{] 8} alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Alkypolyglycosides that can be used satisfy the general formula RO (G) _z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is Is a symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular the others between 1.1 and 1.4. Linear alkyl polyglucosides, ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),

R ^J

R-CO-N- [Z] (I)

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

R ^Ϊ -OR ²

R-CO-N- [Z] (II) in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C _M alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this rest.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

The surfactants described above can be used as pure substances, but also in the form of mixtures or compounds in the process according to the invention. It is also possible, for example, not to introduce nonionic surfactants in the solid bed, but to add them to the supersaturated solutions, before this solution or subsequently as a further granulation aid on the moving solid bed.

Regardless of whether anionic or nonionic surfactants or mixtures from these classes of surfactants and, if appropriate, amphoteric or cationic surfactants are used, methods according to the invention are preferred in which the granules produced are 5 to 60% by weight, preferably 10 to 50% by weight and in particular 15 to 40 wt .-% surfactants, each based on the surfactant granules, contains.

In addition to washing substances, builders are the most important ingredients of detergents and ^"cleaning products. In the granules, but also as part of the solid All builders commonly used in detergents and cleaning agents can be contained in the bed, in particular zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} Η ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na ^ i ^ 'yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.

Amorphous sodium silicates with a NajO: SiO ₂ module of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, which are delayed in dissolution, can also be used and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term "amoφh" is also understood to mean "roentgenamoφh". This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be integrated in such a way that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water have serge glasses are described for example in German patent application DE-A-44 00 024. Particularly preferred are compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray silicates.

If desired, in addition to the amount of zeolite of the P and / or X type introduced by the surfactant granules, further zeolite can be incoφorated into the premix by adding zeolite as a treatment component. The finely crystalline, synthetic and bound water-containing zeolite used is preferably a type A, P, X or Y zeolite. However, zeolite X and mixtures of A, X and / or P are also suitable. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these this. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

The granules produced according to the invention can also contain, as additional cobuilders and graying inhibitors, 0.5 to 5% by weight, preferably 1 to 3% by weight, of a polycarboxylate polymer which contains (meth) acrylate and / or maleate units. These anionic polymers can be used in their acid form or in the partially or completely neutralized salt form. Preferred polymers are homo- and copo- polymers of acrylic acid. Polyacrylates, acrylic acid / maleic acid copolymers and acrylic phosphinates are particularly preferred. Polyacrylates are, for example, under the names Versicol ^® E5, Versicol ^® E7 and Versicol ^® E9 (trademark of the Allied Colloids), Narlex ^® LD 30 and Narlex ^® LD 34 (trademark of the national adhesives), Acrysol ^® LMW-10, Acrysol ^® LMW-20, Acrysol ^® LMW-45 and Acrysol ^® Al-N (trademark of Rohm & Haas) as well as Sokalan ^® PA-20, Sokalan ^® PA-40, Sokalan ^® PA-70 and Sokalan ^® PA-110 (trademark of BASF) commercially available. Ethylene / maleic acid copolymers are sold under the name EMA ^® (trademark of Monsanto), methyl vinyl ether / maleic acid copolymers under the name Gantrez ^® AN 119 (trademark of GAF Coφ.) And acrylic acid / maleic acid copolymers under the name Sokalan ^® CP5 and Sokalan ^® CP7 (trademark of BASF). Acrylic phosphinates are available as DKW ^® (trademark of National Adhesives) and Belperse ^® types (trademark of Ciba-Geigy). In combination with the polymers mentioned or as the sole graying inhibitor, it is also possible to use graft copolymers which are obtained by grafting polyalkylene oxides with molecular weights between 2000 and 100,000 with vinyl acetate. The acetate groups can optionally be saponified up to 15%. Polymers of this type, as EP-A-0219048 (BASF) are described in European patent application, under the name Sokalan ^® HP22 (trademark of BASF).

After the granulation, the granules can be "powdered" with finely divided surface treatment agents. This can be advantageous for the nature and physical properties of the granules. Finely divided powdering agents are well known in the art, mostly zeolites, silicates or other inorganic salts being used. However, the granules are preferably “powdered” with finely divided zeolite, zeolites of the faujasite type being preferred. In the context of the present invention, the term “faujasite-type zeolite” denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4 (see Donald W. Breck: “Zeolite Molecular Sieves”, John Wiley & Sons, New York) , London, Sydney, Toronto, 1974, page 92). In addition to the zeolite X, zeolite Y and faujasite and mixtures of these compounds can also be used, the pure zeolite X being preferred. Mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites, which do not necessarily have to belong to the zeolite structural group 4, can also be used as powdering agents, it being advantageous if at least 50% by weight of the powder means consist of a zeolite of the faujasite type.

