DE69506842T2 - Process for the preparation of granular detergent components or detergent compositions - Google Patents

Description

The present invention relates to a process for the continuous production of a granular detergent composition or component having a high bulk density and good flow properties. In such compositions and components it is known to use crystalline zeolite A, which is a water-insoluble, crystalline material that is well known in the detergent field as a builder which is particularly suitable for removing cations such as calcium and magnesium from hard water.

Crystalline zeolite A is a very finely divided powder. It has become common practice to process the finely divided powder into the form of large granules (typically 400 to 1000 µm) prior to incorporation into finished products, particularly finished detergent compositions. Various granulation processes are known, including spray drying and agglomeration. Conventional agglomeration processes using zeolite A as one of the components have long been known in the art:

GB 2 005 71 S. published on 25 April 1979 describes an agglomeration process based on zeolite A. The zeolite A is agglomerated together with carbonate/bicarbonate to produce non-ionic surfactant agglomerates.

WO 93/25378, published December 23, 1993, describes a process for preparing granular detergents comprising zeolite A. The zeolite A is agglomerated with a highly active, neutralized surfactant paste in a high speed mixer and a moderate speed mixer/agglomerator to make anionic surfactant agglomerates.

EP-B-0 342 043, published on 15 November 1989, describes detergent powders comprising aluminosilicate ion exchange materials including zeolite A, zeolite B, zeolite X, zeolite HS and mixtures thereof.

One of the factors limiting the surfactant activity of the above-mentioned prior art is the capacity of zeolite A to absorb liquid organic materials. It has been suggested that replacing zeolite A with zeolite P (particularly zeolite MAP) could address this problem:

EP 521 635, published on January 7, 1993, describes granular detergents using 10% to 100% zeolite MAP. Zeolite MAP has a different chemical composition than zeolite A. In Example 1 of this patent application it is reported that the oil absorption capacity of zeolite MAP is 41.6 ml/100 g, and that this is higher than in measured samples of zeolite A, for which it is 26 to 35.5 ml/100 g. However, modification of the chemical structure of conventional crystalline zeolite A (ie modification of the stoichiometric ratios of Si, Al, Na, O, H) is not always desirable, since other properties and characteristics of the zeolite are necessarily affected.

The aim of the invention is to provide a granulation process for producing granular detergents which incorporates highly absorbent crystalline zeolite into granular agglomerates without losing builder performance properties, in particular calcium exchange capacity and calcium exchange rate.

According to the invention, this aim is achieved by using a crystalline zeolite consisting essentially of zeolite A, P, X, Y (or mixtures thereof) and zeolite HS (hydroxysodalite). This is in stark contrast to prior art zeolites in which zeolite HS has been considered an impurity and its formation has been avoided. The zeolite of the present invention has modified physical characteristics (i.e. crystallinity, surface characteristics, moisture content) which in turn promotes better ease and flexibility in processing during the manufacture of detergent powders. The basic chemical structure of the zeolite is unchanged, whereby the excellent builder properties of the zeolite can still be utilized.

It is a further object of the present invention to provide a granulation process for producing granular detergents having improved processability and reducing the amount of oversized particles (or "lumps") formed in the process.

Summary of the invention

A process for preparing a granular detergent composition or component having a bulk density of greater than 650 g/l comprising the step of dispersing a liquid binder through a powder stream in a high speed mixer to form granular agglomerates, the powder stream comprising a powder consisting essentially of crystalline zeolite A, P, X, Y or mixtures thereof, and crystalline zeolite HS.

It is preferred that the ratio of zeolite A, P, X, Y or mixtures thereof to crystalline zeolite HS is between 1:1 and 99:1, preferably between 3:1 and 20:1, and that the powder has an oil absorption capacity of at least 40 ml/100 g, more preferably of at least 45 ml/100 g, most preferably of at least 50 ml/100 g.

In a preferred embodiment of the invention, the granular agglomerates are formed by mixing in a high speed mixer for a residence time of 2 seconds to 30 seconds, followed by the step of further mixing in a moderate speed mixer/agglomerator for a residence time through the moderate speed mixer of less than 5 minutes, preferably less than 2 minutes, during which a finely divided powder may optionally be added.

In other embodiments of the invention, the liquid binder is a surfactant paste, an organic polymer or silicone oil. The surfactant paste may include anionic, nonionic, cationic, amphoteric, zwitterionic surfactants and mixtures thereof; with anionic and/or nonionic surfactants being most preferred.

