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WO1993002786A1 - Procede de preparation de granules de zeolithe - Google Patents

Procede de preparation de granules de zeolithe Download PDF

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Publication number
WO1993002786A1
WO1993002786A1 PCT/EP1992/001672 EP9201672W WO9302786A1 WO 1993002786 A1 WO1993002786 A1 WO 1993002786A1 EP 9201672 W EP9201672 W EP 9201672W WO 9302786 A1 WO9302786 A1 WO 9302786A1
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WO
WIPO (PCT)
Prior art keywords
weight
zeolite
liquid
polymeric
granules
Prior art date
Application number
PCT/EP1992/001672
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German (de)
English (en)
Inventor
Wolfgang Seiter
Lothar Pioch
Ulrich Jahnke
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to DE59202099T priority Critical patent/DE59202099D1/de
Priority to EP92916048A priority patent/EP0605436B1/fr
Publication of WO1993002786A1 publication Critical patent/WO1993002786A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites

Definitions

  • the invention relates to a process for the production of zeolite granules with a high bulk density, which have an adsorption capacity for liquid active substances, and the use of the zeolite granules as a preliminary product for the production of detergents and cleaning agents.
  • European patent application 21 267 discloses granules containing zeolites and alkali silicates which have a particle size between 0.15 and 2 mm and a bulk density of 300 to 700 g / l. They are also suitable for adsorbing liquid detergent components, in particular nonionic surfactants. To prepare them, a dry premix of zeolite and alkali metal silicate (mixing ratio 1: 1 to 1: 8) is sprayed with water in a granulator and agglomerated, whereupon the excess water is removed by drying to a residual proportion of less than 5% by weight becomes.
  • German patent application 3838086 describes the production of granules from zeolite and the sodium or potassium salts of polymeric or copolymeric carboxylic acids, the agglomeration or granulation taking place with the addition of a granulating liquid and the agglomerate obtained until a free-flowing granulate is reached a bulk density of 750 to 1,000 g / 1 is dried.
  • the starting point is a homogeneous powdery mixture of a zeolite, which consists of at least 80% of particles with a size of less than 10 ⁇ m, and the salt of the (co) polymeric carboxylic acids and granulated in a further mixture and granule lation stage with the addition of water, which is preferably sprayed onto the powder mixture kept in motion.
  • the polycarboxylates are introduced in solid form and are not added in dissolved form as a constituent of the granulating liquid, since the amount of granulating liquid used is a critical factor and must therefore be able to be metered exactly. Excessive amounts of granulating liquid lead to granules with a broad grain spectrum and an undesirably high coarse fraction (particle size above 2 m length) and to a lower bulk density.
  • the invention relates to a process for the production of granules from zeolite and sodium or potassium salts of polymeric or copolymeric carboxylic acids, the granulation being carried out with the addition of a granulating liquid and the granules obtained having a free-flowing granulate having a bulk density of 750 to 1,000 g / 1 is dried, which is characterized in that part of the zeolite is sprayed Dried form is submitted, at least 90% of the zeolite particles have a diameter between 50 and 700 microns, and the granulating liquid contains a mixture of water, zeolite and (co) polymeric carboxylates.
  • zeolite which generally has a water content of 17 to 25% by weight and is of detergent quality.
  • Suitable zeolites are those of the zeolite A type. Mixtures of zeolite NaA and NaX can also be used, the proportion of zeolite NaX in such mixtures advantageously being less than 30%.
  • the zeolite in spray-dried, solid form preferably consists of at least 90% of particles between 100 and 600 ⁇ m in size. The preferred medium
  • Particle diameter lies between 200 and 500 ⁇ m and in particular between 250 and 400 ⁇ m.
  • those zeolite powder mixtures which consist of 70 to 95% by weight of water-containing zeolite, have a bulk density between 350 and 600 g / l and a small amount of additives such as sodium sulfate, salts of nitrilotriacetic acid, sodium hydroxide, carboxymethyl cellulose and methyl cellulose, particularly mixtures of 'carboxymethylcellulose and methylcellulose, polymeric polycarboxylates, in particular homopolymers and copolymers of acrylic acid, or non-ionic surfactants.
  • Particularly suitable here are the products commercially available under the name Wessalith (R) (products from Degussa).
  • the zeolite used in the granulating liquid is in particular a finely divided zeolite which consists of at most 10% of particles of a size above 30 ⁇ m and in particular of at least 80% of particles of a size of less than 10 ⁇ m.
  • this in particular finely divided zeolite is used in the form of a 45 to 55% by weight aqueous suspension.
  • the granulating liquid contains 10 to 50% by weight and in particular 15 to 30% by weight and with particular advantage up to 25% by weight of this aqueous zeolite suspension.
  • the water content of the suspension and the water content of the suspended and the initially introduced zeolite are included in the calculation of the water balance; the amount of water to be introduced into the granulation stage can be reduced by these shares.
  • the zeolite suspensions used usually additionally contain about 1.5 to 3% by weight, based on the suspension, of stabilizers, which include nonionic surfactants, anionic surfactants, bentonites, smectites or polymeric polycarboxylates.
  • the granules which are produced by the process according to the invention preferably contain 55 to 95% by weight, in particular 60 to 92% by weight, based on the dried granules, of water-containing zeolite. In this case, preferably 1 to 20% by weight and in particular 1.5 to 10% by weight of water-containing zeolite, based on the total amount of water-containing zeolite, is introduced into the granulating liquid as an aqueous suspension.
