DE4201877A1 - Prepn. of granulate contg. carbonate with high bulk wt. - Google Patents

Abstract

In prepn. of a carbonate-contg. granulate with bulk wt. at least 400 g/l, carbonate is granulated in admixture with a liq. which is a liq. or paste under normal pressure and at 20-40 deg.C; granulation is carried out at the same time as drying of the granulate. The granulate contains at least 40 (60-95) wt.% of carbonate, has bulk wt. of 500-1000 g/l (550-850 g/l), contains no particles below 50 microns (below 100 microns), and has a lower rate of dissolution in water than the initial carbonate material. A washing, rinsing or cleaning compsn., with bulk wt. 450-1000 g/l (550-900 g/l) contains a zeolite and/or crystalline laminar silicate, and the carbonate-contg. granulate. The granulate is added to the wash liquor separately from the washing compsn. and at the same time or 1-5 minutes later. The carbonate is pref. Na2CO3, pref. granular or crystallised with bulk wt. 500-1200 g/l (800-100 g/l), with at least 85% of particles of dia. 200-2000 microns and not more than 5% with dia. below 200 microns. The liq. pref. contains components of washing and cleaning compsns., e.g. tensides, silicates, polymeric polycarboxylates, antifoams and/or perfumes, and may be a mixt. of surfactants(s) and non-surfactant liquids contg. (in)organic components, with the surfactant(s) forming 20-75 wt.% of the liq. The liq. may be in 2 parts, of the same or different compsn., liq. or pasty at 20-40 deg.C and normal pressure, pref. 2 portions contg. differing surfactants. Alternatively the liq. may be an aq. silicate soln., pref. 10-60%, and esp. a 30-50% soln. of an alkali silicate with molar ratio of M2O:SiO2 of 1:1.9-4.5 (1:2.3-3.5), or the liq. may be an aq. soln. of a polymeric polycarboxylate. M = Na (pref.) or K.

Description

The invention relates to a method for producing carbonate-containing Granules with high bulk density, a washing, rinsing or cleaning agent tel, which contains these carbonate-containing granules, as well as a washing, Flushing or cleaning process in which a carbonate-containing granulate is used.

A process for producing granules containing carbonate with a Bulk density of at least 400 g / l is already from the German Pa tent registration 23 22 123 known. After that, free-flowing and Silicated sodium carbonate granules with a bulk density of 400 up to 800 g / l by preparing an aqueous sodium silicate solution, Ver mix this solution with anhydrous, fine sodium carbonate with a Grain size below 200 µm, maintaining a mixing temperature that is 51 ° C should not exceed sieving and drying. The granules have a content of 45 to 70 wt .-% sodium carbonate. A disadvantage This method consists in the fact that only a special, very finely divided Sodium carbonate can be used.

The object of the invention was to provide a method for manufacturing to provide heavy and free-flowing granules containing carbonate which the grain size distribution of the starting materials does not have a critical ver represents driving parameters.

The invention accordingly relates to a process for the production carbonate-containing granules with a bulk density of at least 400 g / l, wherein carbonate with the addition of a liquid component, which under Normal pressure at temperatures between 20 and 40 ° C in liquid to  pasty form, is granulated and the granulation in one Device takes place in which a granulation if desired simultaneous drying of the resulting granules can.

The carbonates used in the context of the invention are preferably Al potassium carbonates and in particular commercially available sodium carbonates and Ka lium carbonates. Examples of these commercially available alkali carbonates are both light and compacted, powdered or granular Alkali carbonates with a bulk density between 300 and 1200 g / l as well Roll-compacted alkali carbonates in Schülpen form. Such alkali car Bonates can be found, for example, at the companies Matthes & Weber, Federal Republic Germany, Sodawerk Bernburg GmbH, Federal Republic of Germany, or Deutsche Solvay-Werke GmbH can be obtained. Preferably a sodium carbonate, especially a water-containing or anhydrous granulated or crystallized sodium carbonate with a bulk density between 500 and 1200 g / l, with particular advantage between 800 and 1000 g / l sets, the latter at least 85 wt .-% of particles with a Diameter between 200 and 2000 microns and a maximum of 5 wt .-% of particles with a diameter smaller than 200 microns.

The liquid component used under normal pressure at temperatures between 20 and 40 ° C in liquid to pasty form preferably ingredients of washing and cleaning agents such as surfactants, inorganic salts and in particular silicates, polymeric polycarboxylates, Foam inhibitors, perfume oils or mixtures of these.

