EP0560802B2 - Procede de fabrication de granulats de zeolite - Google Patents

Procede de fabrication de granulats de zeolite Download PDF

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Publication number
EP0560802B2
EP0560802B2 EP91920221A EP91920221A EP0560802B2 EP 0560802 B2 EP0560802 B2 EP 0560802B2 EP 91920221 A EP91920221 A EP 91920221A EP 91920221 A EP91920221 A EP 91920221A EP 0560802 B2 EP0560802 B2 EP 0560802B2
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Prior art keywords
weight
zeolite
granules
liquid
water
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German (de)
English (en)
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EP0560802A1 (fr
EP0560802B1 (fr
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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.
  • European patent application 21 267 describes granules containing zeolites and Alkali silicates which have a particle size between 0.15 and 2 mm and a bulk density of 300 to Have 700 g / l. They are also suitable for adsorbing liquid detergent components, in particular of nonionic surfactants.
  • a dry premix of zeolite and Alkali metal silicate (mixing ratio 1: 1 to 1: 8) sprayed with water and agglomerated in a granulator, whereupon the excess water to a residual content of less than 5 wt .-% Drying is removed.
  • the main disadvantage is the high content of strongly alkaline-reacting alkali silicates, thus the 'use of these granules in neutral to weakly alkaline, for sensitive Textiles suitable detergents is severely restricted.
  • European patent application 149 264 (Unilever) teaches that the adsorption of liquid detergent components, especially non-ionic ones Surfactants commercially available spray-dried zeolites or their mixtures with inorganic salts, such as Sodium sulfate.
  • the bulk density of the relatively fine-particle spray products is in the range from 450 to 600 g / l, the particles having a size between 0.05 and 0.5 mm.
  • German patent application 38 38 086 describes the production of zeolite and granules the sodium or potassium salts of polymeric or copolymeric carboxylic acids, the agglomeration or granulation with the addition of a granulating liquid and the agglomerate obtained up to Reaching a free-flowing granulate with a bulk density of 750 to 1000 g / l is dried.
  • This is based on a homogeneous powdery mixture of zeolite and the salt of the (co) polymers Carboxylic acids and granulates them in a further mixing and granulation step with the addition of Water, which is preferably sprayed onto the powder mixture kept in motion.
  • the polycarboxylates are presented in solid form and not in dissolved form as part of the granulating liquid added because the amount of granulating liquid used is a critical factor and therefore exact must be dosed. Excessive amounts of granulating liquid lead to granules with a wide one Grain spectrum and an undesirably high coarse fraction (particle size above 2 mm in length) as well a lower bulk density.
  • the invention relates to a method for producing granules from zeolite and sodium or Potassium salts of polymeric or copolymeric carboxylic acids, the granulation with the presence of zeolite and subsequent addition of a Granulation liquid takes place and the granules obtained until a free-flowing granulate is reached is dried with a bulk density of 750 to 1,000 g / l, which is characterized in that as Granulating liquid a mixture of water, surfactants and (co) polymeric carboxylates is used, wherein the content of surfactants in the granulating liquid is 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 the zeolite NaX in such mixtures is advantageously below 30%. Preferred zeolites if there are no particles larger than 30 ⁇ m, at least 80% consist of particles one Size of less than 10 microns and are in detergent quality.
  • zeolite powder as such Spray-dried zeolite powder mixtures are also suitable (products from Degussa, trade name Wessalith), the small amounts of additives such as sodium sulfate, salts of nitrilotriacetic acid, sodium hydroxide, Contain carboxymethyl cellulose, (co) polymeric carboxylates or nonionic surfactants.
  • part of the zeolite is in the form of a 45 to 55% by weight aqueous suspension used.
  • zeolite based on the Total amount of zeolite, as an aqueous suspension and 95 to 70 wt .-%, based on the total amount Zeolite, presented as a powder.
  • This water content and the water content of the powdered zeolite are included in the calculation of the water balance; the amount of water to be introduced into the granulation stage can be reduced by these shares.