  • Suitable water-soluble salts of the homopolymeric and / or copolymeric carboxylic acids contained in the granules, of which the sodium salts are preferred are polyacrylic acid, polymethacrylic acid and polymaleic acid, with preference for polyacrylic acid and polymaleic acid, copolymers of acrylic acid or methacrylic acid with maleic acid or vinyl ethers such as Vinyl methyl ether or vinyl ethyl ether, further with vinyl esters such as vinyl acetate or vinyl propionate, acrylamide, methacrylamide and with ethylene, propylene or styrene.
  • copolymeric acids in which one of the components has no acid function, the proportion thereof in the interest of sufficient water solubility is not more than 50 mol%, preferably less than 30 mol%.
  • Copolymers of acrylic acid and methacrylic acid with maleic acid have proven to be particularly suitable. In particular, copolymers are preferred which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid.
  • the relative molecular weight of the homo- or copolymeric polycarboxylates is generally 2,000 to 150,000, preferably 5,000 to 100,000.
  • the polycarboxylates are preferably in the form of 30 to 50% by weight, in particular 35 to 45% by weight .-% aqueous solutions used.
  • the granulating liquid preferably contains 10 to 40% by weight of (co) polymeric carboxylates.
  • water-soluble inorganic salts for example sodium sulfate
  • the polycarboxylates are initially presented in powder form together with the finely divided zeolite. It is preferred to use a maximum of 50% by weight and in particular a maximum of 40% by weight of the polymeric carboxylates in powder form. Zen.
  • the commercially available salts of (co) polymeric carboxylic acids in powder form often contain 5 to 15% by weight of moisture. This proportion of water is also included in the calculation of the water balance.
  • the proportion of the salts in the preparation of the compositions or in the composition of the finished granules is based on anhydrous salt.
  • the dried granules according to the invention preferably contain the salts of the polymeric or copolymeric carboxylic acids in amounts of 2 to 20% by weight and in particular in amounts of 5 to 20% by weight and with particular advantage between 10 and 17% by weight .
  • the granulating liquid preferably contains 40 to 80% by weight of water as a liquid constituent, polymeric or copolymeric carboxylates and zeolite as solid constituents as stated above, as well as anionic and / or nonionic surfactants and in particular nonionic surfactants which are present in liquid form at the granulation temperature.
  • the granulating liquid advantageously consists of 15 to 35% by weight of (co) polymeric carboxylate, 5 to 12% by weight of zeolite (calculated as anhydrous active substance), 2 to 20% by weight from anionic and / or nonionic surfactants and 45 to 75% by weight of water.
  • the granulating liquid consists of 20 to 32% by weight of (co) polymeric carboxylate, 6 to 10% by weight of zeolite (calculated as an anhydrous active substance) and 5 to 15% by weight of nonionic surfactants and 45 to 65% by weight of water.
  • the liquid nonionic surfactants used are preferably ethoxylated and / or propoxylated fatty alcohols, with preference for the ethoxylated fatty alcohols, in particular addition products of 2 to 7 moles of ethylene oxide (E0) with linear primary alcohols, such as, for. B. on coconut oil, tallow fat or oleyl alcohol, or on primary alcohols branched methyl-branched in the 2-position (oxo alcohols).
  • E0 ethylene oxide
  • Preferred ethoxylated fatty alcohols are furthermore those with a narrow homolog distribution (narrow ranks ethoxylates, nre).
  • alkyl glucosides of the general forms R0 (G) x can be used as nonionic surfactants, in which R denotes a primary straight-chain or aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and methyl-branched in the 2-position and G is the symbol that represents a glucose unit.
  • the degree of oligomerization x which indicates the distribution of monoglucosides and oligloglucosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • the granulating liquid can contain, for example, alkyl glucosides in amounts of 1 to 10% by weight, the alkyl glucosides preferably being introduced into the granulating liquid as a 20 to 50% by weight aqueous solution or paste.
  • Suitable anionic surfactants are, for example, the alkali metal salts, sodium or potassium salts, from the class of the sulfonates and sulfates.
  • Preferred surfactants of the sulfonate type are C 1 -C 6 -alkylbenzenesulfonates, in particular C 1-4 alkylbenzenesulfonate, and sulfonates on a fatty chemical basis, such as the esters of ⁇ -sulfofatty acids, the sulfo group being in its salt form (mono salt), e.g. B. the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids into consideration.
  • Suitable surfactants of the sulfate type are, for example, the optionally ethoxylated sulfuric acid monoesters from primary alcohols of natural and synthetic origin, ie. H. from fatty alcohols, such as.
  • the solid, water-soluble anionic surfactants can be incorporated in the liquid constituents of the granulating liquid in powder form or in paste form. If aqueous surfactant pastes are used, the water content is included in the calculation of the liquid constituents, or the amount of liquid introduced into the granule stage can be reduced by this amount.
  • the moist, non-dried granules 100 parts by weight of the zeolite-powder mixture is added or mixed into a homogeneous mixture of zeolite and, if appropriate, powder of the polymeric or copolymeric carboxylic acid granulating liquid in the amount that preferably 15 to 45 parts by weight, in particular 20 to 40 parts by weight and with particular advantage 20 to 32 Parts by weight, based in each case on the moist granules, of liquid constituents are present.
  • the granulation can be carried out batchwise or continuously in conventional mixing and granulating devices. Are suitable for. B.
  • pelletizers which consist of a horizontally arranged or inclined to the horizontal, cylindrical container, in the longitudinal axis of which a shaft equipped with mixing tools and conveyor blades rotates.
  • the granulation liquid can be supplied through the spray nozzle attached to the wall or on the high shaft. If work is carried out continuously, two mixers connected in series can be used, the first mixer being used to produce the dry or, if an aqueous zeolite suspension is used as a component of the granulating liquid, the premix and in the second mixer the granulation with the addition of polycarboxylate. containing and optionally surfactant-containing granulating liquid.
