EP0560802A1 - Process for the production of granular zeolites. - Google Patents

Process for the production of granular zeolites.

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Publication number
EP0560802A1
EP0560802A1 EP91920221A EP91920221A EP0560802A1 EP 0560802 A1 EP0560802 A1 EP 0560802A1 EP 91920221 A EP91920221 A EP 91920221A EP 91920221 A EP91920221 A EP 91920221A EP 0560802 A1 EP0560802 A1 EP 0560802A1
Authority
EP
European Patent Office
Prior art keywords
weight
zeolite
liquid
granules
water
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
EP91920221A
Other languages
German (de)
French (fr)
Other versions
EP0560802B2 (en
EP0560802B1 (en
Inventor
Werner Pichler
Jochen Jacobs
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent 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
    • 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
    • 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

Definitions

  • the invention relates to a process for the production of zeolite granules with a high bulk density, which have a pronounced 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 and agglomerated in a granulator, whereupon the excess water is dried to a residual proportion of less than 5% by weight Will get removed.
  • the bulk density of the relatively fine-particle spray products is in the range from 450 to 600 g / 1, the size of the particles being between 0.05 and 0.5 mm.
  • 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.
  • This is based on a homogeneous powdery mixture of zeolite and the salt of the (co) polymeric carboxylic acids and granulated in a further mixing and granulation stage with the addition of water, which is preferably based on the powder mixture kept in motion is sprayed on.
  • 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 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 mm 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 a mixture of water, surfactants and (co) polymeric carboxylates is used as the granulating liquid, the content of surfactants in the granulating liquid being at least 10% by weight.
  • 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%.
  • Preferred zeolites have no particles larger than 30 ⁇ m, consist of at least 80% particles smaller than 10 ⁇ m and are of detergent quality.
  • zeolite powder in addition to zeolite powder as such, spray-dried zeolite powder mixtures (products from Degussa, trade name Wessalith), the small amounts of additives such as sodium sulfate, salts of nitrilotriacetic acid, sodium hydroxide, carboxymethyl cellulose, (co) polymeric carboxylates or contain nonionic surfactants.
  • part of the zeolite is used in the form of a 45 to 55% by weight aqueous suspension.
  • 5 to 30% by weight of zeolite, based on the total amount of zeolite are introduced as an aqueous suspension and 95 to 70% by weight, based on the total amount of zeolite, as a powder.
  • the zeolite suspensions used usually contain about 1.5 to 3% by weight, based on the suspension, of stabilizers, which also include nonionic surfactants, anionic surfactants or polymeric polycarboxylates. However, the proportion of these active ingredients introduced via the suspension is so small that the effect according to the invention can only be achieved by using additional amounts of surfactants and (co) polymeric carboxylates.
  • the granules which are produced by the process according to the invention preferably contain 50 to 95% by weight, in particular 70 to 92% by weight, based on the dried granules, of water-containing zeolite.
  • 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, polyethacrylic 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, also with vinyl esters such as vinyl acetate or vinyl propionate, acrylic id, methacrylamide and with ethylene, propylene or styrene.
  • 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. Copolymers containing 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid are particularly preferred.
  • 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 30 to 50% by weight, in particular 35 to 45% by weight, in aqueous form Solutions used.
  • water-soluble inorganic salts for example sodium sulfate, can be added to these solutions in amounts of up to 10% by weight, based on the polycarboxylate used.
  • 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.
  • 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 granules according to the invention preferably contain the salts of the polymeric or copolymeric carboxylic acids in amounts of 2 to 12% by weight and in particular in amounts of 4 to 10% by weight.
  • the granulating liquid contains at least water as a liquid component, at least polymeric or copolymeric carboxylates as a solid component and anionic and / or nonionic surfactants.
  • the granulating liquid preferably contains a mixture of water and liquid nonionic surfactants as the liquid constituent.
  • the granulating liquid advantageously consists of 5 to 30% by weight of (co) polymeric carboxylate, 10 to 75% by weight of anionic and / or nonionic surfactants and 7 to 70% by weight of water.
  • the granulating liquid consists of 0 to 25% by weight of (co) polymeric carboxylate and 10 to 65% by weight Nonionic surfactants or 10 to 40% by weight of anionic surfactants and 10 to 68% 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).
  • the water-soluble anionic surfactants are alkali metal salts, sodium or potassium salts from the class of the sulfonates and sulfates.
  • Preferred surfactants of the sulfonate type are Cg-Ci3-alkylbenzenesulfonates, in particular Ci2-alkylbenzenesulfonate, and sulfonates based on oleochemicals, such as the esters of oc-sulfofatty acids, the sulfo group being in its salt form (mono salt), e.g. B. the oc-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 from fatty alcohols, such as, for example, B.
  • 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.
  • granulating liquid is added to 100 parts by weight of zeolite, calculated as an anhydrous substance, or to a homogeneous mixture of zeolite and optionally in the form of powder in the salt of the polymeric or copolymeric carboxylic acids that preferably 15 to 45 parts by weight, in particular 18 to 40 parts by weight, based on the moist granules, of liquid constituents are present.
  • the proportion of free water added, which is not bound as water of crystallization or in a comparable form, in the granulating liquid can be very small and depends solely on the amount and the concentration of the polymeric or copolymeric carboxylate solution used.
  • the granulating liquid preferably contains at least 2 parts by weight, for example 5 to 35 parts by weight and in particular 5 to 25 parts by weight, based on the moist granulate, of free water.
  • the granulation can be carried out continuously or continuously in conventional mixing and granulating devices.
  • B. pelletizers which consist of a horizontally arranged or inclined to the horizontal, cylindrical container, rotates in the longitudinal axis of a shaft equipped with mixing tools and conveyor blades.
  • the granulating liquid can be supplied through the spray nozzle attached in the wall or on the high shaft. If work is carried out continuously, two mixers connected in series can be used, the first mixer producing the dry or, if an aqueous zeolite suspension is used, the wet premix and in the second mixer the granulation with the addition of the surfactant and Polycarboxylate-containing granulating liquid takes place.
  • 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 after transport in a subsequent mixing section with the surfactant and polycarboxylate -containing granulating liquid treated and granulated becomes.
  • 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 the constituents of the granulating liquid or individual constituents one after the other, in particular the surfactant-containing constituents, 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 40 ° C., and generally requires a time of 5 to 15 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 granules have been discharged from the mixer, for example in a vibrating section, 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 85 ° C. and in particular between 65 to 80 ° C. 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.
  • a third mixing zone e.g. B. a fluidized bed
  • water portions which 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-technical 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. H. 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 980 g / 1, in particular 800 to 950 g / 1. Because of their tight packing and their small pore volume, their absorption capacity for liquid or paste-like detergent components, in particular nonionic surfactants and foam inhibitors, for example paraffin oil or silicone oil, is opposed somewhat lighter carrier grains somewhat reduced, but is still 15 to a maximum of 20% by weight without appreciable impairment of the flowability of the granules. In view of the high packing density and the possibly already contained granules of non-ionic surfactants, this still surprisingly high adsorption capacity 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 grain spectrum in which the fine fraction (particle diameter less than 0.1 mm) is generally less than 10% and the coarse fraction (particle diameter greater than 2 m) is generally up to 40% .
  • the content of fine fractions is preferably less than 7% and is in particular 0 to 5%, while the content of coarse fractions is preferably 2 to 32%.
  • 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 do not leave any 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 powder detergent components.
  • the granules contain 2 to 25% by weight of surfactants and in particular 4 to 20% by weight of anionic and / or nonionic surfactants.
  • Particularly advantageous granules contain 75 to 90% by weight of zeolite which has been placed in an aqueous suspension in powder form or as a mixture of 94 to 73% by weight of powder and 6 to 27% by weight, in each case based on zeolite, 2 up to 10% by weight sodium salt of a copolymer of acrylic acid and maleic acid and 4 to 20% by weight liquid nonionic surfactants.
  • the granules contain zeolite as above, 3 to 8% by weight of sodium salt of a copoly- mers from acrylic acid and maleic acid and 6 to 11 wt .-% anionic surfactants, in particular alkylbenzenesulfonate and fatty alcohol sulfate.
  • 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 foam inhibitors.
  • Those components which are present in liquid form at room temperature or at the processing temperature between 25 ° C. and about 80 ° C., preferably up to 75 ° C., are considered to be “liquid”.
  • 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 of alcohols vicina 'len diols, amino nen, thiols, fatty acid and fatty acids. Block polymers of ethylene oxide and propylene oxide, which are commercially available under the name Pluronic (from BASF / Wyandotte), are also suitable. Furthermore, alkyl glycosides or alkyl polyglycosides and mixtures thereof with the ethoxylation products mentioned can 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 (E0) or propylene oxide (PO) are water-soluble or water-dispersible mixtures of compounds with different degrees of alkoxylation, the following the specified number of EO or PO groups corresponds to a statistical mean.
  • ethoxylated fatty alcohols are Ci2-Ci8-coconut alcohols with 3 to 12 EO, C ⁇ 6-Ci8-tallow alcohol with 4 to 16 EO, oleyl alcohol with 4 to 12 EO as well as ethoxylation products with appropriate chain and EO distribution available from other native fatty alcohol mixtures .
  • ethoxylated oxo alcohols for example those of the composition C12-C15 with 5 to 10 EO and C14-C15 with 6 to 12 EO are suitable.
  • alkoxylates which contain EO groups and PO groups
  • Ci2-Ci8 alcohols of the formula R- (P0) a - (E0) b or R- (E0) b- (P0) c , where a is from 1 to 3, b is from 5 to 20 and c is from 1 to 10, where b is to be greater than c.
  • the application of the liquid, optionally heated additives, in particular the application of the nonionic surfactants and the foam inhibitors to the granules can be carried out by admixing, preferably spraying, the carrier material advantageously being kept in motion by suitable mixing devices. Further treatment of the granular adsorbate is not necessary. 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 treatment of the granules with the liquid additives leads to a further increase in the bulk density, which can rise to values of over 1000 g / l.
  • 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)), loose or colored pigments, such as titanium dioxide 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 130 l and a connected one with a speed of 1200 up to 1,500 revolutions / minute operated knife mill.
  • the pulverulent constituents and, if appropriate, the aqueous zeolite suspension were placed in the mixing granulator and processed to form a homogeneous mixture.
  • the granulating liquid was sprayed in by means of nozzles over the course of 1 to 5 minutes 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 (70 ° C.).
  • the fine fraction particle diameter less than 0.1 m
  • the coarse fraction particle diameter greater than 2 mm
  • the zeolite powder used was finely crystalline, spray-dried zeolite of the NaA type, which contained 20% by weight of bound water.
  • the aqueous zeolite suspension was 48% by weight.
  • 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; the amounts given relate to anhydrous substance.
  • zeolite 100 parts by weight of zeolite, based on anhydrous substance, were mixed with 44.2 parts by weight of a granulating liquid consisting of 19.8% by weight of Sokalan CP5, 50.6% by weight of Ci2-Ci8 fatty alcohol 5 EO and 29.6 wt .-% water, sprayed.
  • the granules obtained after drying contained 80.1% by weight of water-containing zeolite, which had been presented as a powder, 5.6% by weight of Sokalan CP5 and 14.3% by weight of C ⁇ 2-Ci8 fatty alcohol with 5 E0.
  • the bulk density before sieving was 900 g / l; the gross share was 5%.
  • zeolite 100 parts by weight of zeolite, based on anhydrous substance, were mixed with 42.5 parts by weight of a granulating liquid consisting of 13.3% by weight of Sokalan CP5, 62.1% by weight of Ci2-Ci8 fatty alcohol 7 E0 and 24.6 wt .-% water sprayed.
  • the granules obtained after drying contained 79.6% by weight of water-containing zeolite, which had been presented as a powder, 3.6% by weight of Sokalan CP5 and 16.8% by weight of Ci2-Ci8 fatty alcohol with 7 E0.
  • the bulk density before screening was 850 g / l; the gross share was 13.9%.
  • zeolite There were 100 parts by weight of zeolite, based on anhydrous substance, with 39 parts by weight of a granulating liquid consisting of 8.9% by weight of Sokalan CP5, 73.3% by weight of Ci2-Ci8 fatty alcohol with 7 E0 and 17.8% by weight of water, sprayed.
  • the granules obtained after drying contained 79.6% by weight of water-containing zeolite, which had been introduced as a powder, 2.2% by weight of Soka lan CP5 and 18.2% by weight of Ci2-Ci8 fatty alcohol with 7 E0.
  • the bulk density was 870 g / 1; the gross share was 2.9%.
  • zeolite 100 parts by weight of zeolite, based on anhydrous substance, were mixed with 47.5 parts by weight of a granulating liquid consisting of 22.7% by weight of Sokalan CP5, 20.5% by weight of sodium dodecylbenzenesulfonate and 56.8% by weight. % Water sprayed.
  • the granules obtained after drying contained 85.9% by weight of water-containing zeolite, which had been presented as a powder, 7.4% by weight of Sokalan CP5 and 6.7% by weight of sodium dodecylbenzenesulfonate.
  • the bulk density before sieving was 860 g / l; the gross share was 30.2%.
  • Example 6 100 parts by weight of zeolite, based on anhydrous substance, were mixed with 47.5 parts by weight of a granulating liquid consisting of 22.7% by weight of Sokalan CP5, 20.5% by weight of sodium dodecylbenzenesulfonate and
  • zeolite There were 100 parts by weight of zeolite, based on anhydrous substance, with 44 parts by weight of a granulating liquid consisting of 11.25% by weight of Sokalan CP5, 35.75% by weight of sodium dodecylbenzenesulfonate and 53% by weight of water , sprayed.
  • the granules obtained after drying contained 85.8% by weight of water-containing zeolite, which had been presented as a powder, 3.4% by weight of Soka lan CP5 and 10.8% by weight of sodium dodecylbenzenesulfonate.
  • the bulk weight was 770 g / 1; the gross share was 29.8%.
  • zeolite 100 parts by weight of zeolite, based on anhydrous substance, were mixed with 46.4 parts by weight of a granulating liquid consisting of 20.25% by weight of Sokalan CP5, 48.7% by weight of C ⁇ 2-C ⁇ 8 fatty alcohol 7 E0 and 31.05 wt .-% water, sprayed.
  • the granules obtained after drying contained 79.6% by weight of water-containing zeolite, 74.4% by weight as powder and 5.2% by weight as suspension, 6 parts by weight of Sokalan CP5 and 14, 4% by weight of C ⁇ 2-C ⁇ 8 fatty alcohol with 7 E0.
  • the bulk density before sieving was 940 g / l; the gross share was 31.1%.
  • zeolite 100 parts by weight of zeolite, based on anhydrous substance, with 42.0 parts by weight of a granulating liquid consisting of 29.5% by weight of Sokalan CP5, 22.9 parts by weight of C ⁇ 2-C ⁇ s fatty alcohol with 5 E0 and 47.6 wt .-% water, sprayed.
  • the granules obtained after drying contained 76.5% by weight of water-containing zeolite, 73.1% by weight as powder and 13.4% by weight as suspension, 7.6% by weight of Sokalan CP5 and 5.9% by weight of Ci2-C ⁇ 8 fatty alcohol with 5 E0.
  • the bulk density before sieving was 830 g / l; the gross proportion was 17.5 5'S.
  • zeolite 100 parts by weight of zeolite, based on anhydrous substance, were mixed with 41.0 parts by weight of a granulating liquid consisting of 19.5% by weight of Sokalan CP5; 31.3% by weight of C ⁇ 2-C ⁇ s fatty alcohol with 7 E0 and 49.2% by weight of water, sprayed.
  • the granules obtained after drying contained 85.5% by weight of water-containing zeolite, 62.5% by weight as powder and 23% by weight as suspension, 5.5% by weight of Sokalan CP5 and 8 ,8th % By weight C ⁇ 2-C ⁇ 8 _ fatty alcohol with 7 EO.
  • the bulk density before sieving was 840 g / l; the gross share was 24.5%.
  • the granules treated with the nonionic surfactant were free-flowing and had a perfect wash-in capacity, both as unblended powder and mixed with a powdered household detergent in a ratio of 1: 4.

