EP0025608A2 - Catalyst for the controlled decomposition of peroxide compounds, its preparation and use; washing or bleaching agent and process for producing a washing or bleaching agent that contains peroxide compounds - Google Patents

Abstract

The catalyst contains or consists of zeolites or silicates with sheet anions or products which have been obtained therefrom by acid treatment and whose exchangeable alkali metal or alkaline earth metal cations have been wholly or partially replaced by cations of one or more heavy metals from groups Ib, Va, Vb, VIIa and/or VIII of the Periodic Table, and washing or bleaching agents containing peroxo compounds and this catalyst. <IMAGE>

Description

The invention relates to a catalyst for the controlled decomposition of peroxo compounds. According to the invention, peroxo compounds are compounds in which the grouping -0- is replaced by the grouping -0-0-. The simplest representative of this group is hydrogen peroxide.

Other representatives are the metal peroxides, especially the alkali and alkaline earth peroxides; the peroxohydrates, i.e. the hydrogen peroxide addition compounds on borates, carbonates, urea and phosphates, e.g. Sodium borate peroxohydrate (also known as sodium perborate), sodium carbonate peroxohydrate (also known as sodium percarbonate), urea peroxohydrate and phosphate peroxohydrate; Peroxyacids, e.g. Peroxophosphoric acid and peroxosulfuric acid. The term “peroxo compounds” is also intended to cover organic peracids, such as peracetic acid or perpropionic acid, which are usually referred to as peroxy compounds.

It is known that peroxo compounds are catalytically decomposed by heavy metal ions to form molecular oxygen. This decomposition must be avoided in most applications of the peroxo compounds, especially in the bleaching process, since molecular oxygen has no bleaching effect. The catalytic decomposition of peroxo compounds can also generate oxygen radicals, which can have a detrimental effect on the substrates to be treated.

The invention has for its object to subject peroxo compounds to controlled decomposition so that the oxygen is released in such a form that on the one hand the substrate to be treated is not damaged and on the other hand the loss of active oxygen caused by the formation of molecular oxygen and thus the bleaching effect is reduced as much as possible.

It has now surprisingly been found that such controlled decomposition of peroxo compounds is possible if the peroxo compounds are combined with certain catalysts containing heavy metal ions.

The invention thus relates to a catalyst for the continuous decomposition of peroxo compounds, which is characterized in that it contains zeolites or silicates with layer anions or products obtained therefrom by acid treatment, their exchangeable alkali metal or alkaline earth metal cations in whole or in part by cations of one or more heavy metals from the Groups Ib, Va, Vb, VIIa and / or VIII of the periodic table are replaced, contains or consists of.

The catalyst according to the invention surprisingly brings about a controlled decomposition of the peroxo compounds, even though it releases some of its heavy metal cations into the solution. This effect is surprising insofar as it was previously believed that heavy metal ions should be excluded as far as possible when working with peroxo compounds.

When the peroxo compounds are brought into contact with the catalyst in aqueous solution, the oxygen release generally begins at about 30 to 35 ° C. and increases steadily as the temperature increases further.

The heavy metal cations are essentially internally crystalline embedded in the zeolites or silicates with layer anions or in the products obtained therefrom by acid treatment. For the zeolites, which are silicates with three-dimensional framework anions, the heavy metal cations are likely to be found inside the cage structure. In the case of silicates with layer anions, the heavy metal cations are located between the layers. In this group of silicates, the attapulgites (sepiolite and palygorskite) form a sub-group. The anion layers of these silicates are rolled up in a tube shape and form cylindrical cavities. The attapulgites are thus between the zeolites and the actual silicates with layer anions. This includes the clays or clay minerals.

This group is divided into the following subgroups:

Clay minerals of the kaolinite structure type. These include the kaolin minerals kaolinite, nacrite, dickite, anauxite and halloysite, the serpentine minerals chrysotile, serpentine, antigorite, amesite.

