KR100258542B1 - Process for producing granular detergent components or compositions - Google Patents

Abstract

The present invention relates to a method for preparing a granular detergent composition or component having a bulk density of greater than 650 g / l, comprising dispersing a liquid binder in a high speed mixer throughout a powder strip to form granular aggregates. The powder stream comprises crystalline zeolite A having an oil absorption capacity of at least 40 ml / 100 g, preferably at least 45 ml / 100 g, most preferably at least 50 ml / 100 g.

Description

[Name of invention]

Process for preparing granular detergent product

Detailed description of the invention

The present invention relates to a continuous preparation of a granular detergent composition or component (product) with a high bulk density and good flow characteristics. In such compositions and components, it is known to use crystalline zeolite A, a water insoluble crystalline material well known in the detergent field, as a particularly suitable builder for removing cations such as calcium and magnesium from hard water. have.

Crystalline zeolite A is a highly finely divided powder. The finely divided powder is usually prepared in larger granular form (typically 400-1000 μm) prior to introduction into the processed product, in particular the processed detergent composition. Granulation methods are known for various granulation methods including spray drying and agglomeration. Conventional flocculation methods in which zeolite A is used as one of the components have been known for a long time in the prior art.

British Patent 2005715, published April 25, 1979, describes a coagulation method based on zeolite A. In this method, zeolite A is coagulated with carbonate / bicarbonate to prepare a nonionic surfactant aggregate.

WO 93/25378, published December 23, 1993, describes a process for preparing granular detergents comprising zeolite A. In this process, zeolite A is agglomerated in a high activity neutral surfactant paste, a high speed mixer, and a mixer of a suitable speed to form an anionic surfactant aggregate.

One of the factors limiting the activity of the surfactants of the prior art mentioned above is the liquid organic substance absorbency of zeolite A. It has been suggested that replacing zeolite A with zeolite P (particularly zeolite MAP) can solve this problem.

European Patent Publication No. 521635, published January 7, 1993, describes granular detergents prepared using 10 to 100% zeolite MAP. Example 1 of the patent application reports that the oil absorption capacity of the zeolite MAP is 41.6 ml / 100 g and this oil absorption capacity is greater than the oil absorption capacity of the zeolite A sample, measured from 26 to 35.5 ml / 100 g. However, changes in the chemical structure of conventional crystalline zeolite A (eg, changes in the stoichiometric ratios of Si, Al, Na, O, H) are always desirable because they essentially affect other properties and characteristics of the zeolite. It is not.

It is an object of the present invention to provide a granulation process for producing granular detergents which introduce superabsorbent crystalline zeolites into granular aggregates without loss of builder capacity, in particular calcium exchange capacity and calcium exchange rate.

This object is achieved according to the invention by using modified crystalline zeolite A with high oil absorption in the process described in claim 1 herein. Rather than modifying the chemical structure to achieve oil absorption of 40 ml / 100 g moving, the physical properties of zeolite A (eg crystallinity, surface area properties, moisture content, etc.) were modified. In this way the excellent builder properties of zeolite A can still be utilized.

The present invention also seeks to provide a granulation process for producing granular detergents having improved processability, in which the amount of excessively sized particles (or “lumps”) formed is reduced.

[Summary of invention]

It is an object of the present invention to apply a liquid binder throughout a powder stream comprising crystalline zeolite A having an oil absorption of at least 40 ml / 100 g, preferably at least 45 ml / 100 g and most preferably at least 50 ml / 100 g in a high speed mixer. Dispersed to form granular aggregates, thereby achieving a granular detergent composition or component having a bulk density greater than 650 g / l.

In a preferred embodiment of the invention, the granular aggregates are added for a residence time of about 2 to about 30 seconds in a high speed mixer and for a residence time of less than about 5 minutes, preferably less than 2 minutes, at a suitable speed of mixer. Formed by mixing with (optionally finely divided powder can be added in this step).

In another embodiment of the present invention, the liquid binder is a surfactant paste, organopolymer or silicone oil. Surfactant pastes may include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof, most preferably anionic surfactants and / or It is a nonionic surfactant.

Detailed description of the invention

Granulation associated with the present invention is itself a granulation, which is an aggregate of particles that behave as particles according to SA Kuti, "Agglomeration-The Practical Alternative", published in Journal American Oil Chemists Society, Volume 55. January 1978. It is defined as the method of preparing the saponified product. Granulation aggregates are defined herein as products of the granulation process above. Kuti continues to describe that aggregates are typically formed by blending solids and liquids that act as adhesives. However, lump-free liquid-solid blends are often difficult to manufacture.