  • the zeolite suspensions used contain usually about 1.5 to 3% by weight, based on the suspension, of stabilizers, including those Nonionic surfactants, anionic surfactants or polymeric polycarboxylates belong.
  • the granules that after the process according to the invention are preferably 50 to 95% by weight, in particular 70 to 92% by weight, based on the dried granules, of water-containing zeolite.
  • Carboxylic acids of which the sodium salts are preferred, are polyacrylic acid, polymethacrylic 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, furthermore with vinyl esters such as vinyl acetate or vinyl propionate, Acrylamide, methacrylamide and with ethylene, propylene or styrene.
  • copolymeric acids in in which one of the components has no acid function, in the interest of one is their proportion sufficient water solubility not more than 50 mole%, preferably less than 30 mole%.
  • Copolymers of acrylic acid and methacrylic acid with maleic acid have proven particularly suitable. Copolymers containing 50 to 90% by weight of acrylic acid and 50 to 10% by weight are particularly preferred. Contain maleic acid.
  • the relative molecular weight of the homo- or copolymeric polycarboxylates is in generally 2,000 to 150,000, preferably 5,000 to 100,000.
  • the polycarboxylates are preferred in the form of 30 to 50% by weight, in particular 35 to 45% by weight, aqueous solutions.
  • this Solutions can, for the purpose of lowering the viscosity, water-soluble inorganic salts, for example Sodium sulfate, in amounts up to 10 wt .-%, based on the polycarboxylate added become.
  • the polycarboxylates are partially combined in powder form presented with the finely divided zeolite. It is preferred to have a maximum of 50% by weight and in particular to use a maximum of 40% by weight of the polymeric carboxylates in powder form.
  • the commercially available salts (co-) polymer Powdered carboxylic acids often contain 5 to 15% by weight of moisture. This proportion of water is also included in the calculation of the water balance.
  • the mathematical is Proportion of the salts in the preparation of the compositions or in the composition of the finished granules obtain anhydrous salt.
  • the granules according to the invention contain the salts of the polymeric or copolymeric carboxylic acids preferably in amounts of 2 to 12 wt .-% and especially in amounts from 4 to 10% by weight.
  • the granulating liquid contains at least water as a liquid component, at least polymer or copolymeric carboxylates as a fixed component and anionic and / or nonionic surfactants.
  • the granulating liquid contains a mixture of water and liquid as a liquid component nonionic surfactants.
  • the granulating liquid advantageously consists of 5 to 30% by weight of (co) polymeric Carboxylate, 10 to 75 wt .-% of anionic and / or nonionic surfactants and 7 to 70 % By weight of water.
  • the granulating liquid consists of 10 to 25% by weight of (co) polymeric Carboxylate, 10 to 65 wt .-% of nonionic surfactants or 10 to 40 wt .-% 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 (EO) with linear primary alcohols, such as, for. B. on coconut oil, tallow oil or oleyl alcohol, or on primary alcohols (oxo alcohols) branched with methyl in the 2-position.
  • EO ethylene oxide
  • C 12 -C 14 alcohols with 3 EO or 4 EO C 13 -C 15 alcohols with 3, 5 or 7 EO
  • C 12 -C 18 alcohols with 2, 3, 5 or 7 EO and mixtures this, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 5 EO.
  • Preferred ethoxylated fatty alcohols are also those with a narrow homolog distribution (narrow range 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 C 9 -C 13 alkylbenzenesulfonates, in particular C 12 alkylbenzenesulfonate, and sulfonates based on oleochemicals such as the esters of ⁇ -sulfofatty acids, the sulfo group being in its salt form (mono salt), e.g. B. the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids into consideration.
  • Suitable surfactants of the sulfate type are, for example, the optionally ethoxylated sulfuric acid monoesters from primary alcohols of natural and synthetic origin, ie from fatty alcohols, such as. 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.
  • the wet content is included in the calculation of the introduced liquid components, or the amount of liquid introduced into the pelletizing stage can this proportion can be reduced.