Abstract

L'invention a pour but de développer un procédé de granulation pour la fabrication de granulats lourds de zéolite, dans lequel la quantité mise en oeuvre de liquide de granulation représente un moindre facteur critique, de telle sorte que des carboxylates (co-)polymères puissent être utilisés sous la forme de constituants dissous du liquide de granulation. Ce but est atteint grâce au fait qu'on utilise comme liquide de granulation un mélange d'eau, d'agents tensioactifs et de carboxylates (co-)polymères, la teneur en agents tensioactifs dans le liquide de granulation étant d'au moins 10 % en poids.The object of the invention is to develop a granulation process for the manufacture of heavy zeolite aggregates, in which the amount of granulation liquid used represents a less critical factor, so that (co-) polymeric carboxylates can be used. be used as dissolved constituents of the granulation liquid. This object is achieved by the fact that a mixture of water, surfactants and (co-) polymeric carboxylates is used as the granulating liquid, the content of surfactants in the granulating liquid being at least 10 % in weight.

Description

"Verfahren zur Herstellung von Zeolith-Granulaten" "Process for the Production of Zeolite Granules"
Die Erfindung betrifft ein Verfahren zur Herstellung von Zeolith-Granula¬ ten mit hohem Schüttgewicht, die ein ausgeprägtes Adsorptionsvermögen für flüssige Wirkstoffe besitzen, und die Verwendung der Zeolith-Granulate als Vorprodukt zur Herstellung von Wasch- und Reinigungsmitteln.The invention relates to a process for the production of zeolite granules with a high bulk density, which have a pronounced 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.
Aus der deutschen Patentanmeldung 33 16 513 (Benckiser) sind bereits Gra¬ nulate bekannt, die durch Sprühtrocknung von wäßrigen Aufschläm ungen her¬ gestellt wurden und feinpulvrige Zeolithe und Salze von (co-)polymeren Carbonsäuren enthalten. Sie weisen ein Schüttgewicht von lediglich 560 bis 610 g/1 auf. Granulate, die Zeolithe, Salze (co-)polymerer Carbonsäuren und zusätzlich geringe Mengen an Alkalimetallsilikaten enthalten und als Trägermaterial für flüssige Waschmittelbestandteile, insbesondere für nichtionische Tenside dienen, werden in der deutschen Patentanmeldung 34 44 960 beschrieben. Das Schüttgewicht dieser durch Sprühtrocknung her¬ gestellten Granulate beträgt maximal 700 g/1 und liegt vorzugsweise zwi¬ schen 500 und 650 g/1.From German patent application 33 16 513 (Benckiser), granules are already known which have been produced by spray drying aqueous slurries and contain finely powdered zeolites and salts of (co) polymeric carboxylic acids. They have a bulk density of only 560 to 610 g / 1. Granules which contain zeolites, salts of (co) polymeric carboxylic acids and additionally small amounts of alkali metal silicates and which serve as carrier material for liquid detergent components, in particular for nonionic surfactants, are described in German patent application 34 44 960. The bulk density of these granules produced by spray drying is a maximum of 700 g / 1 and is preferably between 500 and 650 g / 1.
Aus der europäischen Patentanmeldung 21 267 (PQ) sind Granulate mit einem Gehalt an Zeolithen und Alkalisilikaten bekannt, die eine Teilchengröße zwischen 0,15 und 2 mm und ein Schüttgewicht von 300 bis 700 g/1 aufwei¬ sen. Sie eignen sich ebenfalls zum Adsorbieren flüssiger Waschmittelbe¬ standteile, insbesondere von nichtionischen Tensiden. Zu ihrer Herstellung wird ein trockenes Vorgemisch aus Zeolith und Alkalimetallsilikat (Mi¬ schungsverhältnis 1:1 bis 1:8) in einem Granulator mit Wasser besprüht und agglomeriert, worauf das überschüssige Wasser bis auf einen Restanteil von weniger als 5 Gew.-% durch Trocknung entfernt wird. Nachteilig ist vor allem der hohe Gehalt an stark alkalisch reagierenden Alkalisilikaten, wodurch der Einsatz dieser Granulate in neutral bis schwach alkalisch rea¬ gierenden, für empfindliche Textilien geeigneten Waschmitteln stark ein¬ schränkt ist. Außerdem lassen sich nach den Lehren dieses Dokumentes keine Schüttgewichte von über 700 g/1 erzielen. Die europäische Patentanmeldung 149 264 (Unilever) lehrt, daß man zur Adsorption flüssiger WaschmitteIbe- standteile, insbesondere von nichtionischen Tensiden handelsübliche sprüh¬ getrocknete Zeolithe bzw. deren Gemische mit anorganischen Salzen, wie _ 2 _European patent application 21 267 (PQ) 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 and agglomerated in a granulator, whereupon the excess water is dried to a residual proportion of less than 5% by weight Will get removed. A disadvantage is above all the high content of strongly alkaline-reacting alkali silicates, which severely limits the use of these granules in detergents which are neutral to weakly alkaline and suitable for sensitive textiles. In addition, according to the teachings of this document, bulk densities of over 700 g / 1 cannot be achieved. European patent application 149 264 (Unilever) teaches that for the adsorption of liquid detergent components, in particular nonionic surfactants, commercially available spray-dried zeolites or their mixtures with inorganic salts, such as _ 2 _
Natriumsulfat, verwenden kann. Das Schüttgewicht der relativ feinteiligen Sprühprodukte liegt im Bereich von.450 bis 600 g/1, wobei die Teilchen eine Größe zwischen 0,05 und 0,5 mm aufweisen.Sodium sulfate. The bulk density of the relatively fine-particle spray products is in the range from 450 to 600 g / 1, the size of the particles being between 0.05 and 0.5 mm.
Die deutsche Patentanmeldung 3838086 beschreibt die Herstellung von Gra¬ nulaten aus Zeolith und den Natrium- oder Kalium-Salzen polymerer bzw. copolymerer Carbonsäuren, wobei die Agglomerierung bzw. Granulierung unter Zusatz einer Granulierflüssigkeit erfolgt und das erhaltene Agglomerat bis zum Erreichen eines gut rieselfähigen Granulates mit einem Schüttgewicht von 750 bis 1 000 g/1 getrocknet wird. Dabei geht man von einer homogenen pulvrigen Mischung aus Zeolith und dem Salz der (co-)polymeren Carbonsäu¬ ren aus und granuliert diese in einer weiteren Misch- und Granulations¬ stufe unter Zusatz von Wasser, das vorzugsweise auf das in Bewegung gehal¬ tene Pulvergemisch aufgesprüht wird. Die Polycarboxylate werden in fester Form vorgelegt und nicht in gelöster Form als Bestandteil der Granulier¬ flüssigkeit zugesetzt, da die Einsatzmenge der Granulierflüssigkeit einen kritischen Faktor darstellt und daher exakt dosierbar sein muß. Zu hohe Mengen an Granulierflüssigkeit führen zu Granulaten mit einem breiten Kornspektrum und einem unerwünscht hohen Grobanteil (Teilchengröße ober¬ halb 2 mm Länge) sowie zu einem niedrigeren Schüttgewicht.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. This is based on a homogeneous powdery mixture of zeolite and the salt of the (co) polymeric carboxylic acids and granulated in a further mixing and granulation stage with the addition of water, which is preferably based on the powder mixture kept in motion is sprayed on. 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 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 mm length) and to a lower bulk density.
Es wurde nun gefunden, daß die Menge an Granulierflüssigkeit einen wesent¬ lich geringeren kritischen Faktor darstellt, so daß die (co-)polymeren Carboxylate als gelöster Bestandteil der Granulierflüssigkeit eingesetzt werden können, wenn bestimmte Verfahrensschritte eingehalten werden.It has now been found that the amount of granulating liquid represents a much lower critical factor, so that the (co) polymeric carboxylates can be used as a dissolved component of the granulating liquid if certain process steps are followed.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Granulaten aus Zeolith und Natrium- oder Kaliumsalzen polymerer bzw. copolymerer Car¬ bonsäuren, wobei die Granulierung unter Zusatz einer Granulierflüssigkeit erfolgt und das erhaltene Granulat bis zum Erreichen eines gut rieselfähi¬ gen Granulats mit einem Schüttgewicht von 750 bis 1 000 g/1 getrocknet wird, das dadurch gekennzeichnet ist, daß als Granulierflüssigkeit eine Mischung aus Wasser, Tensiden und (co-)polymeren Carboxylaten verwendet wird, wobei der Gehalt an Tensiden in der Granulierflüssigkeit mindestens 10 Gew.-% beträgt. Bei der Herstellung der Granulate geht man zweckmäßigerweise von sprühge¬ trocknetem, feinpulvrigem Zeolith, der im allgemeinen einen Wassergehalt von 17 bis 25 Gew.-% aufweist, aus. Geeignete Zeolithe sind solche vom Zeolith A-Typ. Brauchbar sind ferner Gemische aus Zeolith NaA und NaX, wobei der Anteil des Zeoliths NaX in derartigen Gemischen zweckmäßiger¬ weise unter 30 % liegt. Bevorzugte Zeolithe weisen keine Teilchen mit einer Größe über 30 μm auf, bestehen zu wenigstens 80 % aus Teilchen einer Größe von weniger als 10 μm und liegen in Waschmittel-Qualität vor. Außer Zeolith-Pulver als solchem eignen sich auch sprühgetrocknete Zeolith-Pul- vermischungen (Produkte der Firma Degussa, Handelsname Wessalith), die geringe Mengen an Zusatzstoffen wie Natriumsulfat, Salzen der Nitrilotri- essigsäure, Natriumhydroxid, Carboxymethylcellulose, (co-)polymere Carboxylate oder nichtionischen Tensiden enthalten. In einer bevorzugten Ausführungsform wird ein Teil des Zeoliths in Form einer 45 bis 55 Gew.