In the present invention, the "solid" referred to by Cutie will include crystalline zeolite A having certain physical properties defined more specifically below. It has now been found that this selection of "solid" contributes greatly to the performance of the preparation of liquid-solid blends without lumps.

An essential component of the particulate aggregate of the present invention is crystalline zeolite A of formula (1).

[Formula 1]

(Na ₂ 0) (Al ₂ O ₃ ) x (SiO ₂ ) wH ₂ O

In Formula 1, x is 1 to 2, w is 0 to 6.

Partially hydrated or hydrated zeolite A with a particle size of 10 μm or less is preferred.

In a particularly preferred embodiment, where x is 2, the zeolite A material is a compound of formula 2 and its particle size is generally less than about 5 microns.

[Formula 2]

Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] · (6w ') H ₂ O

In Formula 2, (6w ') is about 20 to about 30, especially about 27.

In the present invention, the zeolite A material may contain up to about 28% water. Preferred builder materials are in hydrated form and contain about 5 to about 28 weight 5 water. Highly preferred crystalline aluminosilicate ion exchange materials contain about 10 to about 22% water in the crystal matrix. Crystalline zeolite A material contains about 10 to about 22% water in the crystal matrix. Crystalline zeolite A material is further characterized by a particle size diameter of about 0.1 to about 10 microns. Preferred ion exchange materials have a particle size diameter of about 0.2 to about 4 microns. The term “particle size diameter” herein refers to the average particle size diameter per weight of a given ion exchange material measured by conventional analytical techniques such as, for example, microscopic measurements using scanning electron microscopy. The crystalline zeolite A material herein is typically calculated on an anhydrous basis, about 200 mg eq./g, where the unit mg eq./g represents the CaCO ₃ number hardness equivalents (mg) per gram of aluminosilicate. The above is further characterized by the calcium ion exchange capacity of the aluminosilicate, which is generally about 300 to about 352 mg eq./g. Zeolite A materials herein, as more and more, based on the hardness of the calcium ion, from about 2 grains ^{Ca ++ /gal/min/g/gal(0.13 Ca ++ / ℓ /} min / ℓ) or more, in general, From about 2 grains / gal / min / g / gal (0.13 Ca ⁺⁺ / l / min / l) to about 6 grains / gal / min / g / gal (0.39 Ca ⁺⁺ / l / min / l) Characterized by the rate of calcium exchange of aluminosilicates (anhydrous basis). Optimum aluminosilicates for the purpose of builders exhibit calcium ion exchange rates of greater than about 4 grains / gal / min / g / gal (0.13 Ca ⁺⁺ / l / min / l).

Zeolite A materials useful in the practice of the present invention are commercially available. Samples of suitable zeolite A materials include Soprolit; Manufacturer's Ref: 94/099/1] and Enenichem; Manufacturer Reference No. AF1094. Aluminosilicates useful in the present invention are structurally crystalline and may be naturally occurring aluminosilicates or derived for synthesis. Methods of making aluminosilicate materials are discussed in US Pat. No. 3,985,669 to Krummel et al., Issued Oct. 12, 1976, which is incorporated herein by reference.

It is an essential aspect of the present invention that the zeolite A used to form the granular aggregates has an oil absorption capacity of at least 40 ml / 100 g, preferably at least 45 ml / 100 g, most preferably at least 50 ml / 100 g. The method of measuring oil absorption capacity is defined below under the heading "Test Method".

Optionally, other forms of zeolite may be present in a mixture with zeolite A, for example zeolite P, zeolite X and zeolite HS.

Granular aggregates of the present invention also include other detergent components.

Water-soluble salts of higher fatty acids, ie "soaps", are anionic surfactants useful in the compositions of the present invention. Examples thereof include alkali metal soaps such as sodium salts, potassium salts, ammonium salts, and alkylammonium salts of higher fatty acids having about 8 to about 24 carbon atoms, preferably about 12 to about 18 carbon atoms. Soaps can be prepared by direct saponification of fats and oils or by neutralization of our fatty acids. Particularly useful are the sodium and potassium salts, ie sodium or potassium resins and coconut soap, of mixtures of fatty acids derived from coconut oil and tallow.