  • Continuous operation is also possible in a mixer, with either the powder streams and / or the powder streams and the zeolite suspension being combined and homogenized in a first mixing section and the mixture being transported with the polycarboxylate-containing mixture in a subsequent mixing section and, if appropriate, treating and granulating granulating liquid containing surfactant.
  • the granulating liquid is preferably sprayed onto the mixture kept in motion by means of nozzles. It is possible to spray a mixture of all components of the granulating liquid or individual components in succession, in particular the surfactant-containing components before and after the addition of the polycarboxylate solution.
  • the granulation is generally carried out at normal to moderately elevated temperatures, preferably at temperatures between 20 and 60 ° C., in particular between 30 and 55 ° C., and generally requires a time of 1.5 to 10 minutes.
  • the drying can be carried out by introducing hot gases in a third mixing zone, e.g. B. a fluidized bed, or after the discharge of the gra- nulate from the mixer, for example in a vibratory conveyor, a free-fall dryer or in a thin layer on a conveyor belt. Drying in a fluidized bed is preferred, the temperature of the granules preferably being between 60 and 100.degree. The drying is carried out until the water added in the granulation stage is removed to a proportion of less than 5% by weight, preferably less than 3% by weight, based in each case on the dried granules .
  • water components that were originally introduced with the zeolite or a (co) polymeric salt which is not used anhydrous can be removed during drying.
  • Such "over-dried" granules can have application advantages, for example when added to detergents which contain moisture-sensitive active ingredients.
  • the dewatering of the zeolite should preferably not be driven below a water content of 18% by weight, based on zeolite, in order to avoid a reduction in activity.
  • the water content of the granules is expediently in a range in which the water-binding capacity of the zeolite is largely saturated, ie in which the zeolite has a total water content of 19 to 22% by weight.
  • the granules preferably have a bulk density of 780 to 950 g / 1, in particular 800 to 920 g / 1. Due to their tight packing and their small pore volume, their absorption capacity for liquid or paste-like detergent components, in particular nonionic surfactants, is somewhat reduced compared to specifically lighter carrier grains, but is still 15 to a maximum of 20% by weight without any notable impairment ⁇ the flowability of the granules. This surprisingly high adsorptive capacity, given the high packing density and the possibly already contained granules of nonionic surfactants, is completely sufficient for the usual fields of application, in particular for use as a mixture component in detergents and cleaning agents.
  • the granules obtained by the process according to the invention are distinguished by a very uniform grain spectrum, in which the fine fraction (particle diameter less than 0.1 mm) generally less than 2% and the Coarse fraction (particle diameter greater than 2 mm) is generally up to 20% (sieve analysis).
  • the content of particles smaller than 0.2 mm is less than 5%
  • the content of coarser particles (larger than 1.6 mm) is not more than 20% and in particular not more than 15%.
  • the coarse and fine particles are sieved.
  • the coarse fractions are ground and mixed into the product, while the fine fractions or the dust are returned to the granulation.
  • the granules disintegrate quickly and completely in cold water and leave no residues in the washing-up devices of washing machines, ie. H. they have a very good induction ability. This advantageous property is also noticeable after impregnation with nonionic surfactants and in a mixture with other powdery detergent components.
  • the granules can be impregnated with liquid detergent constituents which cannot be incorporated into conventional powdery or granular detergents and cleaning agents in other ways or only with a loss of activity.
  • liquid detergent constituents which cannot be incorporated into conventional powdery or granular detergents and cleaning agents in other ways or only with a loss of activity.
  • foam inhibitors in particular paraffin hydrocarbons, silicones, silicone resins and bis-acylalkylenediamines derived from long-chain fatty acids and mixtures thereof.
  • Further adsorbable active ingredients are fatty acid alkylolamides and cationic plasticizers, such as quaternary ammonium salts containing long-chain fatty residues, and also fat-dissolving solvents such as terpenes.
  • the granules are preferably used as carrier grains for liquid nonionic surfactants and defoamers, in particular paraffin defoamers.
  • liquid nonionic surfactants and defoamers in particular paraffin defoamers.
  • Suitable nonionic surfactants are alkoxylation products with 10 to 20 carbon atoms in the hydrophobic radical and 3 to 20 glycol ether groups. These include ethoxylation products of alcohols, vicinal diols, amines, thioalcohols, fatty acid amides and fatty acids. Also suitable are block polymers of ethylene oxide and propylene oxide, which are commercially available under the name PluronicC R ) (from BASF / Wya ⁇ dotte). Alkylglucosides or alkylpolyglucosides and mixtures thereof with the ethoxylation products mentioned can also be used.
  • Preferred nonionic surfactants which can be adsorbed on the granules and together with them are in the form of a free-flowing mixture, are derived from alcohols having 12 to 18 carbon atoms which are saturated or olefinically unsaturated, linear or methyl-branched in the 2-position (Oxo residue).
  • Their reaction products with ethylene oxide (EO) or propylene oxide (PO) are water-soluble or water-dispersible mixtures of compounds with different degrees of alkoxylation, the number of EO or PO groups given below being a statistical mean corresponds.
  • ethoxylated fatty alcohols are Ci2-C ⁇ 8 coconut alcohols with 3 to 12 EO, Ci6-C ⁇ s-tallow alcohol with 4 to 16 EO, oleyl alcohol with 4 to 12 EO and ethoxylation products of corresponding chain and EO distribution available from other native fatty alcohol mixtures .
  • ethoxylated oxo alcohols for example those of the composition C 2 -C 15 with 5 to 10 EO and C14-C15 with 6 to 12 EO are suitable.
  • alkoxylates which contain EO groups and PO groups, for example C 1 -C 8 -alcohols of the formula R- (P0) a - (E0) D or R- (E0) b ⁇ ( P0) c , in which a is a number from 1 to 3, b is a number from 5 to 20 and c is a number from 1 to 10, where b should be greater than c