-%igen wäßrigen Suspension eingesetzt. Insbesondere werden 5 bis 30 Gew.-% an Zeolith, bezogen auf die Gesamtmenge Zeolith, als wäßrige Suspension und 95 bis 70 Gew.-%, bezogen auf die Gesamtmenge Zeolith, als Pulver vorgelegt. Dieser Wasseranteil sowie der Wassergehalt des pulver- för igen Zeoliths werden in die Berechnung der Wasserbilanz eingebracht; die in die Granulierstufe einzubringende Wassermenge kann um diese Anteile reduziert werden. Die eingesetzten Zeolith-Suspensionen enthalten zwar üblicherweise etwa 1,5 bis 3 Gew.-%, bezogen auf die Suspension, an Stabilisatoren, zu denen auch Niotenside, Aniontenside oder polymere Polycarboxylate gehören. Jedoch ist der Anteil dieser über die Suspension eingebrachten Wirkstoffe so gering, daß der erfindungsgemäße Effekt erst durch den Einsatz zusätzlicher Mengen an Tensiden und (co-)polymeren Carboxylaten erreicht wird. Die Granulate, die nach dem erfindungsgemäßen Verfahren hergestellt werden, enthalten vorzugsweise 50 bis 95 Gew.%, ins¬ besondere 70 bis 92 Gew.-%, bezogen auf das getrocknete Granulat, an wasserhaltigem Zeolith.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 a mixture of water, surfactants and (co) polymeric carboxylates is used as the granulating liquid, the content of surfactants in the granulating liquid being at least 10% by weight. In the preparation of the granules, it is expedient to start from spray-dried, finely powdered zeolite, which generally has a water content of 17 to 25% by weight. 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%. Preferred zeolites have no particles larger than 30 μm, consist of at least 80% particles smaller than 10 μm and are of detergent quality. In addition to zeolite powder as such, spray-dried zeolite powder mixtures (products from Degussa, trade name Wessalith), the small amounts of additives such as sodium sulfate, salts of nitrilotriacetic acid, sodium hydroxide, carboxymethyl cellulose, (co) polymeric carboxylates or contain nonionic surfactants. In a preferred embodiment, part of the zeolite is used in the form of a 45 to 55% by weight aqueous suspension. In particular, 5 to 30% by weight of zeolite, based on the total amount of zeolite, are introduced as an aqueous suspension and 95 to 70% by weight, based on the total amount of zeolite, as a powder. This water content and the water content of the powdery zeolite are included in the calculation of the water balance; the amount of water to be introduced into the pelletizing stage can be reduced by these proportions. The zeolite suspensions used usually contain about 1.5 to 3% by weight, based on the suspension, of stabilizers, which also include nonionic surfactants, anionic surfactants or polymeric polycarboxylates. However, the proportion of these active ingredients introduced via the suspension is so small that the effect according to the invention can only be achieved by using additional amounts of surfactants and (co) polymeric carboxylates. The granules which are produced by the process according to the invention preferably contain 50 to 95% by weight, in particular 70 to 92% by weight, based on the dried granules, of water-containing zeolite.
Geeignete wasserlösliche Salze der in den Granulaten enthaltenen homopoly- meren und/oder copoly eren Carbonsäuren, von denen die Natriumsalze bevor¬ zugt werden, sind Polyacrylsäure, Poly ethacrylsäure und Polymaleinsäure, Copoly ere der Acrylsäure oder Methacrylsäure mit Maleinsäure oder Vinyl- ethern wie Vinylmethylether bzw. Vinylethylether, ferner mit Vinylestern wie Vinylacetat oder Vinylpropionat, Acryla id, Methacrylamid sowie mit Ethylen, Propylen oder Styrol. In solchen copolymeren Säuren, in denen eine der Komponenten keine Säurefunktion aufweist, beträgt deren Anteil im Interesse einer ausreichenden Wasserlöslichkeit nicht mehr als 50 Mol-%, vorzugsweise weniger als 30 Mol-%. Als besonders geeignet haben sich Co- polymere der Acrylsäure bzw. Methacrylsäure mit Maleinsäure erwiesen. Ins¬ besondere werden Copolymerisate bevorzugt, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Die relative Molekülmasse der homo- bzw. copolymeren Polycarboxylate beträgt im allgemeinen 2 000 bis 150000, vorzugsweise 5000 bis 100000. Vorzugsweise werden die Polycarb¬ oxylate in Form 30 bis 50 Gew.-%iger, insbesondere 35 bis 45 Gew.-%iger wäßriger Lösungen eingesetzt. Diesen Lösungen können zum Zwecke der Visko¬ sitätserniedrigung wasserlösliche, anorganische Salze, beispielsweise Na¬ triumsulfat, in Mengen bis zu 10 Gew.-%, bezogen auf eingesetztes Poly- carboxylat, zugesetzt werden. In einer weiteren Ausführungsform werden die Polycarboxylate teilweise in pulvriger Form zusammen mit dem feinteiligen Zeolith vorgelegt. Dabei ist es bevorzugt, maximal 50 Gew.-% und insbeson¬ dere maximal 40 Gew.-% der polymeren Carboxylate in Pulverform einzuset¬ zen. Die handelsüblichen Salze (co-)polymerer Carbonsäuren in pulvriger Form enthalten vielfach Feuchtigkeitsanteile von 5 bis 15 Gew.-%. Dieser Wasseranteil wird ebenfalls in die Berechnung der Wasserbilanz einge¬ bracht. Rechnerisch ist der Anteil der Salze bei der Herstellung der Mit¬ tel bzw. bei der Zusammensetzung der fertigen Granulate auf wasserfreies Salz zu beziehen. Die erfindungsgemäßen Granulate enthalten die Salze der polymeren bzw. copolymeren Carbonsäuren vorzugsweise in Mengen von 2 bis 12 Gew.~% und insbesondere in Mengen von 4 bis 10 Gew.-%.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, polyethacrylic 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, also with vinyl esters such as vinyl acetate or vinyl propionate, acrylic id, methacrylamide and with ethylene, propylene or styrene. In those 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. Copolymers containing 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid are particularly preferred. 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 30 to 50% by weight, in particular 35 to 45% by weight, in aqueous form Solutions used. For the purpose of lowering the viscosity, water-soluble inorganic salts, for example sodium sulfate, can be added to these solutions in amounts of up to 10% by weight, based on the polycarboxylate used. In a further embodiment, 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. 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. In mathematical terms, 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 granules according to the invention preferably contain the salts of the polymeric or copolymeric carboxylic acids in amounts of 2 to 12% by weight and in particular in amounts of 4 to 10% by weight.
Die Granulierflüssigkeit enthält zumindest Wasser als flüssigen Bestand¬ teil, zumindest polymere oder copolymere Carboxylate als festen Bestand¬ teil sowie anionische und/oder nichtionische Tenside. Vorzugsweise enthält die Granulierflüssigkeit als flüssigen Bestandteil eine Mischung aus Was¬ ser und flüssigen nichtionischen Tensiden. Mit Vorteil besteht die Granu¬ lierflüssigkeit zu 5 bis 30 Gew.-% aus (co-)polymerem Carboxylat, zu 10 bis 75 Gew.-% aus anionischen und/oder nichtionischen Tensiden und zu 7 is 70 Gew.-% aus Wasser. Insbesondere besteht die Granulierflüssigkeit zu 0 bis 25 Gew.-% aus (co-)polymerem Carboxylat, zu 10 bis 65 Gew.-% aus Niotensiden oder zu 10 bis 40 Gew.-% aus Aniontensiden und zu 10 bis 68 Gew.-% aus Wasser.The granulating liquid contains at least water as a liquid component, at least polymeric or copolymeric carboxylates as a solid component and anionic and / or nonionic surfactants. The granulating liquid preferably contains a mixture of water and liquid nonionic surfactants as the liquid constituent. The granulating liquid advantageously consists of 5 to 30% by weight of (co) polymeric carboxylate, 10 to 75% by weight of anionic and / or nonionic surfactants and 7 to 70% by weight of water. In particular, the granulating liquid consists of 0 to 25% by weight of (co) polymeric carboxylate and 10 to 65% by weight Nonionic surfactants or 10 to 40% by weight of anionic surfactants and 10 to 68% by weight of water.
Als flüssige nichtionische Tenside werden vorzugsweise ethoxylierte und/oder propoxylierte Fettalkohole mit Bevorzugung der ethoxylierten Fettalkohole eingesetzt, insbesondere Anlagerungsprodukte von 2 bis 7 Mol Ethylenoxid (E0) an lineare primäre Alkohole, wie z. B. an Kokos-, Talg- fett- oder Oleylalkohol, oder an in 2-Stellung methylverzweigte primäre Alkohole (Oxoalkohole). Insbesondere werden Ci2-Ci4-Alkohole mit 3 E0 oder 4 E0, Ci3-Ci5-Alkohole mit 3, 5 oder 7 E0, Ci2-Ci8-Alkohole mit 2, 3, 5 oder 7 E0 und Mischungen aus diesen, wie Mischungen aus Ci2~Ci4-Alkohol mit 3 E0 und Ci2-Ci8-Al ohol mit 5 E0 eingesetzt. Bevorzugte ethoxylierte Fettalkohole sind weiterhin solche mit einer eingeengten HomologenVertei¬ lung (narrow ränge ethoxylates, nre).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). In particular, Ci2-Ci4 alcohols with 3 E0 or 4 E0, Ci3-Ci5 alcohols with 3, 5 or 7 E0, Ci2-Ci8 alcohols with 2, 3, 5 or 7 E0 and mixtures of these, such as mixtures of Ci2 ~ Ci4 alcohol with 3 E0 and Ci2-Ci8 alcohol with 5 E0 used. Preferred ethoxylated fatty alcohols are furthermore those with a narrow homolog distribution (narrow ranks ethoxylates, nre).