Useful anionic surfactants are also water-soluble salts, preferably alkali metal salts, ammonium salts and alkylol ammonium salts of organic sulfur-based reaction products containing alkyl groups having from about 10 to 20 carbon atoms and sulfonic acid or ester sulfate groups in the rich structure [where , The term "alkyl" is an alkyl moiety of an acyl group. Examples of synthetic surfactants of this group are those obtained by sulphating sodium and potassium alkyl sulfates, especially higher alcohols (C ₈ -C ₁₈ ) such as those prepared by reducing the glycerides of resins or coconut oil, and straight or branched chains. Sodium and potassium alkyl benzene sulfonates in an arrangement, wherein the alkyl group contains about 9 to about 15 carbon atoms. And methyl ester sulfonates of the type described in, for example, US Pat. Nos. 2,220,099 and 2,477,383. Of particular value are straight chain alkyl benzene sulfonates having about 11 to 13 carbon atoms in the alkyl group (hereinafter referred to as C ₁₁ -C ₁₃ LAS).

Other anionic surfactants herein include sodium alkyl glyceryl ether sulfonates, especially ethers of higher alcohols derived from resins and coconut oil, sodium coconut oil fatty acid monoglyceride sulfonates and sulfates, about 1 to about 10 per molecule Sodium or potassium salts of alkyl phenolethylene oxide ether sulfates containing ethylene oxide units and having from about 8 to 12 carbon atoms in the alkyl group, and from about 1 to about 10 ethylene oxide units per molecule and containing about 1 to about carbon atoms in the alkyl group. Sodium or potassium salt of alkyl ethylene oxide ether sulfate of from 10 to about 20.

Other anionic surfactants useful herein include water-soluble salts of esters of a-sulfonated fatty acids having about 6 to 20 carbon atoms in the fatty acid group and about 1 to 10 carbon atoms in the fatty acid group, about 2 to 9 carbon atoms in the acyl group Water-soluble salts of 2-acyloxy-alkane-1sulfonic acids having from about 9 to about 23 carbon atoms in alkanes residues, alkyl ether sulfates containing from about 10 to 20 carbon atoms in alkyl groups and containing from about 1 to 30 mol of ethylene oxide, about carbon atoms Water-soluble salts of olefin sulfonates of 12 to 24 and β-alkyloxy alkane sulfonates having from about 1 to about 3 carbon atoms and about 8 to about 20 carbon atoms of an alkane residue. Acid salts are typically discussed and used, but acid neutralization may be performed as part of the microdispersion mixing step.

Water soluble anionic surfactants are also useful as surfactants in the compositions of the present invention. In practice the preferred method uses anionic and nonionic combinations. Such nonionic materials include compounds produced by condensation of alkylene oxide groups (which are hydrophilic in nature) with organic hydrophobic compounds, which may be aliphatic or alkyl aromatic. The length of the polyoxyalkylene group condensed with any particular hydrophobic group can be easily adjusted to yield a water soluble compound having a desired balance between the hydrophilic component and the hydrophobic component.

Suitable nonionic surfactants include polyethylene oxide condensates of alkyl phenols in straight or branched chain configurations having about 4 to 25 mol of ethylene oxide per mole of alkyl phenol, for example condensation products of alkyl phenols having alkyl groups of about 6 to 16 carbon atoms. do.

Preferred nonionic surfactants are water-soluble condensation products of aliphatic alcohols of straight or branched chain C8-C22 having from 1 to 25 mol, in particular from 2 to 7 mol of ethylene oxide units per mol of alcohol. Especially preferred are condensation products of alcohols having alkyl groups of about 9 to 15 carbon atoms and condensation products of propylene glycol with ethylene oxide.

Other preferred nonionic surfactants are polyhydroxy fatty acid amides that can be prepared by reacting fatty acid esters with N-alkyl polyhydroxy amines. Preferred amines for use in the present invention are N- (R ₁ ) -CH ₂ (CH ₂ OH) ₄ -CH ₂ -OH and preferred esters are C ₁₂ -C ₂₀ fatty acid methyl esters. Most preferably it is the reaction product of N-methyl glucamine (which can be derived from glucose) with C ₁₂ -C ₂₀ fatty acid methyl esters.