Thus, a preferably used liquid component contains a mixture of one or more surfactants and a non-surfactant liquid, which has components of an organic and / or inorganic nature. Anionic surfactants which can be used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C ₉ -C ₁₃ alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as those obtained from C ₁₂ -C ₁₈ monoolefins with an end or internal double bond Sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates which are obtainable from C ₁₂ -C ₁₈ alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. In particular, esters of α-sulfofatty acids (ester sulfonates) which are produced by α-sulfonation of the methyl esters of fatty acids of plant and / or animal origin with 8 to 20 C atoms in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts by the process according to the invention Example, the α-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids, as well as the α-sulfofatty acids or their di-salts obtainable by the ester cleavage. The preparation of mixtures of the mono-salts and di-salts with other surfactants, for example with alkylbenzenesulfonates, is also preferred.

Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, ie from fatty alcohols, e.g. B. from coconut fatty alcohols, tallow fatty alcohols, oleyl alcohols, lauryl, myristyl, cetyl or stearyl alcohol, or the C ₁₀ -C ₂₀ oxoal alcohols, and those secondary alcohols of this chain length. The sulfuric acid monoesters of alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ alcohols with an average of 3.5 moles of ethylene oxide, are suitable. Sulfated fatty acid monoglycerides are also suitable. In particular, however, the production of surfactant granules containing C ₁₂ -C ₁₈ alkyl sulfates (FAS) or C ₁₆ -C ₁₈ alkyl sulfates (TAS) alone or together with other surfactants is preferred.

Other anionic surfactants which can be prepared in granular form by the process according to the invention include soaps made from natural or synthetic, preferably saturated or ethylenically unsaturated, fatty acids. Are particularly suitable from natural Fettäu ren, for. B. coconut, palm kernel or tallow fatty acid derived soap mixtures. Preferred are those which are composed of 50 to 100% of saturated C ₁₂ -C ₁₈ fatty acid soaps and 0 to 50% of oleic acid soaps. In particular, granules are produced by the process according to the invention which contain soap mixed with other surfactants. The anionic surfactants can be used in the form of their sodium, potassium, calcium and ammonium salts and as water-soluble salts of organic bases, such as mono-, di- or triethanolamine, with the sodium and potassium salts being preferred. They are preferably used in the form of aqueous preparations, in particular in the form of about 30 to 60% by weight aqueous preparations in which the anionic surfactants are obtained by neutralizing the corresponding acids in their preparation.

It is also possible that the anionic surfactants are wholly or partly in their Acid form can be used.

The preferred nonionic surfactants are liquid ethoxylated, especially primary alcohols with preferably 9 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide per mole of alcohol, in which the alcohol radical can be linear or methyl-branched in the 2-position, or linear and may contain methyl branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, linear residues of alcohols of native origin with 12 to 18 carbon atoms are preferred, such as, for example, coconut oil, tallow oil or oley alcohol. 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 restricted homolog distribution (narrow range ethoxylathes, NRE). In particular, alcohol ethoxylates are preferred which have an average of 2 to 8 ethylene oxide groups. The preferred ethoxylated alcohols, for example C ₉ -C ₁₁ -oxo alcohol with 7 EO, C ₁₃ -C 1 ₅ include oxo alcohol with 3 EO, 5 EO or 7 EO and, more particularly C ₁₂ -C ₁₄ alcohol with 3 EO or 4 EO, C ₁₂ -C ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 EO and C ₁₂ -C ₁₈ alcohol with 5 EO.

Furthermore, nonionic surfactants which can be used are alkyl glycosides of the general formula RO- (G) _x , in which R is a primary straight-chain or aliphatic radical with 8 to 22, preferably 12 to 18, C-atoms, methyl-branched, G is a symbol which stands for a glycose unit with 5 or 6 carbon atoms and the degree of oligomerization x is between 1 and 10, preferably between 1 and 2 and in particular is significantly less than 1.4. In particular, it is preferred that the nonionic surfactants are used in their acid form together with anionic surfactants, for example alkylbenzenesulfonate and / or fatty alkyl sulfate or together with the corresponding anionic surfactants.

The proportion of the surfactants in the liquid component is preferably 20 up to 75% by weight and in particular 35 to 70% by weight.

