EP1913124A1

EP1913124A1 - Method for the production of bleaching catalyst granules

Info

Publication number: EP1913124A1
Application number: EP06776385A
Authority: EP
Inventors: Georg Borchers; Andreas Schottstedt; Michael Wessling
Original assignee: Clariant Produkte Deutschland GmbH
Current assignee: Clariant Produkte Deutschland GmbH
Priority date: 2005-07-28
Filing date: 2006-07-25
Publication date: 2008-04-23
Anticipated expiration: 2026-07-25
Also published as: BRPI0613853A2; EP1913124B1; DE102005035916A1; WO2007012451A1; DE502006004011D1; JP2009502458A; ES2327448T3; US20090256113A1; MX2008001214A; JP5175726B2

Abstract

The invention relates to a method for the production of bleaching catalyst granules, containing a bleaching catalyst, an acidic polymer, a support material and optionally further adjuncts, characterised in that a fluid bed is formed from the support material in a fluidised bed apparatus, an aqueous solution or dispersion is added to the fluid bed, containing the bleaching catalyst, the acidic polymer, and optionally the further adjuncts which is then granulated and dried. The method is particularly suitable for bleaching catalysts of formula (1), where R, R1, R2, R3 and X have the meanings given in the description.

Description

description

Process for the preparation of bleach catalyst granules

The invention relates to a process for the preparation of granules containing a bleach catalyst and an acidic component, and optionally further additives, wherein granulating an aqueous solution or suspension containing a bleach catalyst and an acidic component in a pneumatically generated fluidized bed and drying at the same time. The Wirbelschichtgranuiate characterized by a very good storage stability, uniform morphology and high abrasion resistance.

The use of bleach catalysts in detergents and cleaning agents enables very efficient stain removal even at low wash temperatures at low use concentrations.

Compounds of the formula (1)

or organometallic complex compounds containing these compounds of the formula (1) as a ligand, are very powerful bleach catalysts. In the formula (1) R is hydrogen, fluorine, chlorine, bromine, hydroxyl, means _{Ci-C4-alkoxy,} -NH-CO-H, -NH-CO-C _r C ₄ alkyl, -NH _2, -NH- C _r C ₄ alkyl, R ¹ and R ² are independently C ₁ -C ₄ alkyl, C ₆ -C ₀ aryl or a group containing a hetero atom, preferably (CH ₂₎ _z -2-pyridyl, where z a number from 1 to 5; R ³ Is hydrogen or C ₄ alkyl and X is C = O or - y- [C (R) 2], where y is a number from 0 to 3 and R is hydrogen, hydroxyl, C _r C ₄ alkoxy or C _r C ₄ alkyl ,

The organometallic complex compounds are represented by Formula 2:

[M _a L _k Xn] Y _m (2)

wherein M is Mn (II), Mn (III), Mn (IV), Mn (V), Cu (I), Cu (II), Cu (III), Fe (II), Fe (III), Fe (IV), Fe (V), Co (I), Co (II), Co (III), Ti (Ii), Ti (II), Ti (IV), V (II), V (III), V (IV), V (V), Mo (II),

Mo (III), Mo (IV), Mo (V), Mo (VI) and W (IV), W (V) and W (VI), preferably Fe (II),

Fe (III), Fe (IV), Fe (V),

L is a ligand according to formula (1), preferably dimethyl-2,4-di- (2-pyridyl) -3-methyl-7- (pyridin-2-ylmethyl) -3,7, diazabicyclo (3.3.1) nonane -9-one-one, 5-dicarboxylate or its protonated form,

X is a singly, doubly or triply charged anion or a neutral molecule that can coordinate with M,

Y is a noncoordinating counterion and a is an integer from 1 to 10 k is an integer from 1 to 10 n is an integer from 0 to 10 m is an integer from 0 to 20.

The preparation of the ligands of the formula (1) and of the metal complexes of the formula (2) is described in WO 02/48301.