  • the application of the liquid, optionally heated additives, in particular the application of the nonionic surfactants and the melted paraffins to the granules can be carried out by admixing, preferably spraying, the carrier material advantageously being kept in motion by suitable mixing devices. It is particularly advantageous if the additives are applied directly after the granules have been dried to the granules which are still warm, preferably 40 to 80 ° C. Another aftercare of the granular adsorbates is not required. However, leaving the product to rest for several hours at high contents of applied liquid material can be expedient, since its diffusion into the interior of the grain takes some time.
  • the grains can optionally be dusted with a finely divided powder as a powdering agent or coated on the surface.
  • a finely divided powder as a powdering agent or coated on the surface.
  • Suitable powdering agents have a grain size of 0.001 to at most 0.1 mm, preferably less than 0.05 mm and can be present in proportions of 0.03 to 3, preferably 0.05 to 2% by weight, based on the adsorbent loaded with additive.
  • finely powdered zeolites, silica airgel (Aerosil ( R )), colorless or colored pigments, such as titanium dioxide are suitable. In general, however, such an aftertreatment is superfluous, especially since it does not improve the solution properties.
  • the detergent additives can be combined and mixed in a known manner with the granular or pulverulent detergent, for example a tower spray powder and its mixtures with other powder components, such as persalts, enzyme granules, bleach activators or defoamers.
  • the high bulk density and the favorable detergent retention of the additives according to the invention are transferred to these complex mixtures.
  • the detergents generally contain 10 to 40% by weight of the additive according to the invention.
  • the granulation was carried out in a mixing granulator consisting of a horizontally arranged cylindrical mixer with a rotating shaft rotating in the central axis and equipped with mixing elements (ploughshare mixer, Lödige type) with a capacity of 5 liters. Submitted suspension and processed to a homogeneous mixture. After the mixing, which took about 10 seconds to 1 minute, the granulating liquid was sprayed in over the course of 1 to 5 minutes by means of nozzles and the mixture was granulated for a further 1 to 3 minutes with constant mixing. The granules leaving the mixer were dried in a fluidized bed with hot, flowing dry gases (100 ° C.). In all examples, the fine fraction (particle diameter smaller than 0.2 mm) was less than 5% and the coarse fraction (particle diameter larger than 1.6 mm) was less than 18%.
  • a mixing granulator consisting of a horizontally arranged cylindrical mixer with a rotating shaft rotating in the central axis and equipped with mixing elements (ploughshare mixer,
  • the zeolite powder mixture presented (Wessalith ( R ) CD; commercial product from Degussa / Germany) consisted of 71% by weight of zeolite of the NaA type (calculated as anhydrous active substance) 1 and 5.4% by weight of poly acrylic acid sodium salt (Degapas 4104 Nv R ); Commercial product from Degussa / Germany), calculated as an anhydrous active substance, 3.0% by weight from sodium sulfate, 2.0% by weight which was ethoxylated with 5 ethylene oxide groups (E0), 0.4% by weight of sodium hydroxide and 18.2% by weight of water.
  • the aqueous zeolite suspension was 47% by weight of zeolite of the NaA type (calculated as an anhydrous active substance) and contained 1.3% by weight of tallow alcohol with 5 E0 and 0.3% by weight of sodium hydroxide.
  • the sodium salt of the acrylic acid-maleic acid copolymer used (Sokalan ( R ) cP5 from BASF / Germany) had a relative molecular weight of approximately 70,000 and was used as a 40% by weight solution.
  • zeolite powder mixture 70 parts by weight of the zeolite powder mixture were introduced and sprayed with 30 parts by weight of a granulating liquid consisting of 20% by weight of the zeolite suspension and 80% by weight of Sokalan CP5 solution.
  • the granules obtained after drying contained 63.7% by weight of zeolite (calculated as anhydrous active substance) and 16.2% by weight of (co) polymeric carboxylates (sum of Sokalan CP5 and Degapas).
  • the bulk weight was 850 g / 1.
  • the proportion of particles with a diameter> 1.6 mm (sieve analysis) was 15.8%, the proportion of particles with a diameter ⁇ 0.2 mm was 4.3
  • zeolite powder mixture 70 parts by weight of the zeolite powder mixture were introduced and 30 parts by weight of a granulating liquid consisting of 19% by weight of the zeolite suspension, 76% by weight of the Sokalan CP5 solution and 5% by weight.
  • the granules obtained after drying contained 62.8% by weight of zeolite (calculated as anhydrous active substance, 15.5% by weight of (co) polymeric carboxylates (sum of Sokalan CP5 and Degapas) and 3.5% by weight.
  • the bulk density was 842 g / l.
  • the proportion of particles with a diameter> 1.6 mm was 11.8%, the proportion of particles with a diameter ⁇ 0.2 mm was 4.2%.
  • Example 2 was repeated with a granulating liquid which contained 18% by weight of zeolite suspension, 72% by weight of Sokalan CP5 solution and 10% by weight of Ci2-Ci8 fatty alcohol with 5 E0.
  • the granules obtained after drying contained 62.0% by weight of zeolite (calculated as anhydrous active substance), 14.7% by weight of (co) polymeric carboxylates (sum of Sokalan CP5 and Degapas) and 5.3% by weight.
  • the bulk weight was 859 g / 1.
  • the proportion of particles with a diameter> 1.6 was 13.7, the proportion of particles with a diameter ⁇ 0.2 mm was 3.8%.
  • Example 2 was repeated with a granulating liquid which contained 17% by weight of the zeolite suspension, 68% by weight of Sokalan CP5 solution and 15% by weight of Ci2-Ci8 fatty alcohol with 5 EO.
  • the granules obtained after drying contained 61.2% by weight of zeolite (calculated as anhydrous active substance), 14.0% by weight of (co) polymeric carboxylates (sum of components as above) and 7.0% by weight.
  • -% Ci2-Ci8 fatty alcohol with 5 E0 The bulk density was 908 g / 1.
  • the proportion of particles with a diameter> 1.6 mm is contributed 12.9%, the proportion of particles with a diameter ⁇ 0.2 was 2.3.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