The non-surfactant liquid that contains one or more components can contain, has a boiling point or a normal pressure Boiling range preferably below 250 ° C and especially below 200 ° C. The non-surfactant liquid has a particular advantage parts that boil between 60 and 180 ° C at normal pressure. As given if any organic component of the non-surfactant liquid speed are preferably mono- and / or polyfunctional alcohols for example methanol, ethanol, propanol, isopropanol, butanol, secondary and tertiary butanol, pentanol, ethylene glycol, 1,2 propanediol, glycerin or mixtures of these are used. The proportion is preferably used as a non-surfactant liquid mono- and / or polyfunctional alcohols 0.5 to 10 wt .-%, based on the liquid com component.

In particular, however, it is preferred as the inorganic component of the non-surfactant liquid water, possibly together with orga African components such as ethanol, 1,2-propanediol or glycerin Zen. The proportion of water is preferably 25 to 80% by weight, based on the liquid component. The percentage of non-surfactant Total liquid is preferably 30 to 70 wt .-% and in particular the other 45 to 60 wt .-%, each based on the liquid component.

In a further embodiment, the invention relates to a process for producing carbonate-containing granules, an aqueous silicate solution, preferably a 10 to 60% by weight alkali silicate solution, being used as the liquid component. In particular, it is preferred to use a 30 to 50% by weight akalisilicate solution as the liquid component, the molar ratio M ₂ O to SiO _{2 being} 1: 1.9 to 1: 4.5 and in particular 1: 2.3 is up to 1: 3.5 and M stands for sodium or potassium. In particular, the use of sodium silicate is preferred.

In a further preferred embodiment of the invention are as Liquid component liquid foam inhibitors such as paraffin oils and waxes, which, for example, have a melting point between 0 ° C and 90 ° C, and silicone oils, for example VP 1132 (R) (commercial product from Wak ker, Federal Republic of Germany).

In a further preferred embodiment, the invention provides that aqueous polymeric polycarboxylate solutions used as the liquid component will. The polymeric polycarboxylates are preferably water-soluble Lichen salts of homopolymeric and / or copolymeric carboxylic acids such as Polyacrylic acid, polymethacrylic acid and polymaleic acid, copolymers of Acrylic acid or methacrylic acid with maleic acid or vinyl ethers such as Vinyl methyl ether or vinyl ethyl ether, further with vinyl esters such as Vinyl acetate or vinyl propionate, acrylamide, methacrylamide and ethylene, Propylene or styrene used. In particular, the sodium salts are these homopolymeric and / or copolymeric polycarboxylic acids preferred. In such copolymeric acids in which one of the components has no acid function has their share in the interest of sufficient water solubility not more than 50 mol%, preferably less than 30 mol%. Copolymers of acrylic acid or Proven methacrylic acid with maleic acid. In particular Copolymers preferred, the 50 to 80 wt .-% acrylic acid and 50 to 10 % By weight of maleic acid. The relative molecular mass of the homo- or copolymeric polycarboxylates is generally from 2000 to 15,000 preferably 5,000 to 100,000. The polycarboxylates are preferably in the form 30 to 50 wt .-%, in particular 35 to 45 wt .-% aqueous solutions used.

It is also possible that carbonate together with other temperature-stable solids, which preferably contain ingredients from washing and cleaning agents are introduced into the process. As before attracted other solids come, for example, finely crystalline, synthetic table and bound water containing zeolite, especially zeolite  NaA in detergent quality, crystalline layered silicates, in particular crystalline sodium disilicate, bicarbonate, sulfate or mixtures of this into consideration.