  • the moist, non-dried granules 100 parts by weight of zeolite are calculated as an anhydrous substance, or to a homogeneous mixture of zeolite and optionally in powder form submitted salt of the polymeric or copolymeric carboxylic acid granulating liquid in the amount admixed that preferably 15 to 45 parts by weight, in particular 18 to 40 parts by weight, based on the moist granules, are present in liquid components.
  • the proportion of free, not in the form of water of crystallization or water bound in a similar way in the granulating liquid be small and solely dependent on the amount and concentration of the polymer or copolymeric carboxylate solution.
  • 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 Granules in free water.
  • the granulation can be carried out batchwise or continuously in conventional mixing and granulating devices be performed.
  • B. pelletizers which are arranged horizontally or consist of cylindrical containers inclined to the horizontal, one in the longitudinal axis with Mixing tools and conveyor blades equipped shaft rotates.
  • the feeding of the granulating liquid can be done through the spray nozzle in the wall or on the high shaft.
  • two consecutive mixers can be used first mixer the production of the dry or, if an aqueous zeolite suspension is used, wet premix and in the second mixer the granulation with the addition of surfactant and polycarboxylate Granulating liquid takes place.
  • Continuous work is also possible in a mixer, wherein in a first mixing section either the powder streams and / or the powder streams and the zeolite suspension be combined and homogenized and the mixture after further transport in one subsequent mixing section treated with the surfactant and polycarboxylate-containing granulating liquid and is granulated.
  • the granulating liquid is preferably sprayed onto the fluid in motion Sprayed mixture.
  • the granulation is generally normal to moderately elevated temperatures, preferably at temperatures between 20 and 40 ° C and generally requires 5 to 15 minutes.
  • the drying can be carried out by introducing hot gases in a third mixing section, e.g. B. a fluidized bed, or also after the granules have been discharged from the mixer, for example in a vibratory conveyor, a free fall dryer or in a thin layer on a conveyor belt.
  • a third mixing section e.g. B. a fluidized bed
  • the drying is carried out until the water added in the granulation step to a level of less than 5% by weight, preferably less than 3% by weight, based in each case on the dried granules, is removed.
  • the drying process still contains more water, originally with the zeolite or a non-anhydrous one inserted (co) polymeric salt were removed.
  • Such "over-dried" granules can have application technology advantages, for example when added to detergents contain moisture-sensitive active ingredients.
  • drainage of the zeolite should preferably be used not to be driven below a water content of 18% by weight, based on zeolite, in order to reduce the activity to avoid.
  • the water content of the granules is expediently in a range in which the water binding capacity of the zeolite is largely saturated, d. H. where 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 / l, in particular from 800 to 950 g / l. Due to their tight packing and their small pore volume, their absorption capacity is for liquid or pasty detergent ingredients, especially nonionic surfactants and foam inhibitors, for example paraffin oil or silicone oil, something compared to specifically lighter carrier grains reduced, but is still 15 to a maximum of 20 wt .-% without significant impairment the flowability of the granules. This in view of the high packing density and if necessary already contained in the granules of nonionic surfactants still surprisingly high Adsorption capacity is sufficient for the usual areas of application, in particular for use as Compound component in detergents and cleaning agents, completely from.
  • 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) generally less than 10% and the Coarse fraction (particle diameter greater than 2 mm) is generally up to 40%.
  • the Fines content less than 7% and is in particular 0 to 5%, while the content of Coarse fractions are preferably 2 to 32%.
  • the coarse and fine particles are sieved.
  • the rough shares are ground and mixed into the product, while the fines or dust in the Granulation can be attributed.
  • the granules disintegrate regardless of their high packing density and their high Content of water-insoluble components in cold water quickly and completely and leave in no residue is left in the washing-up devices of washing machines, d. H. they have a very good one Ein HughesFC. This advantageous property is also evident after impregnation with nonionic Surfactants and in a mixture with other powder detergent components are noticeable.