Un procédé de préparation de granulés lourds de zéolithe doit permettre de réduire la quantité de liquide de granulation jusqu'à un facteur critique inférieur à celui connu dans l'état, de sorte que des polycarboxylates (co)polymères puissent être utilisés comme élément en dissolution dans le liquide de granulation. On produit par granulation sous adjonction d'un liquide de granulation des granulés de zéolithe et de sels de sodium ou de potassium d'acides carboxyliques polymères ou (co)polymères ayant une densité apparente comprises entre 750 et 1000 g/l. Une partie de la zéolithe se présente sous forme séchée par pulvérisation et au moins 90 % des particules de zéolithe ont un diamètre compris entre 50 et 700 mum, et le liquide de granulation contient un mélange d'eau, de zéolithe et de carboxylates (co)polymères.
PCT/EP1992/001672 1991-07-31 1992-07-22 Procede de preparation de granules de zeolithe WO1993002786A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE59202099T DE59202099D1 (de) 1991-07-31 1992-07-22 Verfahren zur herstellung von zeolith-granulaten.
EP92916048A EP0605436B1 (fr) 1991-07-31 1992-07-22 Procede de preparation de granules de zeolithe

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4125330.2 1991-07-31
DE4125330A DE4125330A1 (de) 1991-07-31 1991-07-31 Verfahren zur herstellung von zeolith-granulaten