In addition to the constituents mentioned, surfactant and builder, or in their place in the process according to the invention, the granules can additionally contain one or more substances from the group of bleaching agents, bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils , Anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. If cleaning or bleaching agent granules for machine dishwashing are produced, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkyl, but also peroxy-α-naphthoic acid and magnesium monopeφhthalat, (b) the aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [Phthaloimi- noperoxyhexansäure (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, diperamic acid, diperoxydalsacyryl acid, Decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Chlorine or bromine-releasing substances can also be used as bleaching agents in granules for machine dishwashing. Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid,

Dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium are considered. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

In order to achieve an improved bleaching effect when washing or cleaning at temperatures of 60 ° C. and below, bleach activators can be incorporated into the granules. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are polyacylated alkylenediamines, especially tetraacetylethylene diamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triac 5-diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated into the granules. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N- containing tripod ligands and Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest. Peroxidases or oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules in the granules produced according to the invention can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

In addition, the granules can also contain components which have a positive influence on the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear if a textile is contaminated which has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component. The preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred. As optical brighteners, the granules can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-moφholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the Moφholino- Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.

Colorants and fragrances are added to the detergent and cleaning agent granules produced in accordance with the invention in order to improve the aesthetic impression of the products and to provide the consumer with a visually and sensorially "typical and unmistakable" product in addition to the softness performance. Individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutylate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl benzyl propylateionate, propylateionate. The ethers include, for example, benzylethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones, for example, the jonones, oc-isomethylionone and methyl cedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and teineol, the hydrocarbons mainly include the teenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linseed oil denflower oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The dye content of the detergent and cleaning agent granules produced according to the invention is usually less than 0.01% by weight, while fragrances can make up up to 2% by weight of the total formulation.

The fragrances can be incorporated directly into the agents produced according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.

In order to improve the aesthetic impression of the agents produced according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which does not pose any difficulty to the person skilled in the art, have a high storage stability and are insensitive to the other ingredients of the compositions and to light, and have no pronounced substantivity to textile fibers, in order not to dye them.

As described above, it is preferred that the fixed bed moving in the mixer contains ingredients of detergents and cleaning agents in order to produce detergent and cleaning agent granules. It is further preferred that the supersaturated solution used as the granulation aid is a solution of one or more ingredients of washing and cleaning agents.

In particular, those ingredients of detergents and cleaning agents that are usually used in the form of "normal" solutions as granulation aids are particularly suitable. It is particularly preferred that the supersaturated solution is a supersaturated aqueous solution of one or more washing and cleaning agent ingredients from the groups of the complexing agents, pH adjusting agents or solubility improvers. Complexing agents are substances that are able to complex the hardness agents in the water and thus prevent fiber incrustations and deposits on machine parts. Prominent examples of such compounds are, for example, ethylenediaminetetraacetic acid and its salts, nitrilotriacetic acid and its salts, hydroxyvcarboxylic acids and hydroxycarboxylic acid salts, in particular citric acid and citrates, and also the phosphonates, among which the hydroxyethane-l, l-diphosphonic acid and its tetrasodium salt occupy an outstanding position.

The pH adjusting agents mentioned have the task of increasing or decreasing the pH of the wash liquor depending on the desired application. All alkalizing agents or acidifying agents known to the person skilled in the art, for example inorganic and organic acids, acidic salts such as hydrogen sulfates or alkalis such as hydroxides, amines or the like, can be used here. be used.

Solubility improvers are used to improve the solubility of the granules produced according to the invention. This group particularly includes readily soluble compounds and salts, such as sugar and sugar derivatives, as well as countless carbonates, chlorides, sulfates, acetates, citrates, maleates, etc.

Preferred granulation processes are characterized in that the supersaturated aqueous solution by combining an aqueous solution of one or more acidic ingredients of detergents and cleaning agents, preferably from the group of surfactant acids, builder acids and complexing agents, and an aqueous alkali solution, preferably an aqueous alkali hydroxide solution, in particular an aqueous sodium hydroxide solution.

Among the representatives of the compound classes mentioned already described above, the phosphonates in particular have an outstanding position within the scope of the present invention. In preferred granulation processes, therefore, the supersaturated aqueous solution is obtained by combining an aqueous phosphonic acid solution with concentration NEN above 45 wt .-%, preferably above 50 wt .-% and in particular above 55 wt .-%, each based on the phosphonic acid solution and an aqueous sodium hydroxide solution with concentrations above 35 wt .-%, preferably above 40 wt .-% and in particular above 45% by weight, based in each case on the sodium hydroxide solution.