  • 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, in powder form or as a mixture of 94 to 73 % By weight of powder and 6 to 27% by weight, based in each case on zeolite, of an aqueous suspension 2 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 sodium salt of a copolymer of acrylic acid and maleic acid and 6 to 11 % By weight of anionic surfactants, in particular alkylbenzenesulfonate and fatty alcohol sulfate.
  • the granules can be impregnated with liquid detergent ingredients that are on others Because of no or only loss of effectiveness in conventional powder or granular detergents and cleaning agents can be incorporated.
  • liquid detergent ingredients that are on others Because of no or only loss of effectiveness in conventional powder or granular detergents and cleaning agents can be incorporated.
  • foam inhibitors especially paraffin hydrocarbons, Silicones, silicone resins and bis-acyl-alkylenediamines derived from long-chain fatty acids as well as their mixtures.
  • Other adsorbable active ingredients are fatty acid alkylolamides and cationic Plasticizers, such as long-chain fatty quaternary ammonium salts, and also fat-dissolving solvents like terpenes.
  • the granules are preferred as carrier grains for liquid nonionic Surfactants and foam inhibitors used.
  • Those components that are considered “liquid” are those Room temperature or at the processing temperature between 25 ° C and about 80 ° C, preferably up to 75 ° C, in liquid form. It can be advantageous to use components that already exist, for example are liquid at room temperature but have an undesirably high viscosity before impregnation to heat the carrier grains.
  • Suitable nonionic surfactants are alkoxylation products with 10 to 20 carbon atoms in the hydrophobic residue and 3 to 20 glycol ether groups. These include ethoxylation products of alcohols, vicinal diols, amines, thio alcohols, fatty acid amides and fatty acids. Block polymers also come from ethylene oxide and propylene oxide, which are sold under the name Pluronic (BASF / Wyandotte) are customary in the trade. Furthermore, alkyl glycosides or alkyl polyglycosides and their Mixtures with the ethoxylation products mentioned can be used.
  • Preferred nonionic surfactants which can be adsorbed on the granules and with them together as a free-flowing mixture are derived from alcohols with 12 to 18 carbon atoms, which saturated or olefinically unsaturated, linear or methyl-branched in the 2-position (oxo radical).
  • Your Reaction products with ethylene oxide (EO) or propylene oxide (PO) are water-soluble or in water dispersible mixtures of compounds with different degrees of alkoxylation, the following specified number of EO or PO groups corresponds to a statistical mean.
  • Examples of preferred ethoxylated fatty alcohols are C 12 -C 18 coco alcohols with 3 to 12 EO, C 16 -C 18 tallow alcohol with 4 to 16 EO, oleyl alcohol with 4 to 12 EO and ethoxylation products of corresponding chain and EO available from other native fatty alcohol mixtures -Distribution. From the series of ethoxylated oxo alcohols, for example those of the composition C 12 -C 15 with 5 to 10 EO and C 14 -C 15 with 6 to 12 EO are suitable.
  • alkoxylates which contain EO groups and PO groups, for example C 12 -C 18 alcohols of the formula R- (PO) a - (EO) b or R- (EO) b - (PO) 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 on the granules can be added by mixing, preferably Spraying take place, the carrier material expediently by suitable mixing devices in Movement is kept. Further treatment of the granular adsorbate is not necessary. However, leaving the product to rest for several hours at high levels of applied liquid material may be useful, 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 Bulk density, which can rise to values of over 1 000 g / l.
  • the grains can optionally be dusted with a finely divided powder as powdering agent or coated on the surface.
  • a finely divided powder as 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 that with additive loaded adsorbent.
  • finely powdered zeolites, silica airgel (Aerosil (R) ), colorless or colored pigments, such as titanium dioxide are suitable. In general, however, such an aftertreatment is superfluous, especially since it does not improve the solution properties.
  • the detergent additives can be mixed with the granular or powder detergent, for example a tower spray powder and its mixtures with other powder components, such as persalt, enzyme granules, Bleach activators or defoamers containing granules, combined in a known manner and be mixed.