Detailed description of the invention

Granulation in the context of the present invention is defined as a process for producing a granular product which is an agglomerate of particles which behaves as a particle itself (according to S. A. Kuti, "Agglomeration - The Practical Alternative", published in Journal American Oil Chemists' Society, Volume 55, January 1978). The granular agglomerate is defined herein as the product of such a granulation process. Kuti further states that "the agglomerate is usually formed by mixing solids with liquids which serve as adhesives. However, producing a lump-free liquid-solid mixture often presents a difficult task."

In the present invention, the "solids" referred to by Kuti include crystalline zeolite having certain physical characteristics to be further defined below. It has now been found that this choice of "solids" greatly contributes to the achievement of the objective of producing a lump-free liquid-solid mixture.

The essential component of the granular agglomerate of the present invention is crystalline zeolite HS of the formula

(Na 2 O) · (Al 2 O 3 ) · X(SiO 2 ) · wH 2 O

where x is 2 and w is about 2.5 (D. W. Breck, "Zeolite Molecular Sieves", John Wiley & Sons, New York, 1974, page 155). Zeolite HS is also known as zeolite G, sodalite hydrate and hydroxysodalite.

The ideal unit cell composition for sodalite hydrate is:

Na&sub6;AlO&sub6;Si&sub6;O&sub2;&sub4; · 8H2O (Breck, page 269).

When NaOH is intercalated during synthesis, the composition varies according to:

Na&sub6;AlO&sub6;Si&sub6;O&sub2;&sub4; xNaOH(8-2x)H2O (Breck, page 272),

because one NaOH replaces two water molecules. It has been found that sodium hydrate adsorbs water after dehydration.

Breck also states that "silica-rich zeolite A appears to crystallize well within a 1-hour period, followed by rapid conversion in many cases to hydroxysodalite. This is to be expected from sodium-rich compositions of this type. The formation of hydroxysodalite was also accelerated when various anions were added to the gel compositions."

For the purposes of the present invention, it is necessary to regulate reaction conditions so that crystalline zeolite A (or P, X, Y) is formed in the required ratio to zeolite HS. Preferred ways of carrying this out are the use of sodium-rich gels at the zeolite formation, the careful regulation of the presence of various anions and the crystallization temperature.

Electron microscopy has shown crystals of zeolite HS "growing" from the surface of zeolite A. Without wishing to be bound by theory, it is suggested that this surface modification effect leads to the desired higher oil adsorption values of the zeolite powder.

Crystalline zeolites (other than zeolite HS) are also essential features of the present invention. Certain crystalline zeolites are of great importance in most currently marketed heavy-duty granular detergent compositions due to their detergent builder capacities. Aluminosilicate builders include those having the following empirical formula:

Mz(zAlO2 )y] · X H2 O

wherein z and y are integers of at least 6, the molar ratio of z to y is in the range of 1.0 to 0.5, and x is an integer of 15 to 264. Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates may be crystalline or amorphous in structure and may be naturally occurring aluminosilicates or synthetically derived. A process for preparing aluminosilicate ion exchange materials is described in U.S. Patent 3,985,669, Krummel et al., issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), (including Zeolite MAP), Zeolite X, and Zeolite Y. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:

Na 12 [AlO 2 ) 12 (SiO 2 ) 12 ] x H 2 O

where x is 20 to 30, especially about 27. This material is known as zeolite A. Dehydrated zeolites (x = 0-10) and "overdried" zeolites (x = 10-20) may also be used herein. The "overdried" zeolites are particularly useful when a low humidity environment is required, e.g., to improve the stability of detergent bleaches such as perborate and percarbonate. Preferably, the aluminosilicate has a particle size of 0.1 to 10 µm in diameter. Preferred ion exchange materials have a particle size diameter of 0.2 µm to 4 µm. The term "particle size diameter" as used herein means the average particle size diameter by weight of a particular ion exchange material as determined by conventional analytical techniques, such as by microscopic determination using a scanning electron microscope. The crystalline zeolite A materials used herein are usually further characterized by their calcium ion exchange capacity which is at least 200 mg equivalents of CaCO3 water hardness/g aluminosilicate, calculated on an anhydrous basis, and which is generally in the range of 300 mg eq/g to 352 mg eq/g. The zeolite A materials used herein are further characterized by their calcium ion exchange rate which is at least 2 grains Ca++/gallon/minute/gram/gallon (0.13 g Ca++/liter/minute/gram/liter) aluminosilicate (anhydrous basis) and generally in the range of 2 grains/gallon/minute/gram/gallon (0.13 g Ca++/liter/minute/gram/liter) to 6 grains/gallon/minute/gram/gallon (0.39 g Ca+/liter/minute/gram/liter) based on calcium ion hardness. Optimum aluminosilicate for builder purposes exhibits a calcium ion exchange rate of at least 4 grains/gallon/minute/gram/gallon (0.26 g Ca+/liter/minute/gram/liter).