Montmorillonite-Beidellite range. These include montmorillonite, which is the main mineral of bentonite, as well as hectorite, beidellite, saponite and nontronite.

Vermiculite series silicates. These include dioctahedral and trioctahedral vermiculite.

Illite series silicates. These include the fine crystalline mica, the dioctahedral and the trioctahedral illite and the glauconite.

Mica minerals. These include in particular the muscovite and the biotite.

Minerals from the chlorite group. These are derived from the mica-like layered silicates in that a hydroxide layer Me (OH) ₂ or Me (OH) _{3 is} introduced between the silicate layers instead of the intermediate layer cations.

Clay minerals with species disorder (mixed-layer silicates). These clay minerals are built up alternately from layers of different clay minerals.

According to the invention, the minerals from the montmorillonite-beidellite range are particularly suitable, e.g. occur in natural bentonites.

Both the zeolites and the silicates with layered anions can be subjected to an acid treatment, the monovalent and divalent cations being generally dissolved out to a greater or lesser extent while maintaining the anion lattice. With intensive acid treatment, the aluminum is also partially removed. In the case of the acid-treated silicates, the products obtained from clays of the montmorillonite-beidellite series are preferably used according to the invention. The acid-treated products obtained from natural bentonites are generally known as bleaching earths. The acid treatment is generally carried out by heating the clays in aqueous mineral acids such as sulfuric or hydrochloric acid, after which the acid solution is extracted and washed out together with the dissolved cations.

The heavy metal cations, which after the storage instead of the exchangeable alkali or alkaline earth cations sit in the cavities of the silicate lattice or between the silicate layers, catalyze the decomposition of the peroxo compounds dissolved in an aqueous solution in a controlled manner, probably by the fact that the molecules or anions of the peroxy compounds must diffuse into the cavities or into the interlayer spaces to the bound heavy metal ions. This diffusion is obviously the rate-determining process. However, the exact mechanism of the reaction is not yet known.

The catalyst according to the invention is preferably loaded with cations of one or more of the metals nickel, antimony, copper, vanadium, manganese, silver, cobalt or iron. Iron, copper and / or manganese are particularly preferably used. The heavy metal cations are preferably in divalent or trivalent form.

The catalyst according to the invention preferably contains about 3 to 300 meq heavy metal cations per 100 g zeolites or silicates with layer anions. The maximum amount absorbed depends primarily on the ion exchange capacity of the silicate.

The catalyst according to the invention can also be a mechanical mixture of catalysts which are each loaded with different heavy metal cations. The individual catalysts have different activities, and the rate of decomposition can be modified in the desired manner by a suitable selection of the catalysts.

The invention further relates to a process for the preparation of the catalysts described above. This process is characterized in that one or more water-soluble salts of one or more heavy metals are applied to an aqueous suspension of the zeolites or silicate with layer anions or the products obtained therefrom by acid treatment the groups Ib, Va, Vb, VIIa and / or VIII of the Periodic Table, which removes the heavy metal cations not in solution by the silicates and which is in solution, washes the solid residue until practically no heavy metal ions can be detected in the washing liquid, and the washed solid residue dries.

• a) Beladung bis zur Sättigung und Vermischung des erhaltenen Produkts auf mechanischem Wege mit unbehandeltem Silicat bzw. mit einem Silicat, das mit einem weniger aktiven Schwermetall-Kation beladen wurde.
• b) Teilbeladung des Silicats.

The exposure time of the heavy metal salt solution is not particularly critical. However, it is preferred to let the salt solutions act until all exchangeable cations of the silicate have been replaced by heavy metal cations. Do you want one less active catalyst, the following production options are available:

• a) Loading until the product obtained is saturated and mixed mechanically with untreated silicate or with a silicate which has been loaded with a less active heavy metal cation.
• b) partial loading of the silicate.

The catalysts are preferably prepared in such a way that an approximately 0.5 to 3 normal, preferably 1 normal, heavy metal salt solution is allowed to act on the silicate suspension.