The use of these complex compounds in the form of granules in bleach formulations is described in WO 02/066592. The preparation of the granules according to this document takes place in such a way that the

Bleaching catalyst in the form of a dry powder with sodium sulfate and an aqueous solution of a binder, such as an acidic polymer such as Sokalan ^® CP45 is mixed in a high-speed mixer and then the moist granules are dried in a fluidized bed.

On the other hand, if the catalyst is to be formulated from an aqueous solution or suspension, a number of process engineering difficulties may arise.

If one considers the water balance of the system, there is a risk that when adding the catalyst solution, an excessively large amount of water enters the mixer and leads to clumping due to overhydration. In particular, this is to be expected when carrier materials with low

Liquid loading capacity to be used, such as said, particularly preferred sodium sulfate. More suitable support materials may e.g. Silicas, bentonites, zeolites o.a. but most often have the disadvantage of water insolubility or other incompatibilities (e.g., alkaline pH). Nevertheless, even with these carriers there is a risk that the loading limit is exceeded and clumping and increased coarse material formation occurs.

Further difficulties may arise in the selection of the suitable binder. First, it proves to be advantageous in many cases to adjust granules to an acidic pH in order to reduce or prevent the alkaline hydrolysis of the active component in the detergent powder formulation and thus to significantly improve the chemical storage stability. Therefore, particular preference is given to binders which, in addition to the binder function, also allow the setting of an acidic pH. Common are here

Polycarboxylates and their co-polymers, such as the aforementioned Sokalan CP 45. The disadvantage is that these products are often available with the desired pH value function only as an aqueous solution. This circumstance has the consequence that the difficulties described above for controlling the water balance in the mixing process are exacerbated, since over the binder solution additional water fractions are introduced into the system. Another problem may arise when the catalyst solution or suspension is to be metered with the binder solution as a liquid mixture. A common dosage as a mixture is desirable here, because on the one hand reduces the procedural complexity and on the other hand, a uniform granule composition is achieved with optimum acid protection function. However, as is also known from other material systems (eg mixture of some Sokalan binders with cationic surfactants), massive incompatibilities can occur between catalyst solution and binder solution. This can be manifested by direct chemical reaction (eg recognizable by discoloration), but also by precipitations, adhesions, etc., which prevent controllability of the granulation process.

Finally, considering the requirements for the finished granules containing the bleach catalyst, other aspects must be considered in the formulation of a granular formulation. In addition to the requirements of the chemical properties (for example performance, storage stability), physical property requirements must also be fulfilled. Here, easy handling is of great importance, i. the granules should e.g. a low caking tendency, which is often caused by moisture absorption or have a high abrasion resistance. In optimizing the

However, granule composition must not be affected by the performance, which repeatedly shows the contradiction of abrasion stability and good solubility.

Task was therefore to find a suitable method for an improved

To provide granule formulation. On the one hand, the described procedural difficulties are to be avoided and a stable, problem-free process is to be made possible. On the other hand, a formulation should be prepared which meets the requirements described for the granules. , _ _. _ - -

It has surprisingly been found that this object is achieved by a granulation process in which an aqueous mixture of bleach catalyst, acidic component and optionally further additives in one Sprayed fluidized bed onto a suitable support material, granulated and dried at the same time.

The invention thus provides a process for the preparation of bleach activator granules containing a bleach catalyst, an acid

Polymer, a carrier material and optionally further additives. This process comprises forming a fluidized bed from the support material in a fluidized bed apparatus, metering into this fluidized bed an aqueous solution or suspension which contains the bleach catalyst, the acidic polymer and optionally the further additives, granulated and dried.

The granules thus obtained can then be provided with a Coatinghϋlle according to known methods.