The granular agglomerates of the present invention also include other detergent ingredients.

Water-soluble salts of the higher fatty acids, i.e. "soaps", are useful anionic surfactants in the compositions described herein. This includes alkali metal soaps, such as sodium, potassium, ammonium and alkylammonium salts, of higher fatty acids having 8 to 24 carbon atoms, and preferably 12 to 18 carbon atoms. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of mixtures of fatty acids derived from coconut oil and tallow, i.e. sodium and potassium tallow and coconut soaps.

Useful anionic surfactants also include the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfur reaction products containing in their molecular structure an alkyl group of 10 to 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is the alkyl portion of acyl groups). Examples of this group of synthetic surfactants are the sodium and potassium alkyl sulfates, particularly such as those obtained by sulfation of the higher alcohols (C8-C18 carbon atoms), such as those prepared by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkylbenzenesulfonates in which the alkyl group contains 9 to 15 carbon atoms in straight chain or branched chain configuration, e.g. B. those of the type described in U.S. Patent Nos. 2,220,099 and 2,477,383; and methyl ester sulfonates. Particularly valuable are the linear straight-chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is between 11 and 13, abbreviated as C₁₁-C₁₃ LAS.

Other anionic surfactants herein are the sodium alkyl glyceryl ether sulfonates, particularly those higher alcohol ethers derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkylphenol ethylene oxide ether sulfates having 1 to 10 units of ethylene oxide per molecule and wherein the alkyl groups contain 8 to 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates having 1 to 10 units of ethylene oxide per molecule and wherein the alkyl group contains 10 to 20 carbon atoms.

Other useful anionic surfactants herein include the water-soluble salts of esters of α-sulfonated fatty acids having 6 to 20 carbon atoms in the fatty acid group and 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids having 2 to 9 carbon atoms in the acyl group and 9 to 23 carbon atoms in the alkane moiety; alkyl ester sulfates having 10 to 20 carbon atoms in the alkyl group and 1 to 30 moles of ethylene oxide; water-soluble salts of olefin sulfonates having 12 to 24 carbon atoms; and β- Alkoxyalkanesulfonates having 1 to 3 carbon atoms in the alkyl group and 8 to 20 carbon atoms in the alkane moiety. Although the acid salts are typically discussed and used, acid neutralization can be performed as part of the fine dispersion mixing step.

Water-soluble nonionic surfactants are also useful as surfactants in the compositions of the invention. In fact, preferred methods use anionic/nonionic mixtures. Such nonionic materials include compounds prepared by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group condensed with any particular hydrophobic group can be readily adjusted to provide a water-soluble compound with the desired degree of balance between hydrophilic and hydrophobic elements.

Suitable nonionic surfactants include the polyethylene oxide condensates of alkylphenols, e.g. the condensation products of alkylphenols containing an alkyl group containing 6 to 16 carbon atoms in either a straight chain or branched chain configuration with 4 to 25 moles of ethylene oxide per mole of alkylphenol.

Preferred nonionics are the water-soluble condensation products of aliphatic alcohols containing 8 to 22 carbon atoms in either straight-chain or branched-chain configuration with 1 to 25 moles of ethylene oxide per mole of alcohol, especially 2 to 7 moles of ethylene oxide per mole of alcohol. Particularly preferred are the condensation products of alcohols with an alkyl group containing 9 to 15 carbon atoms; and condensation products of propylene glycol with ethylene oxide.

Other preferred nonionics are polyhydroxy fatty acid amides, which can be prepared by the reaction of a fatty acid ester and an N-alkyl polyhydroxyamine. The preferred amine for use in the present invention is N-(R1)-CH2(CH2OH)4- CH2-OH, and the preferred ester is a C12-C20 fatty acid methyl ester. Most preferred is the reaction product of N-methylglucamine (which can be derived from glucose) with a C12-C20 fatty acid methyl ester.