According to the invention, the carbon-containing granules can be produced in all devices in which granulation can be carried out with simultaneous drying of the resulting granules, ie evaporation of inorganic or organic solvents. Examples of this are heatable mixers and granulators, in particular granules of the Turbo dryer ^{(R) type} (device from Vomm, Italy). In a preferred embodiment, however, the invention provides that the combination of these two process steps is carried out in a batch or continuous fluidized bed. It is particularly preferred to carry out the process continuously in the fluidized bed. The carbonate and any other solids that are present can be dusted pneumatically via blow lines and the liquid component can be introduced into the fluidized bed at the same time or in succession via a nozzle or - if the liquid component has been divided into several portions - via several nozzles. It is also possible to add individual components of the liquid component simultaneously, but separately to the rest of the liquid component. The nozzle or the nozzles and the direction of spraying of the products to be sprayed can be arranged as long as a substantially uniform distribution of the liquid components in the fluidized bed is achieved. Preferred fluidized bed apparatuses have base plates with dimensions of at least 0.4 m. In particular, fluidized bed apparatuses are preferred which have a base plate with a diameter between 0.4 and 5 m, for example 1.2 m or 2.5 m. However, fluidized bed apparatuses are also suitable which have a base plate with a larger diameter than 5 m. A perforated plate or a Conidur plate (commercial product from Hein & Lehmann, Federal Republic of Germany) is preferably used as the base plate. The method according to the invention is preferably carried out at fluidizing air speeds between 1 and 8 m / s and in particular between 1.5 and 5.5 m / s. The granules are advantageously discharged from the fluidized bed via a size classification of the granules. This classification can take place, for example, by means of a sieving device or by means of an opposed air flow (classifier air) which is regulated in such a way that only particles of a certain particle size are removed from the fluidized bed and smaller particles are retained in the fluidized bed. In a preferred embodiment, the outflowing air is composed of the heated or unheated classifier air and the heated soil air. The floor air temperature is preferably between 80 and 400 ° C, in particular between 90 and 350 ° C. The fluidized air cools down due to heat losses and the heat of vaporization of the non-surfactant components of the liquid component. In a particularly preferred embodiment, the temperature of the vortex air is about 5 cm above the base plate 60 to 120 ° C, preferably 65 to 90 ° C and in particular 70 to 85 ° C. The air outlet temperature is preferably between 50 and 120 ° C, in particular below 100 ° C and with particular advantage between 60 and 85 ° C. In the process preferably carried out in the fluidized bed, it is necessary that a starting mass is present at the beginning of the process, which serves as an initial carrier for the sprayed-in liquid component. Ingredients of detergents and cleaning agents are particularly suitable as starting mass, especially those which can also be used as solids in the process according to the invention and which have a grain size distribution which corresponds approximately to the grain size distribution of the finished granules. In particular, however, it is preferred to use as the starting mass carbonate-containing granules which have already been obtained in a previous process.

The liquid, non-surfactant substances evaporate in the fluidized bed Components of the liquid component are preferably partially or completely. Dried up to dried germs are formed, which with additional amounts introduced solids and liquid components coated, granulated and again dried at the same time.

In a further embodiment of the invention, the carbonate salts claimed gene granules that according to the inventive method are adjustable. Here are granules with any carbonate content can be produced from about 1% by weight to 98% by weight and on any of the desired Values adjustable. In the context of this invention, however, granules  preferred, which has a carbonate content of at least 40 wt .-% and esp have in particular of at least 50 wt .-%. With particular advantage Granules produced, the 60 to 98 wt .-%, preferably 70 to 95 wt .-% Carbonate, especially alkali carbonate, contain.

The carbonate-containing produced by the process according to the invention Granules preferably have a bulk density between 500 and 1000 g / l, in particular between 550 and 850 g / l, and are dust-free, d. H. they preferably contain no particles with a particle size below 50 µm and in particular no particles with a particle size below 100 µm. Otherwise the grain size distribution corresponds to that of carbonate Granules of the usual grain size distribution of a heavy washing and Prior art cleaning agents. In particular they have granules containing carbonate have a grain size distribution with a maximum of 5 % By weight, preferably at most 3% by weight of particles having a diameter above 2.5 mm and a maximum of 5% by weight, with a particular advantage a maximum of 3% by weight Have a diameter below 0.1 mm. The granules are characterized by their flowability and their regular, especially approximated spherical structure.

In general, the rate of dissolution of the granules containing carbonate in water less than the rate of dissolution in the invention Process used carbonate starting materials up to a maximum equal to the Lö speed of those used in the process according to the invention Carbonate raw materials. The dissolution rate of the carbonate Granules can be produced within the specified range by varying the inventory parts of the liquid component and depending on their quantity can be set.