Die wasserlöslichen anionischen Tenside sind Alkalimetallsalze, Natrium¬ oder Kalium-Salze, aus der Klasse der Sulfonate und der Sulfate. Als Ten¬ side vom Sulfonat-Typ kommen vorzugsweise Cg-Ci3-Alkylbenzolsulfonate, insbesondere Ci2-Alkylbenzolsulfonat, und Sulfonate auf fettchemischer Basis wie die Ester von oc-Sulfofettsäuren, wobei die Sulfogruppe in ihrer Salz-Form vorliegt (Monosalz), z. B. die oc-sulfonierten Methylester der hydrierten Kokos-, Palmkern- oder Taigfettsäuren in Betracht. Geeignet sind außerdem auch die biologisch gut abbaubaren Alkansulfonate, die aus Ci2-Ci8~Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxydation mit anschließender Hydrolyse bzw. Neutralisation gewonnen werden. Die Sulfonatgruppe ist über die gesamte Kohlenstoffkette statistisch verteilt, wobei die sekundären Alkansulfonate überwiegen. Geeignete Tenside vom Sul¬ fat-Typ sind beispielsweise die gegebenenfalls ethoxylierten Schwefel¬ säuremonoester aus primären Alkoholen natürlichen und synthetischen Ur¬ sprungs, d. h. aus Fettalkoholen, wie z. B. Kokosfettalkohol, Taigfett¬ alkohol, Oleylalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylal- kohol, oder den CiQ-C20-0xoalkoholen, sowie die Schwefelsäuremonoester sekundärer Alkohole dieser Kettenlänge, wobei die Schwefelsäuremonoester der primären Alkohole auf fettchemischer Basis bevorzugt sind. Die festen, wasserlöslichen Aniontenside können in Pulverform oder in Pastenform in die flüssigen Bestandteile der Granulierflüssigkeit eingearbeitet werden. Dabei wird im Falle des Einsatzes wäßriger Tensidpasten der Wasseranteil in die Berechnung der flüssigen Bestandteile eingebracht, bzw. die in die Granul erstufe eingebrachte Flüssigkeitsmenge kann um diesen Anteil redu¬ ziert werden.The water-soluble anionic surfactants are alkali metal salts, sodium or potassium salts from the class of the sulfonates and sulfates. Preferred surfactants of the sulfonate type are Cg-Ci3-alkylbenzenesulfonates, in particular Ci2-alkylbenzenesulfonate, and sulfonates based on oleochemicals, such as the esters of oc-sulfofatty acids, the sulfo group being in its salt form (mono salt), e.g. B. the oc-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids into consideration. Also suitable are the readily biodegradable alkanesulfonates, which are obtained from Ci2-Ci8 ~ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The sulfonate group is statistically distributed over the entire carbon chain, with the secondary alkanesulfonates predominating. Suitable surfactants of the sulfate type are, for example, the optionally ethoxylated sulfuric acid monoesters from primary alcohols of natural and synthetic origin, ie from fatty alcohols, such as, for example, B. coconut oil alcohol, Taigfett¬ alcohol, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the CiQ-C20-0xoalcohols, as well as the sulfuric acid monoesters of secondary alcohols of this chain length, the sulfuric acid monoesters of the primary alcohols are preferred on a fatty chemical basis . 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.
Zur Herstellung der feuchten, nicht getrockneten Granulate wird zu 100 Gew.-Teilen Zeolith, berechnet als wasserfreie Substanz, oder zu einer homogenen Mischung aus Zeolith und gegebenenfalls in Pulverform vorgeleg¬ tem Salz der polymeren bzw. copolymeren Carbonsäuren Granulierflüssigkeit in der Menge zugemischt, daß vorzugsweise 15 bis 45 Gew.-Teile, insbeson¬ dere 18 bis 40 Gew.-Teile, bezogen auf das feuchte Granulat, an flüssigen Bestandteilen vorhanden sind. Dabei kann der Anteil an zugesetztem freiem, nicht als Kristallwasser, oder in vergleichbarer Form gebundenem Wasser in der Granulierflüssigkeit sehr gering und allein abhängig sein von der Men¬ ge und der Konzentration der eingesetzten polymeren bzw. copolymeren Carb- oxylat-Lösung. Vorzugsweise enthält die Granulierflüssigkeit jedoch min¬ destens 2 Gew.-Teile, beispielsweise 5 bis 35 Gew.-Teile und insbesondere 5 bis 25 Gew.-Teile, bezogen auf das feuchte Granulat, an freiem Wasser.To produce the moist, non-dried granules, granulating liquid is added to 100 parts by weight of zeolite, calculated as an anhydrous substance, or to a homogeneous mixture of zeolite and optionally in the form of powder in the salt of the polymeric or copolymeric carboxylic acids that preferably 15 to 45 parts by weight, in particular 18 to 40 parts by weight, based on the moist granules, of liquid constituents are present. The proportion of free water added, which is not bound as water of crystallization or in a comparable form, in the granulating liquid can be very small and depends solely on the amount and the concentration of the polymeric or copolymeric carboxylate solution used. However, the granulating liquid preferably contains at least 2 parts by weight, for example 5 to 35 parts by weight and in particular 5 to 25 parts by weight, based on the moist granulate, of free water.
Die Granulierung kann in üblichen Misch- und Granuliervorrichtungen dis¬ kontinuierlich oder kontinuierlich durchgeführt werden. Geeignet sind z. B. Granuliervorrichtungen, die aus einem horizontal angeordneten oder gegen die Horizontale geneigten, zylindrischen Behälter bestehen, in deren Längsachse eine mit Mischwerkzeugen und Förderschaufeln ausgerüstete Welle rotiert. Die Zuführung der Granulierflüssigkeit kann durch die in der Wan¬ dung oder an der hohen Welle angebrachte Sprühdüse erfolgen. Sofern konti¬ nuierlich gearbeitet wird, können zwei hintereinander geschaltete Mischer verwendet werden, wobei im ersten Mischer die Herstellung des trockenen oder, falls eine wäßrige Zeolith-Suspension eingesetzt wird, feuchten Vor¬ gemisches und im zweiten Mischer die Granulierung unter Zusatz der Tensid- und Polycarboxylat-haltigen Granulierflüssigkeit erfolgt. Ein kontinuier¬ liches Arbeiten ist auch in einem Mischer möglich, wobei in einer ersten Mischstrecke entweder die Pulverströme und/oder die Pulverströme und die Zeolith-Suspension vereinigt und homogenisiert werden und das Gemisch nach dem Weitertransport in einer nachfolgenden Mischstrecke mit der Tensid- und Polycarboxylat-haltigen Granulierflüssigkeit behandelt und granuliert wird. Vorzugsweise wird die Granulierflüssigkeit mittels Düsen auf das in Bewegung gehaltene Gemisch aufgesprüht. Dabei ist es möglich, eine Mi¬ schung aus allen Bestandteilen der Granulierflüssigkeit oder einzelne Be¬ standteile nacheinander, insbesondere die Tensid-haltigen Bestandteile vor und nach der Zugabe der Polycarboxylat-Lösung, zu versprühen. Die Granu¬ lierung wird im allgemeinen bei normalen bis mäßig erhöhten Temperaturen, vorzugsweise bei Temperaturen zwischen 20 und 40°C durchgeführt und erfor¬ dert im allgemeinen eine Zeit von 5 bis 15 Minuten.The granulation can be carried out continuously 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, rotates in the longitudinal axis of a shaft equipped with mixing tools and conveyor blades. The granulating liquid can be supplied through the spray nozzle attached in the wall or on the high shaft. If work is carried out continuously, two mixers connected in series can be used, the first mixer producing the dry or, if an aqueous zeolite suspension is used, the wet premix and in the second mixer the granulation with the addition of the surfactant and Polycarboxylate-containing granulating liquid takes place. 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 after transport in a subsequent mixing section with the surfactant and polycarboxylate -containing granulating liquid treated and granulated becomes. 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 the constituents of the granulating liquid or individual constituents one after the other, in particular the surfactant-containing constituents, 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 40 ° C., and generally requires a time of 5 to 15 minutes.
Das Nachtrocknen kann durch Einleiten heißer Gase in einer dritten Misch¬ strecke, z. B. einer Wirbelschicht, oder auch nach dem Austragen der Gra¬ nulate aus dem Mischer beispielsweise in einer RütteIstrecke, einem Frei- falltrockner oder auch in dünner Schicht auf einem Transportband erfolgen. Bevorzugt ist die Trocknung in einer Wirbelschicht, wobei die Temperatur des Granulats vorzugsweise zwischen 60 und 85°C und insbesondere zwischen 65 bis 80°C liegt. Dabei wird die Trocknung so weit durchgeführt, bis das in der Granulationsstufe zugesetzte Wasser bis auf einen Anteil von weni¬ ger als 5 Gew.-%, vorzugsweise weniger als 3 Gew.-%, jeweils bezogen auf das getrocknete Granulat, entfernt ist. Zusätzlich können bei der Trock¬ nung noch weitere Wasseranteile, die ursprünglich mit dem Zeolith bzw. einem nicht wasserfrei eingesetzten (co-)polymeren Salz eingebracht wur¬ den, entfernt werden. Derartige "übertrocknete" Granulate können anwen¬ dungstechnische Vorteile aufweisen, beispielsweise beim Zusatz zu Wasch¬ mitteln, die feuchtigkeitsempfindliche Wirkstoffe enthalten. Vorzugsweise sollte jedoch die Entwässerung des Zeoliths nicht unter einen Wassergehalt von 18 Gew.-%, bezogen auf Zeolith, getrieben werden, um eine Aktivitäts¬ verminderung zu vermeiden. Zweckmäßigerweise liegt der Wassergehalt der Granulate in einem Bereich, bei dem das Wasserbindungsvermögen des Zeo¬ liths weitgehend abgesättigt ist, d. h. bei dem der Zeolith einen Wasser¬ gehalt von insgesamt 19 bis 22 Gew.-% besitzt.The drying can be carried out by introducing hot gases in a third mixing zone, e.g. B. a fluidized bed, or after the granules have been discharged from the mixer, for example in a vibrating section, 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 85 ° C. and in particular between 65 to 80 ° C. 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. In addition, further water portions which 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-technical advantages, for example when added to detergents which contain moisture-sensitive active ingredients. However, 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. H. in which the zeolite has a total water content of 19 to 22% by weight.