Methods for preparing polyhydroxy fatty acid amides have been described in WO 9206073, published April 16, 1992. This application describes the preparation of polyhydroxy fatty acid amides in the presence of solvents. In a highly preferred embodiment of the invention, N-methylglucamine is reacted with a C12-C20 methyl ester. It is also stated that the formulator of granular detergent compositions may find it convenient to run the amidation reaction in the presence of solvents comprising alkoxylated, particularly ethoxylated (EO 3-8) C12-C14 alcohols (page 15, lines 22-27). This leads directly to nonionic surfactant systems suitable for use in the present invention, such as those comprising N-methylglucamide and C12-C14 alcohols having an average of 3 ethoxylate groups per molecule.

Semi-polar nonionic surfactants include water-soluble amine oxides having an alkyl radical of 10 to 18 carbon atoms and 2 radicals selected from the group consisting of alkyl groups and hydroxyalkyl groups of 1 to 3 carbon atoms; water-soluble phosphine oxides having an alkyl radical of 10 to 18 carbon atoms and 2 radicals selected from the group consisting of alkyl groups and hydroxyalkyl groups of 1 to 3 carbon atoms; and water-soluble sulfoxides having an alkyl radical of 10 to 18 carbon atoms and a radical selected from the group consisting of alkyl and hydroxyalkyl radicals of 1 to 3 carbon atoms.

Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be either straight chain or branched chain and wherein one of the aliphatic substituents contains 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water solubilizing group.

Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium phosphonium and sulfonium compounds in which the aliphatic substituents contain 8 to 18 carbon atoms.

Useful cationic surfactants include water-soluble quaternary ammonium compounds of the form R4R5R6R7N+X-, wherein R4 is alkyl of 10 to 20, preferably 12 to 18, carbon atoms, and R5, R6 and R7 are each C1 to C7 alkyl, preferably methyl; X- is an anion, e.g. chloride. Examples of such trimethylammonium compounds include C12-14 alkyl trimethylammonium chloride and cocoalkyl trimethylammonium methosulfate.

The granular detergents of the present invention may contain neutral or alkaline salts which have a pH of 7 or more in solution and may be organic or inorganic in nature. The builder salt helps provide the desired density and bulk to the detergent granules described herein. While some of the salts are inert, many of them also function as detergent builder materials in the laundry solution.

Examples of neutral water-soluble salts include the alkali metal, ammonium or substituted ammonium chlorides, fluorides and sulfates. The alkali metal, and particularly sodium, salts of the above are preferred. Sodium sulfate is typically employed in detergent granules and is a particularly preferred salt. Citric acid and generally any other organic or inorganic acid may be incorporated into the granular detergents of the present invention so long as it is chemically compatible with the remainder of the agglomerate composition.

Other useful water-soluble salts include the compounds commonly known as detergent builder materials. Builders are generally selected from the various water-soluble alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates and polyhydroxysulfonates. Preferred are the alkali metal, especially sodium, salts of the above.

Specific examples of inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of about 6 to 21, and orthophosphate. Examples of polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic acid, and the sodium and potassium salts of ethane-1,1,2-triphosphonic acid. Other phosphorus builder compounds are described in U.S. Patent Nos. 3,159,581, 3,213,030, 3,422,021, 3,422,137, 3,400,176, and 3,400,148.

Examples of non-phosphorus inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate and silicate having a molar ratio of SiO2 to alkali metal oxide of from 0.5 to 4.0, preferably from 1.0 to 2.4. The compositions prepared by the process of the present invention do not require excess carbonate for processing and preferably do not contain more than 2% finely divided calcium carbonate, as described in U.S. Patent No. 4,196,093, Clarke et al., issued April 1, 1980, and are preferably free of the latter.

Polymers

Also useful are various organic polymers, some of which can act as builders to improve detergency. Included among such polymers are sodium carboxy lower alkyl celluloses, sodium lower alkyl celluloses and sodium hydroxy lower alkyl celluloses such as sodium carboxymethyl cellulose, sodium methyl cellulose and sodium hydroxypropyl cellulose, polyvinyl alcohols (which often also include some polyvinyl acetate), polyacrylamides, polyacrylates and various copolymers such as those of maleic and acrylic acids. Molecular weights for such polymers vary widely, but most are in the range of 2,000 to 100,000. Other suitable polymers are polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.