The granulation process described above is outstandingly suitable for the production of granules and is not restricted to detergents and cleaning agents, the latter being a preferred area of application. It can be easily carried out in a wide variety of granulation systems. In a suitable mixing and granulating device, for example in corresponding systems of the type of an Eirich mixer, a Lödige mixer, for example a ploughshare mixer from the Lödige company, or a mixer from the Schugi company, at peripheral speeds of the mixing elements, preferably between 2 and 7 m / s (ploughshare mixer) or 3 to 50 m / s (Eirich, Schugi), in particular between 5 and 20 m / s, a solid bed and subsequently granulated with the addition of the supersaturated solution. At the same time, a predetermined grain size of the granules can be set in a manner known per se. The granulation and mixing process requires only a very short period of time, for example about 0.5 to 10 minutes, in particular about 0.5 to 5 minutes (Eirich mixer, Lödige mixer) to homogenize the mixture with formation of the free-flowing granulate. In the Schugi mixer, on the other hand, a residence time of 0.5 to 10 seconds is usually sufficient to obtain a free-flowing granulate. Suitable for carrying out this process step mixers include for example Eirich ^® mixer Series R or RV (trademark of Maschinenfabrik Gustav Eirich, Hardheim), the Schugi ^® Flexomix, the Fukae ^® FS-G mixers (trade marks of Fukae Powtech, Kogyo Co. , Japan), the Lödige ^® FM, KM and CB mixers (trademarks of Lödige Maschinenbau GmbH, Paderborn) or the Drais ^® series T or KT (trademarks of Drais-Werke GmbH, Mannheim). It is also possible according to the invention to connect several of the mixers mentioned above in series. The following combinations of consecutive mixers are particularly useful here:

- Lödige CB / Lödige KM

- Lödige KM / Schugi Flexomix

Schugi Flexomix / Lödige KM / Schugi Flexomix

Schugi Flexomix / Lödige CB

Lödige CB / Lödige KM / Schugi Flexomix

If several mixers are combined, the supersaturated solution can basically be added to each mixer. In addition to the supersaturated solution, further liquid components can also be added for the granulation. Surfactant pastes, polymer solutions, surfactants and water glass solutions are particularly suitable here. It has proven to be particularly advantageous if the granulate is powdered at the end of the granulation with a finely divided component which has an oil absorption capacity of at least 20 g per 100 g. The oil absorption capacity is a physical property of a substance that can be determined using standardized methods. For example, the British standard methods BS1795 and BS3483: Part B7: 1982 exist, both of which refer to the ISO 787/5 standard. In the test methods, a balanced sample of the substance in question is placed on a plate and refined flaxseed oil (density: 0.93) ^{"3" is added} dropwise from a burette. After each addition, the powder is intensively mixed with the oil using a spatula, the addition of oil is continued until a paste of smooth consistency is reached. This paste should flow or flow without crumbling. The oil absorption capacity is now the amount of the added oil, based on 100 g of absorption agent, and is expressed in ml / 100 g or g / lOOg, whereby conversions about the density of linseed oil are possible without problems Examples of suitable substances are silicates, aluminum silicates and silicas. The universally applicable granulation method according to the invention has so far not been described in the prior art. The use of supersaturated solutions as granulation aids and the use of supersaturated aqueous solutions as granulation aids are also new and therefore a further subject of the present invention.

According to a preferred application, the use of supersaturated solutions as granulation aids in the production of detergents and cleaning agents and the use of supersaturated aqueous solutions as granulation aids in the production of detergents and cleaning agents are further objects of the present invention.

The statements made for the method according to the invention apply mutatis mutandis to all uses according to the invention. In particular, uses are preferred which are characterized in that the supersaturated solutions, when added to the moving solid bed, have a temperature between 35 and 120 ° C, preferably between 40 and 110 ° C, particularly preferably between 45 and 90 ° C and in particular between 50 and 80 ° C.

It is preferred in the context of the present invention if the granules produced according to the invention have bulk densities above 400 g / 1, preferably above 500 g / 1 and in particular above 600 g / 1. The granules obtained by the process described above can, for example, also be incoφorated into the premix of an extrusion, a pelletizing or a compacting. Both the granules produced by the process according to the invention and the extrudates, pellets or compactates produced using premixes which contain the granules prepared according to the invention can - if appropriate after being mixed with other constituents - be pressed to give shaped articles, in particular tablets.