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WO1993002786A1 true WO1993002786A1 (fr) 1993-02-18

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DE (2) DE4125330A1 (fr)
ES (1) ES2071511T3 (fr)
WO (1) WO1993002786A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995029219A1 (fr) * 1994-04-25 1995-11-02 Henkel Kommanditgesellschaft Auf Aktien Procede pour preparer des adjuvants granulaires

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19515256A1 (de) * 1995-04-26 1996-10-31 Degussa Zeolithgranulat, Verfahren zu seiner Herstellung und Verwendung
GB2370843A (en) † 2001-01-08 2002-07-10 Reckitt Benckiser Nv Laundry cleaning agents and their manufacture
DE10116210A1 (de) * 2001-03-31 2002-09-05 Henkel Kgaa Zeolith-haltige Zusammensetzung in Partikelform und Verfahren zu ihrer Herstellung

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3838086A1 (de) * 1988-11-10 1990-05-17 Henkel Kgaa Verfahren zur herstellung zeolithhaltiger granulate hoher dichte

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3838086A1 (de) * 1988-11-10 1990-05-17 Henkel Kgaa Verfahren zur herstellung zeolithhaltiger granulate hoher dichte

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995029219A1 (fr) * 1994-04-25 1995-11-02 Henkel Kommanditgesellschaft Auf Aktien Procede pour preparer des adjuvants granulaires

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EP0605436B1 (fr) 1995-05-03
DE4125330A1 (de) 1993-02-04
EP0605436A1 (fr) 1994-07-13
DE59202099D1 (de) 1995-06-08
ES2071511T3 (es) 1995-06-16

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