  • the detergents contain general 10 to 40 wt .-% of the additive according to the invention.
  • the granulation was carried out in a mixing granulator consisting of a horizontally arranged one cylindrical mixer with a rotating shaft rotating in the central axis and equipped with mixing elements (Ploughshare mixer, type Lödige) with a capacity of 130 l and a connected Knife mill operated at a speed of 1,200 to 1,500 revolutions / minute.
  • mixing elements Ploughshare mixer, type Lödige
  • the pulverulent constituents and optionally the aqueous zeolite suspension were mixed granulators submitted and processed into a homogeneous mixture. After mixing, this is about 10 seconds took 1 minute, the granulating liquid was sprayed in the course of 1 to 5 minutes by means of nozzles sprayed in and the mixture was granulated for a further 1 to 3 minutes with constant mixing.
  • Granules leaving the mixer were placed in a fluidized bed with hot, flowing dry gases (70 ° C.) dried.
  • the fine fraction particle diameter less than 0.1 mm
  • the coarse fraction particle diameter larger 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 quantities refer to anhydrous substance.
  • zeolite 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 C 12 -C 18 fatty alcohol with 5 EO and 66% by weight H 2 O, 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 C 12 -C 18 fatty alcohol with 5 EO.
  • the bulk density before sieving was 810 g / l; the gross share was 17.3%.
  • 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 C 12 -C 18 - Fatty alcohol with 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 12 -C 18 fatty alcohol with 5 EO.
  • 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 C 12 -C 18 - Sprayed fatty alcohol with 7 EO and 24.6 wt .-% water.
  • 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 C 12 -C 18 fatty alcohol with 7 EO.
  • the bulk density before screening was 850 g / l; the gross share was 13.9%.
  • zeolite 100 parts by weight of zeolite, based on anhydrous substance, were mixed with 39 parts by weight of a granulating liquid consisting of 8.9% by weight of Sokalan CP5, 73.3% by weight of C 12 -C 18 fatty alcohol 7 EO and 17.8 wt .-% water, sprayed.
  • the granules obtained after drying contained 79.6% by weight of water-containing zeolite, which had been presented as a powder, 2.2% by weight of Sokalan CP5 and 18.2% by weight of C 12 -C 18 fatty alcohol with 7 EO.
  • the bulk density was 870 g / l; the gross share was 2.9%.
  • zeolite based on anhydrous substance
  • 47.5 parts by weight of one Granulating liquid consisting of 22.7% by weight Sokalan CP5, 20.5% by weight sodium dodecylbenzenesulfonate and 56.8 wt% water.
  • the granules obtained after drying contained 85.9% by weight water-containing zeolite, which had been presented as a powder, 7.4% by weight of Sokalan CP5 and 6.7% by weight Dodecylbenzenesulfonate.
  • the bulk density before sieving was 860 g / l; the bulk was 30.2%.
  • zeolite 100 parts by weight of zeolite, based on anhydrous substance, were mixed with 44 parts by weight of one Granulating liquid consisting of 11.25% by weight Sokalan CP5, 35.75% by weight sodium dodecylbenzenesulfonate and 53% by weight water.
  • the granules obtained after drying contained 85.8% by weight water-containing zeolite, which was presented as a powder, 3.4 wt .-% Sokalan CP5 and 10.8 wt .-% Dodecylbenzenesulfonate.
  • the bulk density was 770 g / l; 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 12 -C 18 - Fatty alcohol with 7 EO 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% by weight of Sokalan CP5 and 14 , 4 wt .-% C 12 -C 18 fatty alcohol with 7 EO.
  • 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, were mixed with 42.0 parts by weight of a granulating liquid consisting of 29.5% by weight of Sokalan CP5, 22.9% by weight of C 12 -C 18 - Fatty alcohol with 5 EO 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 C 12 -C 18 fatty alcohol with 5 EO.
  • the bulk density before sieving was 830 g / l; the gross share was 17.5%.
  • 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 12 -C 18 - Fatty alcohol with 7 EO and 49.2 wt .-% 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 , 8 wt .-% C 12 -C 18 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 indicated perfect induction, both as unblended powder and mixed with a powdered household detergent in a ratio of 1: 4.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Cosmetics (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Claims (7)