The invention further relates to the use of the catalysts described above as a component in detergents or bleaches containing peroxo compounds, in particular in detergents or bleaches to which sodium perborate has been added.

The peroxo compounds contained in the washing or bleaching agents usually only take effect at higher temperatures, in particular at or near the boiling point of the washing liquor. The disintegration occurs more or less uncontrolled, so that a uniform bleaching effect is only achieved if relatively high proportions of peroxo compounds available. These are then broken down only to a relatively small extent, for example 15 to 20%, which makes the overall effort uneconomical and ecologically questionable. Surprisingly, it has been found that the proportion of the peroxo compound decomposed during the washing process is greatly increased by adding a catalyst according to the invention, so that 50 and more percent of the peroxo compound present are evaluated for the bleaching or oxidation process. On the one hand, this enables a considerable increase in the bleaching effect, while at the same time reducing the proportion of excess peroxo compound in the waste water; on the other hand, you can incorporate the added amount of peroxo compound in a considerably smaller amount from the start and still achieve the same bleaching effect.

The amount of heavy metal cations contained in the catalyst is expediently at most equal to the amount of sodium perborate contained in the detergent or bleach. The detergent or bleach contains, per 100 parts by weight, preferably at least 0.1 part by weight of the catalyst according to the invention, the amount of which may be up to about 30% by weight of the total weight of the detergent or bleach. Amounts of catalyst between about 0.5 and 10% by weight are preferred.

For example, 100 parts by weight of a commercial detergent containing sodium perborate was mixed with 1 part by weight of a copper-loaded bentonite (30 meq Cu / 100 g bentonite). This mixture was compared with the copper-free starting product with regard to the bleaching effect. The detergent mixed with the catalyst according to the invention showed a marked increase in the bleaching effect. If a commercially available detergent was compared in the same way as a detergent containing less sodium perborate but mixed with the catalyst according to the invention, the same bleaching effect could be achieved. Analogous results were also obtained when about 1% of a bentonite containing only about 10 to 20 meq Cu / 100 g was added to the detergents.

The invention further relates to detergents or bleaches containing peroxo compounds which are characterized by a content of the catalysts described above. These washing or bleaching agents preferably contain about 0.1 to 30% by weight of catalyst and about 5 to 99% by weight of sodium perborate, the remainder consisting of the usual washing or bleaching agent additives.

The detergents or bleaches according to the invention can be prepared by spray-drying a free-flowing powder from detergent-active and complex-forming substances, builders, fillers and the catalyst according to the invention and this powder, if appropriate, still warm with a peroxo compound, preferably sodium perborate , mixed in the desired amount.

Instead of adding the catalyst to the aqueous, slurry-like mixture intended for spray drying, at least part of the catalyst in powder form can be blown into the space or part of the spray drying system during the spray drying of an aqueous batch of the peroxide-free other constituents, in which the atomized particles of the aqueous batch are dried are, whereupon the peroxy compound is mixed into the powder thus obtained.

Finally, one can also proceed by mixing a washing or bleaching agent obtained in a manner known per se with the catalyst according to the invention and the peroxo compound.

The detergents and bleaches produced in this way can, in addition to the constituents mentioned above, also other components in the production of detergents and bleaches Common additives, such as enzymes, brighteners, dirt carriers, phosphate substitutes, etc. contain.

A known additive for detergents and bleaches is ethylenediaminetetraacetic acid (EDTA), which is usually in salt form. The EDTA reacts with the heavy metal ions in solution to form a complex in which the heavy metal ions are no longer able to catalyze the decomposition of peroxo compounds. Surprisingly, it was found that the catalytic activity of the catalysts according to the invention is largely retained even in the presence of EDTA.