Polymeric polycarboxylate builders are set forth in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid, and methylenemalonic acid.

Silicone oils

Particulate suds suppressors can also be incorporated directly into the agglomerates described herein by means of the powder stream in the agglomeration unit or into the final composition by dry addition. Preferably, the suds suppression activity of these particles is based on fatty acids or silicones.

In one embodiment of the present invention, the silicone oil is adsorbed on the specific zeolite A.

Optional components

Other ingredients that can be conventionally used in detergent compositions can be incorporated into the compositions of the present invention. These include flow aids, color speckles, bleaches and bleach activators, suds boosters or suds suppressors, anti-tarnish and anti-corrosive agents, soil suspending agents, soil release agents, colorants, fillers, optical brighteners, germicides, pH adjusting agents, non-builder alkalinity sources, hydrotropes, enzymes, enzyme stabilizing agents, chelating agents and fragrances.

These optional ingredients, particularly optical fillers, can either be incorporated directly into the agglomerates described herein, or they can be components of separate particles suitable for dry addition to the agglomerates of the present invention.

processing

Useful agglomeration processes are described in EP-A-510 746, published on 28.

October 1992, and in WO 93/25378, published December 23, 1993. These applications describe the agglomeration of solids with a highly active neutralized surfactant paste. However, it will be recognized that the highly active neutralized paste can be replaced in whole or in part by other surfactants, particularly nonionic surfactants (as in EP 643 130, published March 15, 1995), or by organic polymers or silicone oils. Preferred embodiments of the process are described in more detail in the examples below.

TEST PROCEDURE

Oil absorption values can be determined by the following British Standard test BS3483: Part 7 1982 (equivalent to ISO 787/5-1980). A 5 g sample of zeolite with a free alkalinity of 0.5% should be used. The Oil Absorption Value (OAV) is expressed as follows:

OAV = Oil volume (ml)/weight of zeolite sample (g)

EXAMPLES

All values are expressed in wt%. Zeolite contents are expressed on a hydrated basis (including 15 wt% bound water)

Zeolite A/HS* has an oil absorption capacity of 45.5 m11100 g, sold by Industrial Zeolites (GB) Ltd., of Thurrock, Essex, England.

Zeolite A # has an oil absorption capacity of 36 m11100 g, sold by Degussa under the trade name Wessalith®.

C₁₂₋₁₅₅-AS is sodium alkyl sulfate, with the alkyl chains consisting principally of C₁₂-C₁₅. C₁₂₋₁₅-AE3S is sodium alkyl ether sulfate, with the alkyl chains consisting principally of C₁₂-C₁₅, and with an average of 3 ethoxy groups per molecule.

The copolymer is a copolymer of acrylic and maleic acid.

Nonionic surfactant comprises 7 parts ethoxylated alcohol, the alkyl chains comprising principally C₁₂-C₁₅, and with an average of 3 ethoxy groups per molecule; and 3 parts C₁₂₋₁₄-polyhydroxy fatty acid amide.

Miscellaneous mainly includes sulfate and other minor impurities.

Granular agglomerates having the composition of Example 1 were prepared by the following procedure. The powdered raw materials (zeolite AIHS and sodium carbonate) were added to the plate of an Eirich® mixer rotating at 64 rpm and mixed for 10 seconds. The mixing plate was then stopped and preheated surfactant paste (50ºC), 80% active surfactant in aqueous solution, was then added in discs to a cavity formed in the center of the powder. Loose powder was scooped over the paste to completely cover it. The mixer was then restarted with the plate rotating at 64 rpm and choppers set at 2500 rpm. The mixer was stopped when granular agglomerates began to form (at this point the current drawn by the Eirich increased from 2.8 to 3 amps.

The resulting granular agglomerates were free-flowing and contained less than 25 wt% of oversized particles (oversized particles are considered to be those particles with a size greater than 1600 µm).

Granular agglomerates having the composition of Example 2 were prepared by the following procedure.