The release of carbonate ions in the washing, rinsing or cleaning fleet can lead to incrustations, which are caused by the formation of sparingly soluble calcium carbonate are caused when the Carbonate ions in the fleet are released faster than those in the What existing free calcium ions can be removed. Although in Washing, rinsing or cleaning processes are now used means that Contain builder substances, the task of which is, among other things,  the formation of calcium carbonate and thus the formation of incrustations counteract ones. To the modern and most important builder substances The aluminosilicates, especially zeolite, belong to modern times Zeolite NaA in detergent quality. A disadvantage of these zeolites is however, in that in washing, rinsing or cleaning processes in which Agents are used that ent both zeolite and alkali carbonate hold out the formation of the poorly soluble calcium carbonate Alkaline carbonate and the hardness of the water takes place faster than that Cation exchange through the builder substance zeolite. Particularly preferred are therefore granules containing carbonate, their rate of dissolution in water compared to the carbonate starting materials is reduced so that the The carbonate ions are no longer released faster than the cat Ion exchange through the builder substance zeolite.

In a particularly preferred embodiment of the invention, the carbonate-containing granules contain 40% by weight to 95% by weight sodium carbonate and 60% by weight to 5% by weight sodium silicate with a molar ratio of Na ₂ O to SiO ₂ of 1: 1 , 9 to 1: 3.5.

In a further preferred embodiment of the invention, the carbonate-containing granules 40% by weight to 98% by weight sodium carbonate and 2 % By weight to 60% by weight of surfactants and / or anionic surfactants in their acid form, preferably alkylbenzenesulfonate, fatty alkyl sulfate, α- Sulfofatty acid methyl ester and / or their corresponding acids, given if in combination with nonionic surfactants.

The carbonate-containing granules produced according to the invention can be separated advice at the same time as adding a washing, rinsing or cleaning agent agent, which is preferably no alkali carbonate or alkali carbonate does not contain in amounts above 2 wt .-%, or staggered, for example about 1 to 5 minutes after adding a wash, rinse or rice detergent, introduced into the washing, rinsing or cleaning liquor will.

However, the carbonate-containing granules produced according to the invention can also in detergents, dishwashing detergents or cleaning agents in any way  be incorporated. The invention is therefore the subject of another preferred embodiment, a detergent, dishwashing or cleaning agent, ins special a modern agent that has a bulk density between 450 and 1000 g / l, preferably between 550 and 900 g / l and zeolite and / or crystalline layered silicates, for example crystalline sodium disilicates, and the carbonate-containing granules produced according to the invention holds.

Examples example 1

In a plant for fluidized bed granulation from Glatt, Federal Republic of Germany, 20 kg of crystallized sodium carbonate (bulk density 1050 g / l, commercial product from Deutsche Solvay Werke GmbH) were initially introduced and with a 45% by weight aqueous sodium silicate solution with a molar ratio of Na ₂ O: SiO ₂ of 1: 2.75. After setting the operating conditions summarized in Table 1 and an operating time of approx. 3 hours, a dust-free granulate with a high carbonate content was obtained.

Examples 2 to 4

A 17.5 or 35% by weight aqueous sodium silicate solution with a molar ratio Na ₂ O: SiO ₂ of 1: 3.3 as in Example 1 was obtained together with compressed calcined soda (bulk density 900 g / l , Commercial product from Matthes und Weber GmbH) granulated and dried at the same time. Dust-free granules with different carbonate contents and different dissolution rates were obtained (Table 1).

Example 5

A liquid component containing 54% by weight tallow fatty alcohol sulfate and 41 % By weight of water (Sulfopon (R) T55, applicant's commercial product) was over sprayed a nozzle into a Glatt granulation drying system and together with sodium carbonate as a solid (bulk density 620 g / l; Commercial product from Matthes & Weber, Federal Republic of Germany) granulated and dried at the same time. A surfactant and carbonate-containing granules used in a previous Approach (under the same process conditions) and in had approximately the same composition as the finished granulate. The procedure General conditions can be found in Table 1. It became a Obtain dust-free and non-sticky granules (see Table 2).

The proportion of granules with a grain size above 2.5 mm was in all Examples below 5% by weight.  

Table 1

Process parameters

Table 2

Characteristics of the products

Example 6 Delayed release of carbonate ions from one Granules according to Example 1

There were 2 g of the sodium carbonate starting material or one corresponding amount of the carbonate-containing granules of Example 1, which Contained 2 g of sodium carbonate in 100 ml of deionized water with stirring dissolved at 20 ° C. After 0.5, 5, 10, 20 and 30 minutes the Attempt to dissolve, the mixture filtered and the filtrate selectively analyzed for carbonate ions (acidification, collection of the resulting Carbon dioxide in dilute sodium hydroxide solution, back titration). The results are summarized in Table 3.