As the bleach catalyst according to the present invention, there are preferably used the compounds of the formula (1) as defined above and the metal complexes of the above formula (2) containing the compounds of the formula (1) as a ligand. The compound dimethyl-2,4-di- (2-pyridyl) -3-methyl-7- (pyridin-2-ylmethyl) -3,7-diazabicyclo [3.3.1] nonane-9-one is preferably 1,5-dicarboxylate.

The acidic polymers used in the process according to the invention are preferably water-soluble acidic polymers. By water-soluble it is meant that they are soluble at 20 ^° C. to more than 5 g / l. 1% solutions of these polymers have a pH <7, preferably <5.5. The polymers used usually have a molecular weight in the range from 1000 to 280,000, preferably 1500 to 150,000.

Preferred are polymeric polycarboxylates. Polymeric polycarboxylates may homopolymers or copolymers of acrylic, methacrylic or maleic acid, furthermore copolymers of these acids with vinyl ethers, such as vinyl methyl ether or vinyl ethyl ether, vinyl esters, such as vinyl acetate or vinyl propionate, acrylamide, methacrylamide and ethylene, propylene or styrene, and the water-soluble Be salts of these polymers. Particularly suitable are polymers of acrylic acid, modified polyacrylates, copolymers of acrylic acid and maleic acid, as well as copolymers of maleic acid and olefins. Such polymers are, for example, under the name Sokalan ^® commercially. Preference is given to the types Sokalan CP 12S and Sokalan CP 13S.

The support materials used in the process according to the invention can be inorganic and / or organic in nature.

Suitable inorganic carriers are finely crystalline, synthetic zeolites, for example zeolite A, X and / or P or mixtures of these zeolites, as well as amorphous alkali metal silicates or crystalline layered silicates, sodium carbonate, sodium bicarbonate, sodium sulfate and trisodium citrate or mixtures of these carrier substances. Also suitable are alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of these are trisodium phosphate, tetrasodium diphosphate,

Disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of 5 to 1000, in particular 5 to 50, and mixtures of sodium and potassium salts. A preferred carrier material is sodium sulfate.

The bleach catalyst granules produced by the process according to the invention can, based on the finished granules, 30 wt .-% to 99 wt .-%, preferably 50 wt .-% to 90 wt .-%, particularly preferably 80 wt .-% to 88 wt .-% carrier material.

The bleach catalyst granules prepared according to the invention may contain as further substances additional binders, acidic additives or granulation aids.

Suitable binders are cellulose and starch and their ethers or esters, for example carboxymethylcellulose (CMC), methylcellulose (MC) or hydroxyethylcellulose (HEC) and the corresponding starch derivatives, but also film-forming polymers, for example polyacrylic acids or their salts. The amount of binder, based on the finished granules, can be from 0 to 45% by weight, preferably from 1 to 30% by weight.

Sulfuric acid, sodium bisulfate, phosphoric acid, sodium hydrogen phosphate, phosphonic acids and their salts, carboxylic acids or their salts, such as citric acid in anhydrous or hydrated form, glycolic acid, succinic acid, succinic anhydride, glutaric acid, glutaric anhydride, adipic acid, adipic anhydride, maleic acid, maleic anhydride, Tartaric, lactic, mandelic, pyruvic, salicylic, ascorbic, fumaric, retinoic, benzoic, kojic, fruit, malic, gluconic, sulfonic and sulfamic acids.

The amount of acidic additive in addition to the acidic polymers used according to the invention and defined above, in particular in addition to the Sokalan types is such that the proportion of the acidic additive in the finished granules about 0 to 20 wt .-%, preferably 1 to 10 Wt .-%, in particular 2 to 6 wt .-% is.