A process for preparing polyhydroxy fatty acid amides is described in WO 9206073, published April 16, 1992. This application describes the preparation of polyhydroxy fatty acid amides in the presence of a solvent. In a very preferred embodiment of the present invention, N-methyl glucamine is reacted with C ₁₂ -C ₂₀ methyl ester. It will also be appreciated that the formulator of the granular detergent composition is convenient to carry out the amidation reaction in the presence of alkoxylation, in particular in the presence of a solvent comprising ethoxylated (EO _3-8 ) C ₁₂ -C ₁₄ alcohols. Patent application page 15, line 22 to line 27]. This application directly obtains nonionic surfactant systems suitable for use in the present invention, for example those containing C ₁₂ -C ₁₄ alcohol and N-methyl glucamine having an average of three ethoxylate groups per molecule.

Semipolar nonionic surfactants are water-soluble amine oxides containing one alkyl moiety having from about 10 to 18 carbon atoms and two position moieties selected from the group consisting of hydroxyalkyl groups and alkyl groups having from 1 to about 3 carbon atoms, carbon atoms A water-soluble phosphine oxide containing one alkyl moiety of about 10 to 18 and two moieties selected from the group consisting of a hydroxyalkyl group and an alkyl group of about 1 to 3 carbon atoms and one alkyl moiety having about 10 to 18 carbon atoms Water-soluble sulfoxides containing two moieties selected from the group consisting of about 1 to 3 hydroxyalkyl moieties and alkyl moieties.

Amphoteric surfactants are aliphatic derivatives or aliphatic derivatives of heterocyclic secondary and tertiary amines wherein the aliphatic residues may be straight or branched and one of the aliphatic substituents contains about 8 to 18 carbon atoms At least one contains an anionic water solubilization group.

Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium phosphonium, and sulfonium, wherein one of the aliphatic substituents contains about 8 to 18 carbon atoms.

Useful cationic surfactants are water ^- soluble quaternary ammonium compounds of the formula R ₄ R ₅ R ₆ R ₇ N ⁺ X ^- wherein R ₄ is alkyl having 10 to 20 carbon atoms, preferably 12 to 18 carbon atoms, and R ₅ , R ₆ and R ₇ are each C ₁ -C ₇ alkyl, preferably methyl, and X ⁻ is an anion, for example chloride. Examples of such trimethyl ammonium compounds include C ₁₂ -C ₁₄ alkyl trimethyl ammonium chloride and cokealkyl trimethyl ammonium methosulfate.

Granular detergents of the present invention may contain neutral or alkaline salts having a pH of 7 or more in solution and which may be organic or inorganic in nature. Builder salts help to give the detergent granules the desired density and bulk. Some of the salts are inert, but many of them also act as washable builder materials in laundry solutions.

Examples of neutral water soluble salts include alkali metal, ammonium or substituted ammonium chlorides, fluorides and sulfates. The above alkali metal salts, in particular sodium salts, are particularly preferred. In the case of chemically miscibility with the remaining aggregate composition, the citric acid of the composition, and generally any other organic or inorganic acid, may be incorporated into the granular detergent of the present invention.

Other useful water soluble salts include compounds commonly known as detergent builder materials. Builders are generally selected from a variety of water soluble alkali metals, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates and polyhydroxysulfonates. Preferably it is said alkali metal salt, especially sodium salt.

Specific examples of inorganic phosphate builders are sodium and potassium tripolycarbonates, pyrophosphates, polymeric metaphosphates having a degree of polymerization of about 6 to 21, and orthophosphates. Examples of polyphosphate builders include sodium and potassium salts of ethylene diphosphonic acid, sodium salts of potassium ethane 1-hydroxy-1,1-disphosphonic acid and potassium salts and sodium of ethane, 1,1,2-triphosphonic acid Salts and carium salts. Other phosphorus builder compounds are described in the United States, in particular, in US Pat. Nos. 3,159,581, 3,213,030, 3,422,021, 3,422,137, 3,400,176 and 3,400,148, which are incorporated herein by reference.

Examples of nonphosphorus inorganic builders include molar ratios of SiO ₂ to sodium and potassium carbonates, bicarbonates, sesquicarbonates, tetraborate decahydrates, and alkali metal oxides from about 0.5 to about 4.0, preferably about Silicates from 1.0 to about 2.4. Compositions prepared according to the process of the present invention do not require excess carbonate for processing and are preferably described in US Pat. No. 4,196,093 to Clarke et al., Issued April 1, 1980. It does not contain more than 2% finely divided calcium carbonate and preferably they are free.