Die Granulate besitzen vorzugsweise ein Schüttgewicht von 780 bis 980 g/1, insbesondere von 800 bis 950 g/1. Aufgrund ihrer dichten Packung und ihres geringen Porenvolumens ist ihr Aufnahmevermögen für flüssige bzw. pasten- förmige Waschmittelbestandteile, insbesondere nichtionische Tenside und Schauminhibitoren, beispielsweise Paraffinöl oder Silikonöl, gegenüber spezifisch leichteren Trägerkörnern etwas vermindert, beträgt jedoch immer noch 15 bis maximal 20 Gew.- ohne nennenswerte Beeinträchtigung der Rieselfähigkeit der Granulate. Dieses angesichts der hohen Packungsdichte und des gegebenenfalls bereits enthaltenen Gehalts der Granulate an nicht¬ ionischen Tensiden immer noch überraschend hohe Adsorptionsvermögen reicht für die üblichen Anwendungsgebiete, insbesondere für einen Einsatz als Mischungskomponente in Wasch- und Reinigungsmitteln, vollkommen aus.The granules preferably have a bulk density of 780 to 980 g / 1, in particular 800 to 950 g / 1. Because of their tight packing and their small pore volume, their absorption capacity for liquid or paste-like detergent components, in particular nonionic surfactants and foam inhibitors, for example paraffin oil or silicone oil, is opposed somewhat lighter carrier grains somewhat reduced, but is still 15 to a maximum of 20% by weight without appreciable impairment of the flowability of the granules. In view of the high packing density and the possibly already contained granules of non-ionic surfactants, this still surprisingly high adsorption capacity is completely sufficient for the usual fields of application, in particular for use as a mixture component in detergents and cleaning agents.
Die durch das erfindungsgemäße Verfahren erhaltenen Granulate zeichnen sich durch ein Kornspektrum aus, in dem der Feinanteil (Teilchendurchmes- ser kleiner 0,1 mm) im allgemeinen unter 10 % und der Grobanteil (Teil¬ chendurchmesser größer 2 m) im allgemeinen bis 40 % beträgt. Vorzugsweise ist der Gehalt an Feinanteilen kleiner als 7 % und beträgt insbesondere 0 bis 5 %, während der Gehalt an Grobanteilen vorzugsweise 2 bis 32 % be¬ trägt. Die Grob- und Feinanteile werden abgesiebt. Die Grobanteile werden gemahlen und dem Produkt zugemischt, während die Feinanteile bzw. der Staub in die Granulation zurückgeführt werden.The granules obtained by the process according to the invention are distinguished by a grain spectrum in which the fine fraction (particle diameter less than 0.1 mm) is generally less than 10% and the coarse fraction (particle diameter greater than 2 m) is generally up to 40% . The content of fine fractions is preferably less than 7% and is in particular 0 to 5%, while the content of coarse fractions is preferably 2 to 32%. 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.
Überraschenderweise zerfallen die Granulate ungeachtet ihrer hohen Pak- kungsdichte und ihres hohen Gehaltes an wasserunlöslichen Bestandteilen in kaltem Wasser schnell und vollständig und hinterlassen in den Einspülvor¬ richtungen von Waschautomaten keine Rückstände, d. h. sie besitzen ein sehr gutes Einspülvermögen. Diese vorteilhafte Eigenschaft macht sich auch nach dem Imprägnieren mit nichtionischen Tensiden sowie im Gemisch mit anderen pulverförmigen Waschmittelkomponenten bemerkbar.Surprisingly, regardless of their high packing density and their high content of water-insoluble constituents, the granules disintegrate quickly and completely in cold water and do not leave any 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 powder detergent components.
In einer bevorzugten Ausführungsform enthalten die Granulate 2 bis 25 Gew.-% an Tensiden und insbesondere 4 bis 20 Gew.-% an anionischen und/ oder nichtionischen Tensiden. Besonders vorteilhafte Granulate enthalten 75 bis 90 Gew.-% Zeolith, der in Pulverform oder als eine Mischung aus 94 bis 73 Gew.-% Pulver und 6 bis 27 Gew.-%, jeweils bezogen auf Zeolith, einer wäßrigen Suspension vorgelegt wurde, 2 bis 10 Gew.-% Natriumsalz eines Copolymeren aus Acrylsäure und Maleinsäure und 4 bis 20 Gew.-% flüs¬ sige Niotenside. In einer weiteren bevorzugten Ausführungsform enthalten die Granulate Zeolith wie oben, 3 bis 8 Gew.-% Natriumsalz eines Copoly- meren aus Acrylsäure und Maleinsäure und 6 bis 11 Gew.-% Aniontenside, insbesondere Alkylbenzolsulfonat und Fettalkoholsulfat.In a preferred embodiment, the granules contain 2 to 25% by weight of surfactants and in particular 4 to 20% by weight of anionic and / or nonionic surfactants. Particularly advantageous granules contain 75 to 90% by weight of zeolite which has been placed in an aqueous suspension in powder form or as a mixture of 94 to 73% by weight of powder and 6 to 27% by weight, in each case based on zeolite, 2 up to 10% by weight sodium salt of a copolymer of acrylic acid and maleic acid and 4 to 20% by weight liquid nonionic surfactants. In a further preferred embodiment, the granules contain zeolite as above, 3 to 8% by weight of sodium salt of a copoly- mers from acrylic acid and maleic acid and 6 to 11 wt .-% anionic surfactants, in particular alkylbenzenesulfonate and fatty alcohol sulfate.
Die Granulate können mit flüssigen Waschmittelbestandteilen imprägniert werden, die auf anderen Wegen nicht oder nur unter Wirkungsverlust in üb¬ liche pulverför ige bzw. granuläre Wasch- und Reinigungsmittel eingear¬ beitet werden können. Hierzu zählen Schauminhibitoren, insbesondere Pa¬ raffinkohlenwasserstoffe, Silikone, Silikonharze und von langkettigen Fettsäuren abgeleitete Bis-Acyl-Alkylendiamine sowie deren Gemische. Wei¬ tere adsorbierbare Wirkstoffe sind Fettsäurealkylolamide und kationische Weichmacher, wie langkettige Fettreste aufweisende quartäre Ammoniumsalze, ferner fettlösende Lösungsmittel wie Terpene. Bevorzugt werden die Granu¬ late jedoch als Trägerkörner für flüssige nichtionische Tenside und Schauminhibitoren eingesetzt. Als "flüssig" werden diejenigen Bestandteile angesehen, die bei Raumtemperatur oder bei der Bearbeitungstemperatur zwischen 25 °C und etwa 80 °C, vorzugsweise bis 75 °C, in flüssiger Form vorliegen. Dabei kann es von Vorteil sein, Bestandteile, die beispiels¬ weise bereits bei Raumtemperatur flüssig sind, aber eine unerwünscht hohe Viskosität aufweisen, vor der Imprägnierung der Trägerkörner zu erwärmen.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. These include 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. However, the granules are preferably used as carrier grains for liquid nonionic surfactants and foam inhibitors. Those components which are present in liquid form at room temperature or at the processing temperature between 25 ° C. and about 80 ° C., preferably up to 75 ° C., are considered to be “liquid”. In this case, it can be advantageous to heat components which, for example, are already liquid at room temperature but have an undesirably high viscosity, before the impregnation of the carrier grains.
Geeignete nichtionische Tenside sind Alkoxylierungsprodukte mit 10 bis 20 Kohlenstoffatomen im hydrophoben Rest und 3 bis 20 Glykolethergruppen. Hierzu zählen Ethoxylierungsprodukte von Alkoholen, vicina'len Diolen, Ami- nen, Thioalkoholen, Fettsäureamiden und Fettsäuren. Ebenso kommen auch Blockpolymere aus Ethylenoxid und Propylenoxid, die unter der Bezeichnung Pluronic (Firma BASF/Wyandotte) handelsüblich sind, in Betracht. Weiterhin können Alkylglykoside bzw. Alkylpolyglykoside sowie deren Gemische mit den genannten Ethoxylierungsprodukten verwendet werden.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 of alcohols vicina 'len diols, amino nen, thiols, fatty acid and fatty acids. Block polymers of ethylene oxide and propylene oxide, which are commercially available under the name Pluronic (from BASF / Wyandotte), are also suitable. Furthermore, alkyl glycosides or alkyl polyglycosides and mixtures thereof with the ethoxylation products mentioned can be used.
Bevorzugte nichtionische Tenside, die an dem Granulat adsorbiert sein kön¬ nen und mit diesen zusammen als rieselfähiges Gemisch vorliegen, leiten sich von Alkoholen mit 12 bis 18 C-Atomen ab, die gesättigt oder olefi- nisch ungesättigt, linear oder in 2-Stellung methylverzweigt (Oxo-Rest) sein können. Ihre Umsetzungsprodukte mit Ethylenoxid (E0) bzw. Propylen¬ oxid (PO) sind wasserlösliche bzw. in Wasser dispergierbare Gemische von Verbindungen mit unterschiedlichem Alkoxylierungsgrad, wobei die im fol- genden angegebene Anzahl der EO- bzw. PO-Gruppen einem statistischem Mit¬ telwert entspricht.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 (E0) or propylene oxide (PO) are water-soluble or water-dispersible mixtures of compounds with different degrees of alkoxylation, the following the specified number of EO or PO groups corresponds to a statistical mean.