The following examples further illustrate the subject matter of the invention without restricting it: Examples:

1. Preparation of a supersaturated solution:

60% by weight hydroxyethane-l, l-diphosphonic acid and 50% by weight sodium hydroxide solution were combined in a weight ratio of 51.7 to 48.3. The neutralization mixture warmed from room temperature (individual components) to 51 ° C. This supersaturated solution crystallizes on cooling to room temperature to a solid which does not revert to a supersaturated solution even when heated to 70 ° C.

2. Granulation:

2.5 kg of crystalline TAED were placed in a 20-liter Lödige ploughshare mixer and, with the chopper switched on, granulated by adding 0.7 kg of the not yet crystallized supersaturated solution, the mixing time being 5 minutes. After the granulation, the product was spread out on a plate and, after cooling (two hours' storage), sieved between 600 and 1600 μm. The proportion <600 μm was 5% by weight, the proportion> 1600 μm was 75% by weight.

If the granulate discharged from the mixer is not dried by spreading out on a plate, but in a fluidized bed apparatus (Glatt company) for 30 minutes at 25 ° C supply air temperature, the proportion <600 μm after sieving is 44% by weight Proportion> 1600 μm at 30% by weight.

Claims

Claims: 1. Granulation process in which a liquid granulation aid is placed on a moving solid bed, characterized in that a supersaturated solution is used as the granulation aid. 2. Granulation process according to claim 1, characterized in that an oversaturated aqueous solution is used as the granulation aid. 3. Granulation process according to one of claims 1 or 2, characterized in that the supersaturated solution used as the granulation aid when added to the moving solid bed has a temperature between 35 and 120 ° C, preferably between 40 and 110 ° C, particularly preferably between 45 and 90 ° C and in particular between 50 and 80 ° C. 4. Granulation process according to one of claims 1 to 3, characterized in that the supersaturated solution used as granulation aid solidifies to a solid at room temperature. 5. Granulation process according to one of claims 1 to 4, characterized in that the supersaturated solution used as a granulation aid is prepared by dissolving the solute in heated solvent. 6. Granulation process according to one of claims 1 to 4, characterized in that the supersaturated solution used as a granulation aid is prepared by combining two or more solutions. 7. Granulation process according to one of claims 1 to 6, characterized in that the weight ratio between supersaturated solution and solid bed in the range from 5: 1 to 1: 100, preferably from 2: 1 to 1:50 and in particular from 1: 1 to 1 : 10, lies. 8. Granulation process according to one of claims 1 to 7, characterized in that the moving solid bed contains ingredients of detergents and cleaning agents, in particular from the groups of surfactants, builders, bleaching agents, bleach activators and mixtures thereof. 9. Granulation process according to one of claims 1 to 8, characterized in that the supersaturated solution used as a granulation aid is a solution of one or more ingredients of washing and cleaning agents. 10. Granulation process according to one of claims 1 to 9, characterized in that the supersaturated solution is a supersaturated aqueous solution of one or more washing and cleaning agent ingredients from the groups of complexing agents, pH adjusting agents or solubility improvers. 11. Granulation process according to claim 10, characterized in that the supersaturated aqueous solution by combining an aqueous solution of one or more acidic ingredients of detergents and cleaning agents, preferably from the group of surfactant acids, builder acids and complexing agents, and an aqueous alkali solution, preferably an aqueous alkali hydroxide solution, especially an aqueous sodium hydroxide solution. 12. Granulation process according to claim 11, characterized in that the supersaturated aqueous solution by combining an aqueous phosphonic acid solution with concentrations above 45 wt .-%, preferably above 50 wt .-% and in particular above 55 wt .-%, each based on the phosphonic acid solution and an aqueous sodium hydroxide solution with concentrations above 35% by weight, preferably above 40% by weight and in particular above 45% by weight, in each case based on the sodium hydroxide solution. 13. Use of supersaturated solutions as a granulation aid. 14. Use of supersaturated aqueous solutions as granulation aids. 15. Use of supersaturated solutions as granulation aids in the production of washing and cleaning agents. 16. Use of supersaturated aqueous solutions as granulation aids in the production of washing and cleaning agents. 17. Use according to any one of claims 13 to 16, characterized in that the supersaturated solutions, when added to the moving solid bed, a temperature between 35 and 120 ° C, preferably between 40 and 110 ° C, particularly preferably between 45 and 90 ° C and in particular between 50 and 80 ° C.