[polymer]

Various organic polymers are also useful, some of which may also serve as builders to improve cleanability. Such polymers include sodium carboxy-lower alkyl cellulose, and sodium hydroxy-lower alkyl cellulose [eg; Sodium carboxymethyl cellulose, sodium methyl cellulose and sodium hydroxypropyl cellulose]. Polyvinyl alcohols, which often also include polyvinyl acetate, polyacrylamide polyacrylates and various copolymers such as copolymers of maleic acid and acrylic acid may be mentioned. The molecular weight of such polymers can 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, polyvinyloxazolidone and polyvinylimidazole or mixtures thereof .

Polymeric polycarboxylate builders are shown in US Pat. No. 3,308,067 to Diehl, issued March 7, 1967. Such materials include homopolymers and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconic acid, citraconic acid and methylenemalonic acid.

[Silicone oil]

Granular foam inhibitors may also be incorporated directly into the flocculating unit by a powder stream in the aggregate or by dry addition in the processed composition. Preferably the antifoam activity of these particles is based on fatty acids or silicones.

In one embodiment of the invention, the silicone oil is absorbed into a particular zeolite A.

[Optional ingredients]

Other ingredients conventionally used in detergent compositions can be included in the compositions of the present invention. These other ingredients include flow aids, color speckles, bleaches, bleach activators, foam accelerators, foam inhibitors, antitarnishes, preservatives, dirt suspensions, dirt release agents, dyes, fillers, fluorescents Brighteners, fungicides, ph regulators, nonbuilder alkalinity sources, hydrotropes, enzymes, enzyme stabilizers, chelating agents and flavoring agents.

These optional components, in particular fluorescent brighteners, may be introduced directly into the aggregates or may be components of separate particles suitable for dry addition to the aggregates of the present invention.

[Processing]

Useful flocculation processes are defined in European Patent Application No. 510746 published October 28, 1992 and WO093 / 25378 published December 23, 1993. The patent applications describe the coagulation of solids with highly active neutralized surfactant pastes. However, the highly active neutralized pastes may be completely or partially replaced with other surfactants, in particular nonionic surfactants (European Patent No. 643130 published March 15, 1995) or organic polymers or silicone oils. Can be. Preferred embodiments of this process are described in more detail in the Examples below.

[Test Methods]

Oil absorption values can be measured according to the following British standard, BS3483: Part 7: 1982 [corresponding to ISO 787 / 5-1980]. In this case, 5 g of zeolite sample having a free alkalinity of less than 0.5% should be used. The oil absorption value (0AV) is represented by equation (1).

[Equation 1]

EXAMPLE

All values are expressed in weight percent. The amount of zeolite is indicated on a hydrated basis (including 15 wt.% Of binding water).

TABLE 1

Zeolite A ^* has an oil absorption of 45.5 mL / 100 g and is supplied by Industrial Zeolites (UK) Ltd. of Essex Thurrock, UK. Zeolite A # is supplied under the trade name used (Wessalith ') raised by the gateway speaking (Degussa), and to hold the 36㎖ / 100g five days absorption capacity .C ₁₂ - ₁₅ AS is the number of carbon atoms of the alkyl chain mainly 12 to 15 of Sodium alkyl sulfate. C ₁₂ - ₁₅ AE3S is the number of carbon atoms of the alkyl chain mainly 12 to 15 and is a sodium alkyl ether sulfate having an average of three ethoxy groups on each molecule. The copolymer is a copolymer of acrylic acid and maleic acid. Nonionic surfactants include 7 parts of an ethoxylated alcohol and 3 parts of a polyhydroxy fatty acid amide having an alkyl chain of mainly 12 to 15 carbon atoms and an average of three ethoxy groups per molecule. Trace components are sulfates with some minor amounts of impurities.

,혼합기(Eirich, mixer)의 팬에 가하고 10초 동안 혼합한다. 이어서, 혼합기 팬을 정지시키고 계면활성제 페이스트를 예열하고(50℃), 수용액 중에서 활성인 80%계면활성제를 슬라이스 중에서 분말의 중앙에 형성된 구멍에 가한다. 느슨한 분말이 페이스트 위에 스쿠핑(scooping)되어 이를 완전히 피복한다. 이어서, 혼합기를 64rpm으로 회전하는 팬으로 재차 시동시키고 초퍼(chopper)를 2500rpm으로 설정한다. 입상 응집물이 형성되기 시작하면(에리히에 의해 회수된 전류가 2.8amp에서 3amp로 상승하는 시점에서)혼합을 중단한다.Granular aggregates having the composition of Example 1 were prepared according to the following method. Erich rotating the powdered raw materials (zeolite A and sodium carbonate) at 64 rpm

Add to pan of mixer (Eirich, mixer) and mix for 10 seconds. The mixer pan is then stopped and the surfactant paste is preheated (50 ° C.) and 80% surfactant active in aqueous solution is added to the hole formed in the center of the powder in the slice. Loose powder is scooped over the paste to completely cover it. The mixer is then started again with a fan rotating at 64 rpm and the chopper is set to 2500 rpm. When the granular aggregates begin to form (the point at which the current recovered by Erich rises from 2.8 amps to 3 amps) the mixing is stopped.