The course of the decomposition curves of the peroxo compounds depends on various factors, for example on the concentration of the catalyst, on the concentration and type of heavy metal cations in the catalyst and on the mixing ratio of the catalyst components loaded with different heavy metal cations. If a mixture is used, the most favorable conditions between the individual catalysts can easily be determined on the basis of simple experiments. The decomposition curves for the individual catalysts are determined at the desired temperature and time parameters. If, for example, the slope of the decomposition curve obtained with a catalyst is too large, it will become Catalyst mixed with another catalyst in which the decomposition curve shows a flatter slope. Too steep a decomposition curve can also be optimized by adding a silicate to the catalyst containing the heavy metal cations that has not been loaded with heavy metal ions.

The time course of the release of oxygen during the decomposition of the peroxo compounds as a function of temperature can expediently be measured using the apparatus described below:

The gas development vessel is a narrow-necked Erlenmeyer flask (100 ml), which is equipped with a rubber stopper through which an internal thermometer and a glass tube bent at right angles are passed. The other end of the glass tube is connected via a short rubber hose connection to a U-shaped glass tube, which is used as an inlet tube in a 200 ml measuring cylinder. The measuring cylinder is in a drip pan. The Erlenmeyer flask is in a water bath that is heated by a hotplate with a magnetic stirrer. There is a contact thermometer and a magnetic rod in the water bath. Another magnetic rod is in the Erlenmeyer flask.

Weigh out one gram of a peroxo compound (accurate to 0.1 mg) into the Erlenmeyer flask, then the sample to be examined with the Heavy metal ions coated catalyst. A magnetic rod and 50 ml of distilled water (20 ° C.) are then added, and the apparatus is immediately closed by fitting the rubber stopper and connected to the measuring cylinder filled with water. The flask is now inserted into the water bath (20 ° C) so that the level of the water bath is higher than that of the suspension to be examined.

The apparatus is now heated using the rate of heating described below.

First, the air displacement of the apparatus (volume expansion of the air in the flask) is determined as a zero value with a weight of 50 ml of distilled water while heating from 20 to 60 ° C, for example. The values from the zero value curve are subtracted from the values of the individual decomposition curves at the respective temperatures. The zero value after 15 minutes, i.e. after reaching a temperature of 60 ° C, is about 18.3 ml. In the drawing only the net decomposition curves, i.e. after deduction of the respective zero value.

For example, the theoretical decomposition value of 1 g sodium perborate (MW 153.84, purity> 98%, 6.5 mmol) is 72.8 ml 0 ₂ (3.25 mmol). The practical decomposition value of 1 g sodium perborate was found to be 79.5 ml. That this value is higher than the theoretical decomposition value is due to the fact that the gas volume saturated with water vapor in the measuring cylinder at room temperature. The practical decomposition value was not converted to normal conditions, since all curve values were obtained under the same conditions. The practical decomposition value could therefore be set as 100%.

Some decomposition curves are shown in the drawing. 1.0 g of peroxo compound in 50 ml of distilled water were each decomposed using the catalysts according to Examples 1 to 7. The numbering of the curves corresponds to the numbering of the examples. 1 and 2 show the decomposition of perborate solutions. 3 shows the decomposition of H ₂ 0 ₂ solutions, in each case when heating up to 60 ° C.

example 1 Manufacture of copper bentonite

a) America cleaned by slurrying and wet sieving over a 63 _/ u sieve. Raw clay was treated with a 1 n solution of CuS0 ₄ . The quantitative ratios were 1300 g of clay (dried) in 24 liters of water (5.4% suspension) and 1248 g (5 mol) of CuS0 ₄ -5H ₂ 0 in 10 liters of water (1n) or to 100 g of bentonite clay 770 mVal Cu ions. After a reaction time of 16 hours, the mixture was filtered off, washed until largely free of ions, dried at 90 ° C. and ground. The copper bentonite had 91 mVal exchangeable Cu ions per 100 g; it was cut down to 60mVal / 100g with untreated bentonite.

b) According to another embodiment, amer. Bentonite and Moosburger bentonite specifically coated with copper ions. For this purpose, 5% aqueous bentonite suspensions were mixed with dilute Cu-SO ₄ solutions, the following proportions being used:

To 100 g amer. Bentonite 20 or 100 mVal Cu ions

On 100 g Moosburger bentonite 20, 50 or 100 mVal Cu ions

After a reaction time of 16 hours, the mixture was filtered, washed until largely free of ions, dried (130 ° C.) and ground (finer than 63μ).