  1. Procédé de fabrication de granulats en zéolite et sels de sodium ou potassium d'acides carboxyliques polymères ou copolymères, dans lequel la granulation a lieu en ajoutant premièrement la zéolite et ensuite un liquide de granulation et le granulat obtenu est séché jusqu'à obtention d'un granulat capable d'un bon écoulement avec une densité apparente de 750 à 1000 g/l, caractérisé en ce que comme liquide de granulation on utilise un mélange d'eau, de tensioactifs et de carboxylates (co-)polymères, la teneur en tensioactifs dans le liquide de granulation se montant à au moins 10 % en poids.
  2. Procédé selon la revendication 1, caractérisé en ce que la zéolite est mise en oeuvre comme une poudre avec une teneur en eau de 17 à 25 % en poids ou comme un mélange de 70 à 95 % en poids, par rapport à la quantité totale de zéolite, de poudre et de 5 à 30 % en poids, par rapport à la quantité totale de zéolite, d'une suspension aqueuse de 45 à 55 % en poids.
  3. Procédé selon une des revendications 1 ou 2, caractérisé en ce que le liquide de granulation se compose pour 5 à 30 % en poids de carboxylate (co-)polymère, pour 10 à 75 % en poids de tensioactifs anioniques et/ou non ionique et pour 7 à 70 % en poids d'eau.
  4. Procédé selon une des revendications 1 à 3, caractérisé en ce que le liquide de granulation est mélangé à 100 parties en poids de zéolite, calculée comme substance anhydre, ou à un mélange homogène de zéolite et éventuellement de sel préparé sous forme de poudre des acides carboxyliques polymères ou copolymères en quantité telle que 15 à 45, en particulier 18 à 40 parties en poids, rapportées aux granulats humides, de composants liquides sont présents, tandis que le liquide de granulation contient au moins 2 parties en poids et en particules 5 à 25 parties en poids, rapportées au granulat humide, d'eau libre.
  5. Procédé selon une des revendications 1 à 4, caractérisé en ce que le liquide de granulation est pulvérisé au moyen de buses sur le mélange maintenu en mouvement.
  6. Procédé selon une des revendications 1 à 5, caractérisé en ce qu'on obtient des granulats séchés, qui contiennent 70 à 92 % en poids de zéolite, 2 à 12 % en poids de sel de sodium d'acides carboxyliques polymères ou copolymères et 4 à 20 % en poids de tensioactifs anioniques et/ou non ioniques et qui ont une densité apparente de 780 à 980 g/l.
  7. Agent produit selon une des revendications 1 à 6, caractérisé en ce qu'il est imprégné jusqu'à 20 % en poids, rapporté au produit adsorbé, avec au moins un composant liquide de détergent, de préférence avec un non tensioactif liquide ou un inhibiteur de mousse.
EP91920221A 1990-12-04 1991-11-25 Procede de fabrication de granulats de zeolite Expired - Lifetime EP0560802B2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4038609 1990-12-04
DE4038609A DE4038609A1 (de) 1990-12-04 1990-12-04 Verfahren zur herstellung von zeolith-granulaten
PCT/EP1991/002209 WO1992010559A1 (fr) 1990-12-04 1991-11-25 Procede de fabrication de granulats de zeolite