As granulation auxiliaries it is possible to use anionic or nonionic surfactants or polyalkylene glycols. Preferred anionic surfactants are alkali salts, ammonium salts, amine salts and salts of amino alcohols of the following compounds: alkyl sulfates, alkyl ether sulfates, alkyl amide sulfates and ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkyl sulfonates, alkyl amide sulfonates, alkylaryl sulfonates, alpha-olefin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkyl amide sulfosuccinates, alkyl sulfoacetates, Alkyl polyglycerol carboxylates, alkyl phosphates, alkyl ether phosphates, alkyl sarcosinates, alkyl polypeptides, alkyl amido coppeptides, alkyl isethionates, alkyl taurates, alkyl polyglycol ether carboxylic acids or fatty acids such as oleic acid, ricinoleic acid, palmitic acid, coconut oil acid salt or hydrogenated

Copra. The alkyl radical of all these compounds normally contains 8 to 32, preferably 8 to 22 C atoms. Particularly preferred are linear straight-chain alkylbenzenesulfonates, in particular having a C ₈ -C ₂₀ -, especially preferably with a Cn- _13- alkyl group or arylsulfonates, for example cumene sulfonate.

As nonionic surfactants, it is possible to use polyethoxylated, polypropoxylated or polyglycerolated ethers of fatty alcohols, polyethoxylated, polypropoxylated and polyglycerolated fatty acid esters, polyethoxylated esters of fatty acids and of sorbitol, polyethoxylated or polyglycerolated fatty amides.

The method according to the invention is carried out in detail as follows. An aqueous solution or suspension of the bleach catalyst containing about 5 wt% to 50 wt%, preferably 10 wt% to 40 wt%, more preferably 20 to 35 wt% of bleach catalyst, based on aqueous solution or suspension is at 10 ⁰ C to 40 ⁰ C, preferably at room temperature with an aqueous solution containing 5 to 80 wt .-%, preferably 10 to 60 wt .-%, particularly preferably 20 to 55 wt .-% of acidic polymer, for example Sokalan CP 13.

The mixing ratio of bleach catalyst to acidic polymer is preferably in the range of 1: 1 to 1: 3, preferably 1: 5: 2.5, more preferably 1: 6: 2 parts by weight.

This mixture is then sprayed onto the carrier material in a fluidized bed apparatus.

For the preparation of the bleach catalyst granules fluidized bed apparatuses are used, which may be preferably cylindrical or conical or rectangular.

In a preferred embodiment, the fluidized bed apparatuses are round and have bottom plates with dimensions of at least 0.4 m in diameter. In particular, fluidized bed apparatuses are preferred which have a bottom plate with a diameter between 0.4 m and 3 m, for example 1, 2 m or 2.5 m. In a further preferred embodiment, the fluidized bed apparatuses may have a rectangular shape, wherein the inflow surface from 0.2 to 10 m ² , for example, 1, 25 m ² or 7.5 m ² . As a bottom plate, a perforated bottom plate or a Conidurplatte, a wire mesh or a combination bottom of a perforated plate with a grid can be used.

The granulation process according to the invention can be carried out either batchwise or continuously. In the case of batchwise operation, the support material is initially introduced into the apparatus and then sprayed with the granulation liquid containing the bleach catalyst, the acidic polymer and optionally the other additives. The process parameters are set in such a way that granulation takes place to achieve the desired particle sizes. After reaching the required concentration of the bleach catalyst spraying is stopped. In the case of a continuous process, the solid carrier material and the granulating liquid are metered into the apparatus at the same time. It is important to ensure that both product streams are dosed in the right proportion to each other in order to achieve the required granule composition.

An additional solids feed, for example of dust-like fines of the finished granules or of powdered formulation components may be advantageous.

A further process variant is that the aqueous mixture of bleach catalyst, acidic polymer and optionally further additives prepared by mixing at room temperature, optionally heated to a temperature of 25 ° C to 85 ⁰ C, pumped via a suitable pump to the nozzle and of is sprayed into the fluidized bed below. The air inlet temperature is between 90 and 97 ° C. The vortex air cools due to heat loss and the heat of evaporation of the solvent. As a result, the temperature of the layer mass in the fluidized bed at 50 to 7O ⁰ C, a. The air outlet temperature is between 55 ° C and 65 ° C. In fluidized bed granulation, the water content of the products can be set within wide limits. In the process according to the invention, drying takes place simultaneously with the granulation in the fluidized bed. In a preferred embodiment of the invention, the process is conducted so that the water content of the finished granules is <2 wt .-%.