Example 2 Production of a catalyst with different heavy metal cations on acid activated clay

For acid activation, 100 parts by weight of Moosburger bentonite were heated at 36 ° C. for 8 hours with 36 parts by weight of HCl in the form of a 31.17% strength hydrochloric acid. The excess acid in which the cations released from the silicate lattice are dissolved was filtered off, and the residue was washed with water or weak acid until practically no dissolved cations were detectable in the washing liquid. The residue was then dried.

500 g of an acid-activated bentonite (hereinafter referred to as H-bentonite) thus obtained were each mixed with 1 liter of a 1N solution of (a) MnCl ₂ , (b) CuSO ₄ and (c) NiCl ₂ and after a stirring time of 16 hours filtered off. After washing until substantially free of ions, the products at 120 ^° C were dried and milled (finer than 63 _/ u). In all cases, 200 mVal heavy metal ions were used for 100 g of silicate.

Example 3

Preparation of a catalyst with vanadium on bentonite.

In the manner described in Example 1 (b), a slurry of 100 g of Moosburger clay in 3 liters of distilled water was mixed with 100 mmol VOSO ₄ . 5H ₂ 0 and stirred for 16 hours. The reaction product was then filtered off, washed largely free of ions and dried. The bentonite had 8.7 mmol vanadium per 100 g as exchangeable ions (determined after NH ₄ Cl exchange).

Example 4

Production of a catalyst with different heavy metal cations on zeolite

• a) 100 mVal Cu²⁺ (aus CuS0₄)
• b) 100 mVal Mn²⁺ (aus MnCl₂)

A commercial type 4A synthetic zeolite was coated with copper and manganese ions according to the procedure of Example 1 (b), the following molar amounts of heavy metal cations being applied to 100 g of zeolite:

• a) 100 mVal Cu ²⁺ (from CuS0 ₄ )
• b) 100 mVal Mn ²⁺ (from MnCl ₂ )

An approximately 20% zeolite suspension was used

Example 5

Production of copper attapulgite

100 g of granulated attapulgite were shaken with 1 liter of 1N copper sulfate solution for 16 hours, then filtered off and washed out until the ions were largely free of ions. The copper attapulgite obtained had 112 mVal exchangeable Cu ions per 100 g.

Example 6

Production of a catalyst with iron on bentonite

In the manner described in Example 1 (b), iron bentonite was prepared by treating 100 g of Moosburger clay in 2 liters of distilled water with 100 mVal Fe ³⁺ (from FeCl ₃ .6H ₂ O). The bentonite had 29.4 meq of exchangeable iron ions per 100 g (determined by extraction with 0.1 N hydrochloric acid).

Example 7

Preparation of a catalyst with antimony on bentonite

15.2 g (66 mmol) of SbCl ₃ were dissolved in 500 ml of distilled water, the hydrolysis being prevented by simultaneous addition of hydrochloric acid. 100 g of Moosburger clay were stirred into the clear solution and then stirred for 16 hours. The bentonite loaded with antimony was filtered and washed with dilute hydrochloric acid (pH 1.5) until almost free of cations. The occupied bentonite had 22.3 meq of antimony III ions per 100 g (determined by extraction ^/ with 8% sulfuric acid).

Before the decomposition tests with peroxo compounds were carried out with the above-mentioned catalysts, the amounts of the heavy metal cations bound to the individual silicates were first determined, since the bound fraction is generally lower than the fraction used. Since there are certain relationships to the ion exchange capacity (IUF) of the silicate, these values are also mentioned for some examples. To determine the heavy metal ions, the occupied samples were extracted either with NH ₄ Cl solutions or with dilute hydrochloric acid or sulfuric acid.