Beispiele für bevorzugte ethoxylierte Fettalkohole sind Ci2-Ci8-Kokosalko- hole mit 3 bis 12 EO, Cχ6-Ci8-Talgalkohol mit 4 bis 16 EO, Oleylalkohol mit 4 bis 12 EO sowie aus anderen nativen Fettalkoholgemischen erhältliche Ethoxylierungsprodukte entsprechender Ketten- und EO-Verteilung. Aus der Reihe der ethoxylierten Oxoalkohole sind beispielsweise solche der Zusam¬ mensetzung C12-C15 mit 5 bis 10 EO und C14-C15 mit 6 bis 12 EO geeignet. Weiterhin sind Alkoxylate geeignet, die EO-Gruppen und PO-Gruppen enthal¬ ten, beispielsweise Ci2-Ci8-Alkohole der Formel R-(P0)a-(E0)b bzw. R-(E0)b-(P0)c, worin a Zahlen von 1 bis 3, b Zahlen von 5 bis 20 und c Zahlen von 1 bis 10 bedeuten, wobei b größer als c sein soll.Examples of preferred ethoxylated fatty alcohols are Ci2-Ci8-coconut alcohols with 3 to 12 EO, Cχ6-Ci8-tallow alcohol with 4 to 16 EO, oleyl alcohol with 4 to 12 EO as well as ethoxylation products with appropriate chain and EO distribution available from other native fatty alcohol mixtures . From the series of ethoxylated oxo alcohols, for example those of the composition C12-C15 with 5 to 10 EO and C14-C15 with 6 to 12 EO are suitable. Also suitable are alkoxylates which contain EO groups and PO groups, for example Ci2-Ci8 alcohols of the formula R- (P0) a - (E0) b or R- (E0) b- (P0) c , where a is from 1 to 3, b is from 5 to 20 and c is from 1 to 10, where b is to be greater than c.
Das Aufbringen der flüssigen, gegebenenfalls erwärmten Zusatzstoffe, ins¬ besondere das Aufbringen der nichtionischen Tenside und der Schauminhibi¬ toren auf das Granulat kann durch Zumischen, vorzugsweise Aufsprühen er¬ folgen, wobei das Trägermaterial zweckmäßigerweise durch geeignete Misch¬ vorrichtungen in Bewegung gehalten wird. Eine weitere Nachbehandlung des körnigen Adsorbates ist nicht erforderlich. Allerdings kann ein mehrstün¬ diges Ruhenlassen des Produktes bei hohen Gehalten an aufgebrachtem flüssigen Material zweckmäßig sein, da dessen Diffusion in das Korninnere einige Zeit in Anspruch nimmt. Die Behandlung der Granulate mit den flüssigen Zusatzstoffen führt zu einem weiteren Anstieg des Schüttge¬ wichtes, das bis auf Werte von über 1000 g/1 ansteigen kann.The application of the liquid, optionally heated additives, in particular the application of the nonionic surfactants and the foam inhibitors to the granules, can be carried out by admixing, preferably spraying, the carrier material advantageously being kept in motion by suitable mixing devices. Further treatment of the granular adsorbate is not necessary. 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 treatment of the granules with the liquid additives leads to a further increase in the bulk density, which can rise to values of over 1000 g / l.
Nach dem Aufbringen des flüssigen Zusatzstoffes können die Körner gegebe¬ nenfalls noch mit einem feinteiligen Pulver als Puderungsmittel bestäubt bzw. oberflächlich beschichtet werden. Hierdurch kann die bei hohen, 15 % übersteigenden Gehalten an nichtionischen Tensiden die Rieselfähigkeit der Granulate verbessert und das Schüttgewicht geringfügig erhöht werden. Ge¬ eignete Puderungsmittel weisen eine Korngröße von 0,001 bis höchstens 0,1 mm, vorzugsweise von weniger als 0,05 mm auf und können in Anteilen von 0,03 bis 3, vorzugsweise 0,05 bis 2 Gew.-%, bezogen auf das mit Zusatz¬ stoff beladene Adsorptionsmittel, angewendet werden. In Frage kommen bei¬ spielsweise feinpulvrige Zeolithe, Kieselsäureaerogel (Aerosil(R)), färb- lose oder farbige Pigmente, wie Titandioxid. Im allgemeinen ist eine sol¬ che Nachbehandlung jedoch überflüssig, zumal durch sie die Lösungseigen¬ schaften nicht verbessert werden.After the application of the liquid additive, the grains can optionally be dusted with a finely divided powder as a powdering agent or coated on the surface. As a result, the free-flowing properties of the granules can be improved and the bulk density can be increased slightly if the content of nonionic surfactants exceeds 15%. 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. For example, finely powdered zeolites, silica airgel (Aerosil (R)), loose or colored pigments, such as titanium dioxide. In general, however, such an aftertreatment is superfluous, especially since it does not improve the solution properties.
Die Waschmitteladditive können mit dem körnigen bzw. pulverförmigen Wasch¬ mittel, beispielsweise einem Turmsprühpulver sowie dessen Gemischen mit weiteren Pulverkomponenten, wie Persalze, Enzymgranulate, Bleichaktivato¬ ren bzw. Entschäumer enthaltenden Granulaten, in bekannter Weise vereinigt und vermischt werden. Das hohe Schüttgewicht und das günstige Einspülver¬ halten der erfindungsgemäßen Additive überträgt sich auf diese komplexen Gemische. In der Praxis enthalten die Waschmittel im allgemeinen 10 bis 40 Gew.-% des erfindungsgemäßen Additivs. 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. In practice, the detergents generally contain 10 to 40% by weight of the additive according to the invention.
B e i s i e l eB e i s i e l e
Die Granulierung erfolgte in einem Mischgranulator, bestehend aus einem horizontal angeordneten zylindrischen Mischer mit einer in der Mittelachse rotierenden, mit Mischorganen bestückten Drehwelle (Pflugscharmischer, Bauart Lödige) mit einem Fassungsvermögen von 130 1 und einer daran ange¬ schlossenen, mit einer Drehzahl von 1 200 bis 1 500 Umdrehungen/Minute betriebenen Messermühle. In dem Mischgranulator wurden die pulverförmigen Bestandteile sowie gegebenenfalls die wäßrige Zeolith-Suspension vorgelegt und zu einem homogenen Gemisch verarbeitet. Nach dem Mischen, das ca. 10 Sekunden bis 1 Minute in Anspruch nahm, wurde mittels Düsen die Granulier¬ flüssigkeit im Verlauf von 1 bis 5 Minuten eingesprüht und das Gemisch unter ständigem Mischen noch weitere 1 bis 3 Minuten granuliert. Das den Mischer verlassende Granulat wurde in einer Wirbelschicht mit heißen, strömenden Trockengasen (70°C) getrocknet. In allen Beispielen betrug der Feinanteil (Teilchendurchmesser kleiner 0,1 m ) weniger als 7 % und der Grobanteil (Teilchendurchmesser größer 2 mm) weniger als 32 %.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 130 l and a connected one with a speed of 1200 up to 1,500 revolutions / minute operated knife mill. The pulverulent constituents and, if appropriate, the aqueous zeolite suspension were placed in the mixing granulator and processed to form a homogeneous mixture. After the mixing, which took about 10 seconds to 1 minute, the granulating liquid was sprayed in by means of nozzles over the course of 1 to 5 minutes 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 (70 ° C.). In all examples, the fine fraction (particle diameter less than 0.1 m) was less than 7% and the coarse fraction (particle diameter greater than 2 mm) was less than 32%.
Das eingesetzte Zeolith-Pulver war feinkristalliner, sprühgetrockneter Zeolith vom Typ NaA, der 20 Gew.-% gebundenes Wasser enthielt. Die wäßrige Zeolith-Suspension war 48 Gew.-%ig. Das Natriumsalz des verwendeten Acryl- säure-Maleinsäure-Copolymers (Sokalan(R)cP5 der Firma BASF/Deutschland) wies eine relative Molekülmasse von ca. 70 000 auf und wurde als 40 Gew.-%ige Lösung eingesetzt; die Mengenangaben beziehen sich auf wasser¬ freie Substanz.The zeolite powder used was finely crystalline, spray-dried zeolite of the NaA type, which contained 20% by weight of bound water. The aqueous zeolite suspension was 48% by weight. 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; the amounts given relate to anhydrous substance.
Beispiel 1:Example 1:
Es wurden 100 Gew.-Teile Zeolith, bezogen auf wasserfreie Substanz, mit 49,5 Gew.-Teilen einer Granulierflüssigkeit, bestehend aus 20 Gew.% Soka- lan CP5, 14 Gew.-% Cχ2-Ci8-Fettalkohol mit 5 E0 und 66 Gew.-% H2O, be¬ sprüht. Das nach der Trocknung erhaltene Granulat enthielt 88,1 Gew.-% wasserfreien Zeolith, der als Pulver vorgelegt worden war, 7 Gew.-% Soka- lan CP5 und 4,9 Gew.-% Cχ2-Ci8-Fettalkohol mit 5 E0. Das Schüttgewicht betrug vor dem Sieben 810 g/1; der Grobanteil betrug 17,3 %. Beispiel 2:There were 100 parts by weight of zeolite, based on anhydrous substance, with 49.5 parts by weight of a granulating liquid consisting of 20% by weight of Sokalan CP5, 14% by weight of Cχ2-Ci8 fatty alcohol with 5 E0 and 66% by weight of H2O, sprayed. The granules obtained after drying contained 88.1% by weight of anhydrous zeolite, which had been introduced as a powder, 7% by weight of Sokalan CP5 and 4.9% by weight of Cχ2-Ci8 fatty alcohol with 5 E0. The bulk density before sieving was 810 g / l; the gross share was 17.3%. Example 2:
Es wurden 100 Gew.-Teile Zeolith, bezogen auf wasserfreie Substanz, mit 44,2 Gew.-Teilen einer Granulierflüssigkeit, bestehend aus 19,8 Gew.-% Sokalan CP5, 50,6 Gew.-% Ci2-Ci8-Fettalkohol mit 5 EO und 29,6 Gew.-% Was¬ ser, besprüht. Das nach dem Trocknen erhaltene Granulat enthielt 80,1 Gew.-% wasserhaltigen Zeolith, der als Pulver vorgelegt worden war, 5,6 Gew.-% Sokalan CP5 und 14,3 Gew.-% Cχ2-Ci8-Fettalkohol mit 5 E0. Das Schüttgewicht betrug vor dem Sieben 900 g/1; der Grobanteil betrug 5 %.100 parts by weight of zeolite, based on anhydrous substance, were mixed with 44.2 parts by weight of a granulating liquid consisting of 19.8% by weight of Sokalan CP5, 50.6% by weight of Ci2-Ci8 fatty alcohol 5 EO and 29.6 wt .-% water, sprayed. The granules obtained after drying contained 80.1% by weight of water-containing zeolite, which had been presented as a powder, 5.6% by weight of Sokalan CP5 and 14.3% by weight of Cχ2-Ci8 fatty alcohol with 5 E0. The bulk density before sieving was 900 g / l; the gross share was 5%.