Publications (3)

Publication Number Publication Date
EP0560802A1 EP0560802A1 (fr) 1993-09-22
EP0560802B1 EP0560802B1 (fr) 1995-05-10
EP0560802B2 true EP0560802B2 (fr) 2002-08-28

Family

ID=6419545

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91920221A Expired - Lifetime EP0560802B2 (fr) 1990-12-04 1991-11-25 Procede de fabrication de granulats de zeolite

Country Status (8)

Country Link
US (1) US5399287A (fr)
EP (1) EP0560802B2 (fr)
JP (1) JP3167721B2 (fr)
KR (1) KR0181978B1 (fr)
AT (1) ATE122382T1 (fr)
DE (2) DE4038609A1 (fr)
ES (1) ES2071345T5 (fr)
WO (1) WO1992010559A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19549411C2 (de) * 1994-02-11 1999-05-12 Degussa Zeolithgranulate
DE19504043C2 (de) * 1994-02-11 1998-07-09 Degussa Zeolithgranulate
DE19515256A1 (de) * 1995-04-26 1996-10-31 Degussa Zeolithgranulat, Verfahren zu seiner Herstellung und Verwendung
AU6740496A (en) * 1995-09-04 1997-03-27 Unilever Plc Detergent compositions and process for preparing them
DE19844522A1 (de) 1998-09-29 2000-03-30 Henkel Kgaa Granulationsverfahren
KR100750190B1 (ko) * 2004-06-16 2007-08-31 요업기술원 골 수복에 효과적인 골 충전재 및 그의 제조 방법
GB0811302D0 (en) * 2008-06-20 2008-07-30 Dow Corning Shampoo compositions
JP5705525B2 (ja) * 2010-12-16 2015-04-22 花王株式会社 ゼオライト複合粒子群
RU2615506C1 (ru) * 2015-10-13 2017-04-05 Александр Адольфович Ламберов Способ гранулирования цеолита в качестве компонента синтетических моющих средств

Family Cites Families (12)

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Publication number Priority date Publication date Assignee Title
DE2652488C3 (de) * 1976-11-18 1983-03-10 Kali-Chemie Ag, 3000 Hannover Verfahren zur Herstellung von Granulaten aus Zeolithen und sauerstoffabgebenden Verbindungen
DE3316513A1 (de) * 1983-05-06 1984-11-08 Joh. A. Benckiser Gmbh, 6700 Ludwigshafen Abriebfeste granulate auf basis von alkalialuminiumsilikat
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 (de) * 1984-12-10 1986-06-12 Henkel KGaA, 4000 Düsseldorf Koerniges adsorptionsmittel
GB8526999D0 (en) * 1985-11-01 1985-12-04 Unilever Plc Detergent compositions
DE3545947A1 (de) * 1985-12-23 1987-07-02 Henkel Kgaa Phosphatfreies, granulares waschmittel
DE3614779A1 (de) * 1986-05-02 1987-11-05 Henkel Kgaa Granulares, phosphatfreies wasserenthaertungsmittel
DE3838086A1 (de) * 1988-11-10 1990-05-17 Henkel Kgaa Verfahren zur herstellung zeolithhaltiger granulate hoher dichte
CA2017921C (fr) * 1989-06-09 1995-05-16 John Michael Jolicoeur Preparation de granules detergentes par voie de separation d'une pate detergente
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

Also Published As

Publication number Publication date
DE4038609A1 (de) 1992-06-11
DE59105474D1 (de) 1995-06-14
ES2071345T5 (es) 2003-03-16
JPH06503109A (ja) 1994-04-07
EP0560802A1 (fr) 1993-09-22
US5399287A (en) 1995-03-21
ATE122382T1 (de) 1995-05-15
JP3167721B2 (ja) 2001-05-21
KR930703424A (ko) 1993-11-30
KR0181978B1 (ko) 1999-04-15
ES2071345T3 (es) 1995-06-16
EP0560802B1 (fr) 1995-05-10
WO1992010559A1 (fr) 1992-06-25

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