The heavy metal ions were then determined analytically from the extraction solutions. The results are shown in Table I.

The catalysts prepared according to the examples were decomposed in the apparatus specified above. The results are given in the application examples below.

Application example 1

Decomposition of perborate

1.0 g of sodium perborate, dissolved in 50 ml of water, were each decomposed using the catalysts given below.

The weights and the heavy metal ion concentrations are given in Table II.

The decomposition values are given in Table III below and shown in FIGS. 1 and 2. From the values it can be seen that the greater the amount of copper on offer, the faster the copper bentonites decompose the perborate. Manganese hydrogen bentonite and manganese zeolite decompose the perborate relatively quickly, even with small amounts of manganese. Nickel hydrogen bentonite decomposes the perborate extremely slowly. Copper zeolite and copper attapulgite behave similarly to copper bentonite.

In a further comparative experiment, 1 g of sodium perborate, dissolved in 50 ml of water, was heated to 60 ° C. for 60 minutes without the addition of heavy metals, no decomposition being observed.

The catalysts with the lower activity can be mixed with the catalysts with the higher activity so that a medium activity can be obtained.

Example of use 2

Decomposition of hydrogen peroxide

788.5 mg of hydrogen peroxide (30.8% strength) were diluted with 50 ml of water, and 132.9 mg of copper bentonite 100 (Moosburg) from Example 1b (0.044 meq Cu) were added in the apparatus specified above. 5.5 mg (0.044 meq Cu) CuSO ₄ .5H ₂ O was used as the comparative catalyst on the same amount of hydrogen peroxide. In a further comparison experiment, the diluted hydrogen peroxide solution was heated without the addition of heavy metals. The results are shown in Table IV and (with the exception of the second comparison test) shown in FIG. 3.

Example of use 3

Perborate decomposition in a heavy duty detergent

Provided in a sealed with rubber stoppers and with contact thermometer, reflux condenser and sampler 4 liter round bottom flask were added to 2 liters of tap water (15 ⁰ dH, Ca: 1: Mg = 2), where g stirring 22.5 detergent with 20% sodium perborate. The detergent also contained the following ingredients:

Die Zersetzung wurde (A) ohne Zusatz eines erfindungsgemäßen Katalysators, (B + C) nach Zusatz von Cu-Bentonit gemäß Beispiel 1 und (D) nach Zusatz von Cu-Sulfat durchgeführt, wobei in den Fällen (B + C) und (D) die in Tabelle V angegebenen Mengen verwendet wurden.

The decomposition was carried out (A) without the addition of a catalyst according to the invention, (B + C) after the addition of Cu bentonite according to Example 1 and (D) after the addition of Cu sulfate, in the cases (B + C) and (D ) the amounts given in Table V were used.

The experiment was started by turning on the heating. The heating power was set so that the test temperature of 95 ° C was reached after 45 minutes and then held for 20 minutes. After about 15 minutes, i.e. after the solution had warmed to about 30 ° C. and the perborate had completely dissolved, the perborate content in a first sample of 50 ml was determined titrimetrically with potassium permanganate and set at 100% as a starting value. In the further course of the test, the perborate content of the solution was determined in the same way from 50 ° C. every 10 ° C. and after reaching the test temperature every 5 minutes.

• (a) ungebleichte Baumwolle (Nessel) der Firma G. Koch, Kerpen,
• (b) Immedialschwarz auf Baumwolle (EMPA 115).

To determine the bleaching effect, various test fabrics were washed once in a "Linites" model washing machine. The amount of alkali was 250 ml, the liquor ratio 1: 20. Detergent formulations, detergent concentration and temperature profile were the same as in the perborate decomposition experiments. The following were used as test fabrics:

• (a) unbleached cotton (nettle) from G. Koch, Kerpen,
• (b) Immedial black on cotton (EMPA 115).