Beispiel 3:Example 3:
Es wurden 100 Gew.-Teile Zeolith, bezogen auf wasserfreie Substanz, mit 42,5 Gew.-Teilen einer Granulierflüssigkeit, bestehend aus 13,3 Gew.-% Sokalan CP5, 62,1 Gew.-% Ci2-Ci8-Fettalkohol mit 7 E0 und 24,6 Gew.-% Was¬ ser besprüht. Das nach dem Trocknen erhaltene Granulat enthielt 79,6 Gew.-% wasserhaltigen Zeolith, der als Pulver vorgelegt worden war, 3,6 Gew.-% Sokalan CP5 und 16,8 Gew.-% Ci2-Ci8-Fettalkohol mit 7 E0. Das Schüttgewicht betrug vor dem Sieben 850 g/1; der Grobanteil betrug 13,9 %.100 parts by weight of zeolite, based on anhydrous substance, were mixed with 42.5 parts by weight of a granulating liquid consisting of 13.3% by weight of Sokalan CP5, 62.1% by weight of Ci2-Ci8 fatty alcohol 7 E0 and 24.6 wt .-% water sprayed. The granules obtained after drying contained 79.6% by weight of water-containing zeolite, which had been presented as a powder, 3.6% by weight of Sokalan CP5 and 16.8% by weight of Ci2-Ci8 fatty alcohol with 7 E0. The bulk density before screening was 850 g / l; the gross share was 13.9%.
Beispiel 4:Example 4:
Es wurden 100 Gew.-Teile Zeolith, bezogen auf wasserfreie Substanz, mit 39 Gew.-Teilen einer Granulierflüssigkeit, bestehend aus 8,9 Gew.-% Sokalan CP5, 73,3 Gew.-% Ci2-Ci8-Fettalkohol mit 7 E0 und 17,8 Gew.-% Wasser, be¬ sprüht. Das nach dem Trocknen erhaltene Granulat enthielt 79,6 Gew.-% was¬ serhaltigen Zeolith, der als Pulver vorgelegt worden war, 2,2 Gew.-% Soka¬ lan CP5 und 18,2 Gew.-% Ci2-Ci8-Fettalkohol mit 7 E0. Das Schüttgewicht betrug 870 g/1; der Grobanteil betrug 2,9 %.There were 100 parts by weight of zeolite, based on anhydrous substance, with 39 parts by weight of a granulating liquid consisting of 8.9% by weight of Sokalan CP5, 73.3% by weight of Ci2-Ci8 fatty alcohol with 7 E0 and 17.8% by weight of water, sprayed. The granules obtained after drying contained 79.6% by weight of water-containing zeolite, which had been introduced as a powder, 2.2% by weight of Soka lan CP5 and 18.2% by weight of Ci2-Ci8 fatty alcohol with 7 E0. The bulk density was 870 g / 1; the gross share was 2.9%.
Beispiel 5:Example 5:
Es wurden 100 Gew.-Teile Zeolith, bezogen auf wasserfreie Substanz, mit 47,5 Gew.-Teilen einer Granulierflüssigkeit, bestehend aus 22,7 Gew.-% Sokalan CP5, 20,5 Gew.- Natriumdodecylbenzolsulfonat und 56,8 Gew.-% Was¬ ser, besprüht. Das nach dem Trocknen erhaltene Granulat enthielt 85,9 Gew.-% wasserhaltigen Zeolith, der als Pulver vorgelegt worden war, 7,4 Gew.-% Sokalan CP5 und 6,7 Gew.-% Natriumdodecylbenzolsulfonat. Das Schüttgewicht betrug vor dem Sieben 860 g/1; der Grobanteil betrug 30,2 %. Beispiel 6:100 parts by weight of zeolite, based on anhydrous substance, were mixed with 47.5 parts by weight of a granulating liquid consisting of 22.7% by weight of Sokalan CP5, 20.5% by weight of sodium dodecylbenzenesulfonate and 56.8% by weight. % Water sprayed. The granules obtained after drying contained 85.9% by weight of water-containing zeolite, which had been presented as a powder, 7.4% by weight of Sokalan CP5 and 6.7% by weight of sodium dodecylbenzenesulfonate. The bulk density before sieving was 860 g / l; the gross share was 30.2%. Example 6:
Es wurden 100 Gew.-Teile Zeolith, bezogen auf wasserfreie Substanz, mit 44 Gew.-Teilen einer Granulierflüssigkeit, bestehend aus 11,25 Gew.-% Sokalan CP5, 35,75 Gεw.-% Natriumdodecylbenzolsulfonat und 53 Gew.-% Wasser, be¬ sprüht. Das nach dem Trocknen erhaltene Granulat enthielt 85,8 Gew.-% was¬ serhaltigen Zeolith, der als Pulver vorgelegt worden war, 3,4 Gew.-% Soka¬ lan CP5 und 10,8 Gew.-% Natriumdodecylbenzolsulfonat. Das Schüttgewicht betrug 770 g/1; der Grobanteil betrug 29,8 %.There were 100 parts by weight of zeolite, based on anhydrous substance, with 44 parts by weight of a granulating liquid consisting of 11.25% by weight of Sokalan CP5, 35.75% by weight of sodium dodecylbenzenesulfonate and 53% by weight of water , sprayed. The granules obtained after drying contained 85.8% by weight of water-containing zeolite, which had been presented as a powder, 3.4% by weight of Soka lan CP5 and 10.8% by weight of sodium dodecylbenzenesulfonate. The bulk weight was 770 g / 1; the gross share was 29.8%.
Beispiel 7:Example 7:
Es wurden 100 Gew.-Teile Zeolith, bezogen auf wasserfreie Substanz, mit 46,4 Gew.-Teilen einer Granulierflüssigkeit, bestehend aus 20,25 Gew.-% Sokalan CP5, 48,7 Gew.-% Cχ2-Cχ8-Fettalkohol mit 7 E0 und 31,05 Gew.-% Wasser, besprüht. Das nach dem Trocknen erhaltene Granulat enthielt 79,6 Gew.-% wasserhaltigen Zeolith, wobei 74,4 Gew.-% als Pulver und 5,2 Gew.-% als Suspension vorgelegt worden waren, 6 Gew.- Sokalan CP5 und 14,4 Gew.-% Cχ2-Cχ8-Fettalkohol mit 7 E0. Das Schüttgewicht betrug vor dem Sie¬ ben 940 g/1; der Grobanteil betrug 31,1 %.100 parts by weight of zeolite, based on anhydrous substance, were mixed with 46.4 parts by weight of a granulating liquid consisting of 20.25% by weight of Sokalan CP5, 48.7% by weight of Cχ2-Cχ8 fatty alcohol 7 E0 and 31.05 wt .-% water, sprayed. The granules obtained after drying contained 79.6% by weight of water-containing zeolite, 74.4% by weight as powder and 5.2% by weight as suspension, 6 parts by weight of Sokalan CP5 and 14, 4% by weight of Cχ2-Cχ8 fatty alcohol with 7 E0. The bulk density before sieving was 940 g / l; the gross share was 31.1%.
Beispiel 8:Example 8:
Es wurden 100 Gew.-Teile Zeolith, bezogen auf wasserfreie Substanz, mit 42,0 Gew.-Teilen einer Granulierflüssigkeit, bestehend aus 29,5 Gew.-% Sokalan CP5, 22,9 Gew.- Cχ2-Cχs-Fettalkohol mit 5 E0 und 47,6 Gew.-% Was¬ ser, besprüht. Das nach dem Trocknen erhaltene Granulat enthielt 76,5 Gew.-% wasserhaltigen Zeolith, wobei 73,1 Gew.-% als Pulver und 13,4 Gew.-% als Suspension vorgelegt worden waren, 7,6 Gew.-% Sokalan CP5 und 5,9 Gew.-% Ci2-Cχ8-Fettalkohol mit 5 E0. Das Schüttgewicht betrug vor dem Sieben 830 g/1; der Grobanteil betrug 17,5 5'S-.100 parts by weight of zeolite, based on anhydrous substance, with 42.0 parts by weight of a granulating liquid consisting of 29.5% by weight of Sokalan CP5, 22.9 parts by weight of Cχ2-Cχs fatty alcohol with 5 E0 and 47.6 wt .-% water, sprayed. The granules obtained after drying contained 76.5% by weight of water-containing zeolite, 73.1% by weight as powder and 13.4% by weight as suspension, 7.6% by weight of Sokalan CP5 and 5.9% by weight of Ci2-Cχ8 fatty alcohol with 5 E0. The bulk density before sieving was 830 g / l; the gross proportion was 17.5 5'S.
Beispiel 9:Example 9:
Es wurden 100 Gew.-Teile Zeolith, bezogen auf wasserfreie Substanz, mit 41,0 Gew.-Teilen einer Granulierflüssigkeit, bestehend aus 19,5 Gew.-% Sokalan CP5; 31,3 Gew.-% Cχ2-Cχs-Fettalkohol mit 7 E0 und 49,2 Gew.-% Was¬ ser, besprüht. Das nach dem Trocknen erhaltene Granulat enthielt 85,5 Gew.-% wasserhaltigen Zeolith, wobei 62,5 Gew.-% als Pulver und 23 Gew.-% als Suspension vorgelegt worden waren, 5,5 Gew.-% Sokalan CP5 und 8,8 Gew.-% Cχ2-Cχ8_Fettalkohol mit 7 EO. Das Schüttgewicht betrug vor dem Sie¬ ben 840 g/1; der Grobanteil betrug 24,5 %.100 parts by weight of zeolite, based on anhydrous substance, were mixed with 41.0 parts by weight of a granulating liquid consisting of 19.5% by weight of Sokalan CP5; 31.3% by weight of Cχ2-Cχs fatty alcohol with 7 E0 and 49.2% by weight of water, sprayed. The granules obtained after drying contained 85.5% by weight of water-containing zeolite, 62.5% by weight as powder and 23% by weight as suspension, 5.5% by weight of Sokalan CP5 and 8 ,8th % By weight Cχ2-Cχ8 _ fatty alcohol with 7 EO. The bulk density before sieving was 840 g / l; the gross share was 24.5%.
Die Wiederholung der Versuche 1 bis 9, bei der 40 % der Menge des einge¬ setzten Polymers in fester Form zusammen mit dem Zeolith vorgelegt wurden, führte zu analogen Ergebnissen. Der Anteil des Wassers in der Granulier¬ flüssigkeit konnte entsprechend reduziert werden.The repetition of experiments 1 to 9, in which 40% of the amount of the polymer used was introduced in solid form together with the zeolite, led to analogous results. The proportion of water in the granulating liquid could be reduced accordingly.
Beispiel 10:Example 10:
Die Granulate aus den Versuchen 2, 8 und 9 wurden in einem Sprühmischer mit einem auf 40°C erwärmten, flüssigen, nichtionischen Tensid besprüht, bestehend aus einem mit 5 Mol EO umgesetzten Gemisch von Kokos- und Talg¬ alkohol im Verhältnis 1:4. Nach einer Standzeit von einer Stunde wiesen die Adsorbate die folgenden Schüttgewichte auf:The granules from experiments 2, 8 and 9 were sprayed in a spray mixer with a liquid, nonionic surfactant heated to 40 ° C., consisting of a mixture of coconut oil and tallow alcohol in a ratio of 1: 4 reacted with 5 mol EO. After standing for one hour, the adsorbates had the following bulk densities:
Die mit dem nichtionischen Tensid behandelten Granulate waren gut riesel¬ fähig und wiesen ein einwandfreies Einspülvermögen auf, und zwar sowohl als unverschnittenes Pulver wie auch vermischt mit einem pulverförmigen Haushaltswaschmittel im Verhältnis 1:4. The granules treated with the nonionic surfactant were free-flowing and had a perfect wash-in capacity, both as unblended powder and mixed with a powdered household detergent in a ratio of 1: 4.