In the case of a continuous process, the discharge of the finished granulate from the fluidized bed is advantageously carried out by size classification of the granules. This classification can be carried out by a visible discharge, which is regulated so that only particles above a certain particle size discharged from the fluidized bed and smaller particles are retained in the fluidized bed. The particles discharged from the gas stream above the fluidized bed are separated (e.g., by dust filters). The separated dust is returned to the fluidized bed in the area of the spray nozzle where re-wetting occurs.

Granules preferred according to the invention have a d50 value between 0.2 and 0.9 mm. In a particularly preferred embodiment, the Komanteil is greater than 1, 0 mm, returned. This coarse fraction can be added after grinding as a solid component of the fluidized bed.

The inventive method allows simultaneous granulation and drying, so that the composition of the granulating liquid to be processed can be varied within very wide limits without encountering process-limiting limits. This flexibility allows a problem-free adaptation of the necessary additive content to the granulate requirements.

The granules obtained according to the invention are suitable directly for use in detergents and cleaners. They are characterized by a good chemical and physical storage stability, high abrasion stability and still good solubility in the application.

In addition, however, they can be provided with a coating shell according to methods known per se. For this purpose, the granules in an additional Step wrapped with a film-forming substance, whereby the product properties can be significantly influenced. Suitable coating agents are all film-forming substances such as waxes, silicones, fatty acids, fatty alcohols, soaps, anionic surfactants, nonionic surfactants, cationic surfactants, anionic and cationic polymers, polyethylene glycols and polyalkylene glycols. Particularly preferred are polymeric polycarboxylates. Polymeric polycarboxylates may be homo- or copolymers of acrylic, methacrylic or maleic acid, copolymers of these acids with vinyl ethers such as vinyl methyl ether or vinyl ethyl ether, vinyl esters such as vinyl acetate or vinyl propionate, acrylamide, methacrylamide and ethylene, propylene or styrene, and the water-soluble salts of these polymers. Particularly useful are polymers of acrylic acid, modified polyacrylates, copolymers of acrylic acid and maleic acid, and copolymers of maleic acid and olefins, especially Sokalan ^® grades from BASF, particularly preferably Sokalan CP 13S.

In principle, C ₈ -C ₃ i fatty acids (for example: lauric, myristic, stearic acid), dicarboxylic acids, for example glutaric acid, adipic acid or their anhydrides are also suitable. Phosphonic acids, optionally phosphonic acids in admixture with other common coating agents, in particular fatty acids, for example stearic acid, C ₈ -C ₃ i-fatty alcohols; Polyalkenyl glycols (eg

Polyethylene glycols having a molecular weight of 1,000 to 50,000 g / mol); Nonionics (eg C ₈ -C ₃ i-fatty alcohol polyalkoxylates with 1 to 100 moles EO); Anionics (eg alkanesulfonates, alkylbenzenesulfonates, α-olefinsulfonates, alkyl sulfates, alkyl ether sulfates with Cβ-Car hydrocarbon radicals); Polymers (eg polyvinyl alcohols); Waxes (eg: montan waxes, paraffin waxes, ester waxes, polyolefin waxes); Silicones.

In addition, other substances which do not soften or melt in this temperature range can be present in dissolved or suspended form in the coating substance, for example polymers (for example homo-, co- or

Graft copolymers of unsaturated carboxylic acids and / or sulfonic acids and their alkali metal salts, cellulose ethers, starch, starch ethers, polyvinylpyrrolidone); Organic substances (eg mono- or polybasic carboxylic acids, Hydroxycarboxylic acids or ether carboxylic acids having 3 to 8 C atoms and salts thereof); dyes; Inorganic substances (eg: silicates, carbonates, bicarbonates, sulfates, phosphates, phosphonates).