The bleaching tests were evaluated by remission measurement with the Zeiss-Elrepho device, based on Mg0 = 100%. The data refer to% reflectance difference (ΔR) between unwashed and washed fabric, the values given in Table V being average values.

Claims (17)

1. Catalyst for the controlled decomposition of peroxo compounds, characterized in that it contains zeolites or silicates with layer anions or products obtained therefrom by acid treatment, their exchangeable alkali metal or alkaline earth metal cations in whole or in part by cations of one or more heavy metals from groups Ib, Va, Vb, VIIa and or VIII of the periodic table are replaced, contains or consists of. 2. Catalyst according to claim 1, characterized in that the heavy metal cations are incorporated internally crystalline in the zeolites or silicates with layer anions or in the products obtained therefrom by acid treatment. 3. Catalyst according to claim 1 or 2, characterized in that the silicates with layer anions represent attapulgite or clays or clay minerals, in particular from the montmorillonite-beidellite series. 4. Catalyst according to one of claims 1 to 3, characterized in that it is loaded with cations of one or more of the metals nickel, copper, vanadium, manganese, silver, antimony, cobalt or iron. 5. Catalyst according to one of claims 1 to 4, characterized in that it contains about 3 to 300 mVal heavy metal cations per 100 g of zeolites or silicates with layer anions. 6. Catalyst according to one of claims 1 to 5, characterized in that it is a mechanical mixture of catalysts, each loaded with different heavy metal cations. 7. A process for the preparation of the catalysts according to any one of claims 1 to 6, characterized in that one or more water-soluble salts of one or more heavy metals from the on an aqueous suspension of the zeolites or silicates with layer anions or the products obtained therefrom by acid treatment Groups Ib, Va, Vb, VIIa and / or VIII of the periodic table, which removes the heavy metal cations not in solution by the silicates and which is in solution, washes the solid residue until practically no heavy metal ions can be detected in the washing liquid, and drying the washed solid residue. 8. The method according to claim 7, characterized in that about 0.5 to 3-normal, preferably 1-normal heavy metal salt solution is allowed to act on the silicate suspension. 9. Use of a catalyst according to any one of claims 1 to 6 as a component in detergents or bleaches containing peroxo compounds. 10. Use of a catalyst according to one of claims 1 to 6 as a component in detergents or bleaches to which sodium perborate is added. 11. Use according to claim 10, characterized in that the amount of heavy metal cations contained in the catalyst is at most equal to the amount of sodium perborate contained in the detergent or bleach. 12. Use of a catalyst according to one of claims 1 to 6 in detergents or bleaches, characterized in that the detergent or bleach contains 100 parts by weight of at least 0.1 part by weight of catalyst and at least 5 parts of sodium perborate. 13. A detergent or bleach containing peroxo compounds, characterized in that it contains a catalyst according to one of claims 1 to 6. 14. washing or bleaching agent according to claim 13, characterized in that it contains 0.1 to 20 wt .-% catalyst and 5 to 99 wt .-% sodium perborate .. 15. A process for the preparation of a detergent or bleach containing peroxo compounds as claimed in claim 13 or 14, characterized in that a free-flowing powder composed of detersive and complex-forming substances, builders, in a manner known per se, Fillers and the catalyst according to one of Claims 1 to 6 are produced by spray drying and this powder is optionally mixed while still warm with a peroxo compound, preferably sodium perborate. 16. The method according to claim 15, characterized in that blowing in at least part of the catalyst in powder form during the spray drying of an aqueous batch of the peroxide-free other constituents into the space in which the atomized particles of the aqueous batch are dried, and the powder thus obtained admixes the peroxo compound. 17. A process for the preparation of a detergent or bleach containing peroxo compounds according to claim 13 or 14, characterized in that a detergent or bleach obtained in a conventional manner is mixed with the catalyst according to one of claims 1 to 6 and with the peroxo compound.

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