Claims

P a t e n t a n s p r ü c h e Patent claims
1. Verfahren zur Herstellung von Granulaten aus Zeolith und Natrium- oder Kalium-Salzen polymerer bzw. copolymerer Carbonsäuren, wobei die Gra¬ nulierung unter Zusatz einer Granulierflüssigkeit erfolgt und das er¬ haltene Granulat bis zum Erreichen eines gut rieselfähigen Granulates mit einem Schüttgewicht von 750 bis 1000 g/1 getrocknet wird, dadurch gekennzeichnet, daß als Granulierflüssigkeit eine Mischung aus Wasser, Tensiden und (co-)polymeren Carboxylaten verwendet wird, wobei der Gehalt an Tensiden in der Granulierflüssigkeit mindestens 10 Gew.-% beträgt.1. Process for the production of granules from zeolite and sodium or potassium salts of polymeric or copolymeric carboxylic acids, the granulation taking place with the addition of a granulating liquid and the granules obtained until a free-flowing granulate having a bulk density of 750 is reached up to 1000 g / l is dried, characterized in that a mixture of water, surfactants and (co) polymeric carboxylates is used as the granulating liquid, the content of surfactants in the granulating liquid being at least 10% by weight.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der Zeolith als Pulver mit einem Wassergehalt von 19 bis 22 Gew.-% oder als Mischung aus 70 bis 95 Gew.-%, bezogen auf die Gesamtmenge Zeolith, Pulver und 5 bis 30 Gew.-%, bezogen auf die Gesamtmenge Zeolith, einer 45 bis 55 Gew.-%igen wäßrigen Suspension eingesetzt wird.2. The method according to claim 1, characterized in that the zeolite as a powder with a water content of 19 to 22 wt .-% or as a mixture of 70 to 95 wt .-%, based on the total amount of zeolite, powder and 5 to 30 wt .-%, based on the total amount of zeolite, a 45 to 55 wt .-% aqueous suspension is used.
3. Verfahren nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß die Granulierflüssigkeit zu 5 bis 30 Gew.-% aus (co-)polymerem Carboxylat, zu 10 bis 75 Gew.-% aus anionischen und/oder nichtioni¬ schen Tensiden und zu 7 bis 70 Gew.-% aus Wasser besteht.3. The method according to any one of claims 1 or 2, characterized in that the granulating liquid to 5 to 30 wt .-% of (co) polymeric carboxylate, to 10 to 75 wt .-% of anionic and / or non-ionic surfactants and consists of 7 to 70 wt .-% of water.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß zu 100 Gew.-Teilen Zeolith, berechnet als wasserfreie Substanz, oder zu einer homogenen Mischung aus Zeolith und gegebenenfalls in Pulverform vorgelegtem Salz der polymeren bzw. copolymeren Carbonsäu¬ ren Granulierflüssigkeit in der Menge zugemischt wird, daß 15 bis 40 Gew.-Teile, bezogen auf die feuchten Granulate, an flüssigen Bestand¬ teilen vorhanden sind, wobei die Granulierflüssigkeit mindestens 2 Gew.-Teile und insbesondere 5 bis 25 Gew.-Teile, bezogen auf das feuchte Granulat, an freiem Wasser enthält.4. The method according to any one of claims 1 to 3, characterized in that to 100 parts by weight of zeolite, calculated as an anhydrous substance, or to a homogeneous mixture of zeolite and optionally powdered salt of the polymeric or copolymeric Carbonsäu¬ ren granulating liquid is mixed in the amount that 15 to 40 parts by weight, based on the moist granules, of liquid constituents are present, the granulating liquid at least 2 parts by weight and in particular 5 to 25 parts by weight, based on the moist granules, contains free water.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Granulierflüssigkeit mittels Düsen auf das in Bewegung gehal¬ tene Gemisch aufgesprüht wird. 5. The method according to any one of claims 1 to 4, characterized in that the granulating liquid is sprayed onto the mixture in motion by means of nozzles.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß eine Mischung aus allen Bestandteilen der Granulierflüssigkeit oder einzelne Be¬ standteile nacheinander versprüht werden.6. The method according to claim 5, characterized in that a mixture of all components of the granulating liquid or individual components are sprayed in succession.
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß getrocknete Granulate erhalten werden, die 70 bis 92 Gew.-% Zeolith, 2 bis 12 Gew.-% Natriumsalz polymerer bzw. copolymerer Car¬ bonsäuren und 4 bis 20 Gew.-% flüssige Niotenside enthalten und die ein Schüttgewicht von 780 bis 980 g/1 aufweisen.7. The method according to any one of claims 1 to 6, characterized in that dried granules are obtained, the 70 to 92 wt .-% zeolite, 2 to 12 wt .-% sodium salt of polymeric or copolymeric carboxylic acids and 4 to 20 wt .-% contain liquid nonionic surfactants and have a bulk density of 780 to 980 g / 1.
8. Mittel, hergestellt nach einem der Ansprüche 1 bis 7.8. Agent produced according to one of claims 1 to 7.
9. Mittel nach Anspruch 8, dadurch gekennzeichnet, daß es mit bis zu 20 Gew.-%, bezogen auf das Adsorbat, mindestens eines flüssigen Wasch¬ mittelbestandteils, vorzugsweise mit einem flüssigem Niotensid oder einem Schauminhibitor, imprägniert ist.9. Composition according to claim 8, characterized in that it is impregnated with up to 20 wt .-%, based on the adsorbate, of at least one liquid detergent component, preferably with a liquid nonionic surfactant or a foam inhibitor.
10. Verwendung eines Mittels, hergestellt nach einem der Ansprüche 1 bis 9, als Pulverkomponente in Wasch- und Reinigungsmitteln. 10. Use of an agent, produced according to one of claims 1 to 9, as a powder component in washing and cleaning agents.
EP91920221A 1990-12-04 1991-11-25 Process for the production of granular zeolites Expired - Lifetime EP0560802B2 (en)

Applications Claiming Priority (3)

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DE4038609A DE4038609A1 (en) 1990-12-04 1990-12-04 METHOD FOR PRODUCING ZEOLITE GRANULES
DE4038609 1990-12-04
PCT/EP1991/002209 WO1992010559A1 (en) 1990-12-04 1991-11-25 Process for the production of granular zeolites

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6683042B1 (en) 1998-09-29 2004-01-27 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Granulation method
RU2615506C1 (en) * 2015-10-13 2017-04-05 Александр Адольфович Ламберов Method for granulation of zeolite as synthetic detergent component

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19504043C2 (en) * 1994-02-11 1998-07-09 Degussa zeolite granules
DE19549411C2 (en) * 1994-02-11 1999-05-12 Degussa Zeolite granulates with good re:dispersibility and high bulk density
DE19515256A1 (en) * 1995-04-26 1996-10-31 Degussa Zeolite granules, process for its preparation and use
CA2230310A1 (en) * 1995-09-04 1997-03-13 Unilever Plc Detergent compositions and process for preparing them
KR100750190B1 (en) * 2004-06-16 2007-08-31 요업기술원 Effective bone filler and manufacturing methods thereof
GB0811302D0 (en) * 2008-06-20 2008-07-30 Dow Corning Shampoo compositions
JP5705525B2 (en) * 2010-12-16 2015-04-22 花王株式会社 Zeolite composite particles

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2652488C3 (en) * 1976-11-18 1983-03-10 Kali-Chemie Ag, 3000 Hannover Process for the production of granules from zeolites and oxygen-releasing compounds
DE3316513A1 (en) * 1983-05-06 1984-11-08 Joh. A. Benckiser Gmbh, 6700 Ludwigshafen Abrasion resistant granular materials based on alkali metal aluminium silicate
GB8329880D0 (en) * 1983-11-09 1983-12-14 Unilever Plc Particulate adjuncts
US4552681A (en) * 1983-12-10 1985-11-12 Henkel Kommanditgesellschaft Auf Aktien Granular, free-flowing detergent component and method for its production
DE3444960A1 (en) * 1984-12-10 1986-06-12 Henkel KGaA, 4000 Düsseldorf GRAINY ADSORPTION
GB8526999D0 (en) * 1985-11-01 1985-12-04 Unilever Plc Detergent compositions
DE3545947A1 (en) * 1985-12-23 1987-07-02 Henkel Kgaa PHOSPHATE-FREE, GRANULAR DETERGENT
DE3614779A1 (en) * 1986-05-02 1987-11-05 Henkel Kgaa GRANULAR, PHOSPHATE-FREE WATER SOFTENER
DE3838086A1 (en) * 1988-11-10 1990-05-17 Henkel Kgaa METHOD FOR PRODUCING HIGH DENSITY GRANULES CONTAINING ZEOLITE
CA2017921C (en) * 1989-06-09 1995-05-16 John Michael Jolicoeur Formation of detergent granules by deagglomeration of detergent dough
US5205958A (en) * 1989-06-16 1993-04-27 The Clorox Company Zeolite agglomeration process and product
US5024782A (en) * 1989-06-16 1991-06-18 The Clorox Company Zeolite agglomeration process and product

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9210559A1 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6683042B1 (en) 1998-09-29 2004-01-27 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Granulation method
RU2615506C1 (en) * 2015-10-13 2017-04-05 Александр Адольфович Ламберов Method for granulation of zeolite as synthetic detergent component

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US5399287A (en) 1995-03-21

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