Table 3

Proportions of dissolved sodium carbonate (normalized to the theoretical maximum value)

Claims (18)

1. A process for the production of carbonate-containing granules with a bulk density of at least 400 g / l, characterized in that carbonate is granulated with the addition of a liquid component which is in liquid to pa-soluble form under normal pressure at temperatures between 20 and 40 ° C, wherein the granulation takes place in a device in which granulation, if desired, can be carried out with simultaneous drying of the resulting granules. 2. The method according to claim 1, characterized in that as carbonate a sodium carbonate, preferably granulated or crystallized Sodium carbonate with a bulk density between 500 to 1200 g / l, preferably between 800 and 1000 g / l, the latter at least 85 wt .-% of particles with a diameter between 200 and 2000 microns and a maximum of 5% by weight of particles with a diameter smaller than 200 µm exists, is used. 3. The method according to claim 1 or 2, characterized in that the used liquid component ingredients of washing and cleaning agents, such as surfactants, silicates, polymeric polycarboxylates, Contains foam inhibitors, perfume oils or mixtures of these. 4. The method according to claim 3, characterized in that as a liquid component a mixture of one or more surfactants and one non-surfactant liquid, the components of organic and / or has inorganic nature, is used, the proportion of Surfactants in the liquid component is 20 to 75% by weight. 5. The method according to claim 3, characterized in that an aqueous silicate solution, preferably a 10 to 60 wt .-% silicate solution and in particular a 30 to 50 wt .-% alkali silicate solution is used as the liquid component, the molar ratio M20 to SiO _{2 being} 1: 1.9 to 1: 4.5 and in particular 1: 2.3 to 1: 3.5 and M being sodium or potassium, in particular sodium. 6. The method according to claim 3, characterized in that as a liquid component aqueous polymeric polycarboxylate solutions are used. 7. The method according to any one of claims 1 to 6, characterized in that that carbonate together with temperature-stable solids, preferably with fine crystalline, synthetic and containing bound water Zeolite, crystalline layered silicates, bicarbonate, sulfate or Mi from these, is introduced into the process. 8. The method according to any one of claims 1 to 7, characterized in that the granulation and simultaneous drying of the resulting Granules in a fluidized bed, batchwise or continuously, before preferably continuously. 9. The method according to claim 8, characterized in that the liquid component via a nozzle or - if the liquid component in meh more portions has been divided - simultaneously or one after the other several nozzles are introduced into the fluidized bed. 10. The method according to claim 8 or 9, characterized in that the Vortex air velocity between 1 and 8 m / s, preferably between 1.5 and 5.5 m / s. 11. The method according to any one of claims 8 to 10, characterized in that that the discharge of the granules from the fluidized bed over a size the granules are classified. 12. The method according to any one of claims 8 to 11, characterized in that that the soil air temperature between 80 and 400 ° C, preferably between 90 and 350 ° C, the temperature of the vortex air about 5 cm above the base plate between 60 and 120 ° C, preferably between 65 and 90 ° C and especially between 70 and 85 ° C, and the air outlet temperature between 50 and 120 ° C, preferably below 100 ° C and is in particular between 60 and 85 ° C.   13. Carbonate-containing granules, produced according to one of claims 1 to 12, characterized in that it has a carbonate content of at least 40% by weight, preferably at least 50% by weight and in particular of Has 60 to 95 wt .-%. 14. Carbonate-containing granules according to claim 13, characterized in that that there is a bulk density between 500 and 1000 g / l, preferably between between 550 and 850 g / l. 15. Carbonate-containing granules according to claim 13 or 14, characterized records that there are no particles with a particle size below 50 µm, preferably below 100 µm, contains. 16. Carbonate-containing granules according to one of claims 13 to 15, characterized characterized in that it has a lower dissolving rate in water has as the carbonate starting material. 17. washing, rinsing or cleaning agent, characterized in that it a bulk density between 450 and 1000 g / l, preferably between 550 and 900 g / l, and has zeolite and / or crystalline layered silicates and a carbonate-containing granulate according to any one of claims 13 to 16 contains. 18. Washing, rinsing or cleaning process, with a carbonate Granules according to one of claims 13 to 16 is used, thereby characterized in that the carbonate-containing granules separately and the same early with the addition of a detergent, dishwashing detergent or cleaning agent or about 1 to 5 minutes after the addition of a washing, rinsing or cleaning agent agent introduced into the washing, rinsing or cleaning liquor becomes.