Depending on the desired properties of the coated

Bleach catalyst granules, the content of coating substance 1 to 30 wt .-%, preferably 5 to 15 wt .-%, based on coated bleach catalyst granules amount.

To apply the coating substances, it is possible to use mixers (mechanically induced fluidized bed) and particularly preferably fluidized bed apparatuses (pneumatically induced fluidized bed). As a mixer, e.g. Ploughshare mixers (continuous and batchwise), ring layer mixers or even Schugi mixers possible. Both in the mixing process and in the fluidized bed process, the coating substance can be sprayed on a single-component or a two-component nozzle device.

By using these coating materials, the storage stability and hygroscopicity, as well as the compatibility with other detergent ingredients, in particular strongly alkaline components can be further improved and the reaction kinetics can be selectively influenced, in this way

Prevent interactions between the bleach catalyst and other components before the washing process.

The granules according to the invention are characterized by a very good storage stability in powdered washing, cleaning and

Disinfectant formulations from. They are ideal for use in heavy-duty detergents, stain salts, machine dishwashing detergents and powdery all-purpose cleaners. Example 1: Granulation with acidic component

For laboratory experiments, a batch-working laboratory fluidized bed of the type GPCG 1.1, Fa. Glatt was used with a flow diameter of D = 150 mm, the spray nozzle sprayed from below into the fluidized bed.

Sodium sulfate was introduced as a fine free-flowing product in the fluidized bed apparatus in batches and then warmed up by the fluidizing air. After reaching the starting temperature, the liquid metering was started and via a two-fluid nozzle, the liquid mixture containing dimethyl-2,4-di- (pyridyl) -3-methyl-7- (pyridin-2-ylmethyl-3,7-diazabicyclo (3.3.1 ) Nonan-9-one-1, 5-dicarboxylate as a bleach activator and an acid-modified (meth) acrylic acid copolymer (Sokalan CP 13S) as an acidic polymer were atomized into the moving fluidized bed The amount of spray liquid conveyed with a peristaltic pump was detected gravimetrically by means of a balance . the inlet air temperature was approximately 95 - set 97 ⁰ C. with the optimal spray performance, a temperature set in a fluidized bed of approx. 64 - 65 ° C, where this temperature level was kept stable after a trial period of about 64. After the cooling and subsequent drying of the granules, a fractionation was carried out by screening off the coarse fractions> 1000 μm and fines <200 μm n experimental settings, a granule yield of about 90.4% was achieved for the target grain area. The bulk density of the granules was about 884 g / l, the abrasion content was 12.9%. The final granulate was composed as follows:

Bleach catalyst (dry) 6.01%

Sokalan CP 13 S (dry) (acid component) 10.01%

Sodium sulfate 83.48%

Residual moisture 0.5% Example 2: Granulation with acidic component and addition of a further additive

Sodium sulfate was introduced as a fine free-flowing product in the fluidized bed apparatus in batches and then warmed up by the fluidizing air. After reaching the starting temperature, the Fiüssigkeitsdosierung was started and via a two-fluid nozzle, the liquid mixture containing the same bleach activator and the same acidic polymer as in Example 1 and maleic acid (additive) was atomized into the moving fluidized bed. The amount of spray liquid delivered with a peristaltic pump was recorded gravimetrically by means of a balance. The supply air temperature was set to approx. 95 - 97 ° C. With adjustment of the optimum spraying power, a temperature in the fluidized bed of about 65 to 70 ^° C. was established, whereby this temperature level could be kept stable. After a test run time of about 90 minutes, the required amount of liquid was metered. After cooling and drying of the granules, fractionation was carried out by screening off the coarse fractions> 1000 μm and fines

<200 μm. With these experimental settings, a granule yield of about 75.8% was achieved for the target grain area. The bulk density of the granules was about 972 g / l, the abrasion content was 1.2%. The final granulate was composed as follows:

Bleach catalyst (dry) 5.8%

Sokalan CP 13 S (dry) acidic component 12.1%

Maleic acid (additive) 10.08

Sodium sulphate 71, 52%

Residual moisture 0.5%

Claims

claims

1. A process for the preparation of bleach catalyst granules comprising a bleach catalyst, an acidic polymer, a support material and optionally further additives, characterized in that forming a fluidized bed in a fluidized bed apparatus from the support material, in this fluidized bed an aqueous solution or suspension metered, the the bleach catalyst, the acidic polymer and optionally the other additives, granulated and dried.

2. The method according to claim 1, characterized in that the coated bleach catalyst granules are subsequently coated with a coating layer.

3. The method according to claim 1, characterized in that as a bleach catalyst, a compound of formula (1)

where R is hydrogen, fluorine, chlorine, bromine, hydroxyl, C ₁ -C ₄ alkoxy, -NH-CO-H, -NH-CO-C _r C ⁴ alkyl, -NH ₂ , -NH-d-OrAlkyl R ¹ and R ² independently of one another are C ₁ -C ₄ alkyl, C ₆ -C 10 aryl or a group containing a heteroatom, preferably (CH ₂ ) _z -2-pyridyl, where z is a number from 1 to 5 stands; R ^{3 is} hydrogen or C ₁ -C ₄ alkyl and n is a number from 0 to 4 and X is C = O or - [C (R) 2] y-, where y is a number from 0 to 3 and R is hydrogen, hydroxyl, C ₁ -C ₄ - alkoxy or C _r C ₄ alkyl.

4. The method according to claim 1, characterized in that the bleach catalyst is a compound of formula (2)

[M _a L _k X _n ] Y _m (2)

where M is Mn (II), Mn (III), Mn (IV), Mn (V), Cu (I), Cu (II), Cu (III), Fe (II),

Fe (III), Fe (IV), Fe (V), Co (I), Co (II), Co (III), Ti (II), Ti (III), Ti (IV), V (II) V (III), V (IV),

V (V), Mo (II), Mo (III), Mo (IV), Mo (V), Mo (VI) and W (IV), W (V) and W (VI) are preferable

Fe (II), Fe (III), Fe (IV), Fe (V), L a ligand according to the formula (1), preferably dimethyl-2,4-di- (2-pyridyl) -3-methyl-7 - (pyridin-1-ylmethyl) -3,7-diazabicyclo [3.3.1] nonane-9-one-1, 5-dicarboxylate or its protonated form,

X is a singly, doubly or triply charged anion or a neutral molecule that can coordinate with M, Y is a noncoordinating counterion and a is an integer from 1 to 10 k is an integer from 1 to 10 n is an integer from 0 to 10 m is an integer from 0 to 20.

5. The method according to claim 1, characterized in that as a bleach catalyst dimethyl-2,4-di- (pyridyl) -3-methyl-7- (pyridin-2-ylmethyl) -3,7-diazabicyclo (3.3.1) nonan-9-one-one, 5-dicarboxylate or a metal complex of the formula (2) containing this compound as a ligand.

6. The method according to claim 1, characterized in that one takes as the carrier sodium sulfate.

7. - The method according to claim 1, characterized in that one takes as the acidic polymer, which is soluble at 2O ⁰ C to more than 5 g / l in water and the 1% solution as a pH of less than 7 having.

8. The method according to claim 1, characterized in that one additionally uses an acidic additive.

9. The method according to claim 1, characterized in that the total amount of support material is introduced as a fluidized bed and granulated batchwise with the aqueous solution or suspension containing bleach catalyst, acidic polymer and optionally further additives.

10. The method according to claim 1, characterized in that the carrier material and the aqueous solution or suspension containing

Bleaching catalyst, acidic polymer and optionally further additives, continuously metered into the fluidized bed apparatus.