A paste comprising the surfactants was prepared by sulfating and neutralizing suitable alcohols. The resulting paste had a water content of 18%. The paste was pumped into a high shear mixer (Loedige CB®). At the same time, zeolite A/HS and sodium carbonate were introduced into the high shear mixer and mixed intimately with the highly viscous paste present therein. The resulting mixture was transferred directly to a low shear mixer (Loedige KM®) where agglomerates were formed. After exiting the low shear mixer, the agglomerates were sieved to remove oversized "lumps" and fines. Finally, the agglomerates were cooled and stored in a fluid bed before dry blending with other detergent powders to form a finished product. The residence time in the high shear mixer was about 8 seconds and the residence time in the low shear mixer was about 35 seconds.

Granular agglomerates having the composition of Example 3 were prepared by the same procedure as Example 2, replacing the anionic surfactant paste with the nonionic surfactant kept as a viscous paste at 70°C.

Granular agglomerates having the composition of Comparative Example A were prepared by the same procedure as in Example 1, using the same time for mixing the powders and the paste as used in Example 1. The resulting granular agglomerates had more than 25 wt.% of oversized particles (oversized particles are considered to be those particles with a size greater than 1600 µm).

Claims (13)

1. A process for producing a granular detergent composition or component having a bulk density of more than 650 g/l, comprising the step of dispersing a liquid binder through a powder stream in a high speed mixer to form granular agglomerates, characterized in that the powder stream comprises a powder consisting essentially of crystalline zeolite A, P, X, Y or mixtures thereof, and crystalline zeolite HS. 2. The process according to claim 1, wherein the powder consisting essentially of crystalline zeolite A, B, X, Y or mixtures thereof and crystalline zeolite HS has an oil absorption capacity of at least 40 ml / 100 g. 3. Process according to claim 2, wherein the ratio of zeolite A, P, X, Y or mixtures thereof to crystalline zeolite HS is 1:1 to 99:1, preferably 3:1 to 20:1. 4. Process according to at least one of claims 1 to 3, wherein the powder stream comprises a powder consisting essentially of crystalline zeolite A and crystalline zeolite HS. 5. Process according to at least one of claims 1 to 3, wherein the powder stream comprises a powder consisting essentially of crystalline zeolite P and crystalline zeolite HS. 6. A process according to any one of claims 1 to 5, wherein the granular agglomerates are formed by mixing in the high speed mixer for a residence time of 2 seconds to 30 seconds, followed by the step of further mixing in a moderate speed mixer/agglomerator for a residence time through the moderate speed mixer of less than 5 minutes, preferably less than 2 minutes, during which a finely divided powder may optionally be added. 7. The method of claim 6, wherein the liquid binder is a paste, which comprises at least 10% by weight of a neutralized anionic surfactant, the paste having a viscosity of at least 10,000 mPas. 8. The method of claim 7, wherein the liquid binder is a surfactant paste comprising at least 70% by weight surfactant, wherein the surfactant is selected from the group consisting of anionic, nonionic, cationic, amphoteric, zwitterionic surfactants and mixtures thereof. 9. A process according to claim 7, wherein the granular detergent composition or component comprises: a) 20 to 80% by weight of a powder consisting essentially of crystalline zeolite A, P, X, Y or mixtures thereof, and crystalline zeolite HS; b) at least 20% by weight surfactant. 10. A process according to claim 7, wherein the granular detergent composition or component comprises: a) 20 to 70% by weight of a powder consisting essentially of crystalline zeolite A, P, X, Y or mixtures thereof, and crystalline zeolite HS; b) at least 30% by weight of anionic surfactant; where the ratio of crystalline zeolite A to anionic surfactant is less than 1:1. 11. A process according to claim 7, wherein the granular detergent composition or component comprises: a) 20 to 80% by weight of a powder consisting essentially of crystalline zeolite A, P, X, Y or mixtures thereof, and crystalline zeolite HS; b) at least 20% by weight of non-ionic surfactant; where the ratio of crystalline zeolite A to non-ionic surfactant is less than 2:1. 12. A process according to claim 3, wherein the granular detergent composition or component comprises: a) 20 to 70 wt.% of a powder consisting essentially of crystalline zeolite A, P, X, Y or mixtures thereof, and crystalline zeolite (b) at least 30% by weight of an organic polymer: 13. A process according to claim 3, wherein the granular detergent composition or component comprises: a) 20 to 70% by weight of a powder consisting essentially of crystalline zeolite A, P, X, Y or mixtures thereof, and crystalline zeolite HS; b) at least 30% by weight of a silicone oil.