The resulting granular agglomerates are free flowing and have an amount of less than 25% by weight of particles of excessive size (excess sized particles are considered to have a particle size exceeding 1600 μm). Pastes comprising surfactants are prepared by sulphating and neutralizing the appropriate alcohol. The moisture content of the resulting paste is 18%. The paste is pumped into a high shear mixer (Loedige DB). At the same time zeolite A and sodium carbonate are fed into a high shear mixer and mixed evenly with the high shear paste. The resulting mixture is transferred directly to a low shear mixer to form agglomerates. The aggregates exiting the low shear mixer are screened to separate excess size “lumps” and fines. Finally, the aggregates are stored before anhydrous mixing with other detergent powder to cool in the fluid phase and form the processed product. The residence time in the high shear mixer is approximately 8 seconds and the residence time in the low shear mixer is approximately 35 seconds.

Granular aggregates having the composition of Example 3 were prepared in the same manner as in Example 2, except that the anionic surfactant paste was replaced with a nonionic surfactant whose viscosity was maintained at 70 ° C. in the paste state.

Granular aggregates having the composition of Comparative Example A were prepared in the same manner as in Example 1 using the same mixing time of powder and paste as used in Example 1. The resulting granular agglomerate has an amount of oversized particles in excess of 25% by weight, where the oversized particles are considered to have a particle size exceeding 1600 μm.

Claims (9)

Surfactant pastes selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof; Sodium carboxy-lower alkyl cellulose, sodium lower alkyl cellulose, sodium hydroxy-lower alkyl cellulose, polyvinyl alcohol, polyacrylamide, polyacrylate, polyamine N-oxide polymer, N-vinylpyrrolidone and N-vinylimida Organic polymers selected from the group consisting of copolymers of sol, polyvinylpyrrolidone polymers, polyvinyloxazolidone and polyvinylimidazole and mixtures thereof; Silicone oils; And dispersing a liquid binder selected from the group consisting of mixtures throughout the powder stream comprising crystalline zeolite A having an oil absorption capacity of at least 40 ml / 100f in a high speed mixer to form granular aggregates. To produce a granular detergent product having a value of more than 650 g / l. The method of claim 1, wherein the particulate agglomerates are further mixed for a residence time of 2 to 30 seconds in a high speed mixer and for a residence time of less than 5 minutes through a moderate speed mixer in a moderate speed mixer / aggregator. Formed by the step of making. The method of claim 1 wherein the liquid binder is a paste comprising at least 10% by weight of a neutralized anionic surfactant and having a viscosity of at least 10,000 mPas. The method of claim 3, wherein the liquid binder comprises at least 70% by weight of a surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof. How to. 4. The method of claim 3, wherein the granular detergent product comprises 20 to 80% by weight of crystalline zeolite A having an oil absorption capacity of at least 40 ml / 100 g and at least 20% by weight of (b) anionic surfactant. The crystalline zeolite A of claim 3, wherein the granular detergent product comprises (a) 20 to 70% by weight of crystalline zeolite A having an oil absorption capacity of at least 40 ml / 100 g and (b) at least 30% by weight of anionic surfactant. The ratio of to anionic surfactant is less than 1: 1. The crystalline zeolite A of claim 3, wherein the granular detergent product comprises (a) 20 to 80% by weight of crystalline zeolite A having an oil absorption capacity of at least 40 ml / 100 g and (b) at least 20% by weight of nonionic surfactant. The ratio of nonionic surfactant to less than 2: 1. The process of claim 1 wherein the granular detergent product comprises 20 to 70% by weight of crystalline zeolite A having an oil absorption capacity of at least 40 ml / 100 g and at least 30% by weight of organic polymer (b). The process of claim 1 wherein the granular detergent product comprises (a) 20 to 70% by weight of crystalline zeolite A having an oil absorption capacity of at least 40 ml / 100 g and (b) at least 30% by weight of silicone oil.