EP0635049B1 - Verfahren zur erhöhung des schüttgewichts sprühgetrockneter waschmittel - Google Patents

Verfahren zur erhöhung des schüttgewichts sprühgetrockneter waschmittel Download PDF

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Publication number
EP0635049B1
EP0635049B1 EP93908860A EP93908860A EP0635049B1 EP 0635049 B1 EP0635049 B1 EP 0635049B1 EP 93908860 A EP93908860 A EP 93908860A EP 93908860 A EP93908860 A EP 93908860A EP 0635049 B1 EP0635049 B1 EP 0635049B1
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EP
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Prior art keywords
weight
spray
powder
nonionic surfactant
tower
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EP93908860A
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German (de)
English (en)
French (fr)
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EP0635049A1 (de
Inventor
Hans Eugster
Herbert Reuter
Beat Buser
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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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles

Definitions

  • the present invention relates to a process for the production of granular detergents which are primarily intended for textile washing.
  • Detergents especially those intended for household use, are generally not marketed as simple mixtures of their constituents, but rather in the form of granular preparations in which all or the majority of the constituents are mixed intimately in the individual grains available.
  • This form has various advantages when using detergents, of which only the extensive absence of dust and the security against segregation during transport should be mentioned.
  • Such granular detergents can be produced in various ways. Methods are known for converting the individual constituents of the detergents into the granular form by compacting granulation, for example using extrusion presses. There are also processes in which the finely divided constituents are agglomerated to form larger particles with the aid of liquids, for example alkali silicate solutions (US Pat. No. 4,207,197, US Pat. No.
  • the spray drying process has long been preferred for the continuous production of large quantities of granular detergents.
  • an aqueous slurry of the detergent components is dried in free tow by hot gases to form granular products in large towers.
  • these products also have various technical advantages over detergents obtained by other processes.
  • a disadvantage has recently emerged, however, that the granular detergents obtained by spray drying usually have only low bulk densities of rarely more than 550 g / l, because this means that relatively large containers are required and a lot of packaging material is required. For this reason, efforts have recently been made to find ways to do it allow to retain the advantages of spray drying, but to increase the bulk density of the products so produced.
  • the present invention is also based on the object of producing a spray-dried detergent with a higher bulk density, although the disadvantages of the previously known processes are to be avoided.
  • the invention relates to a method for increasing the bulk density of spray-dried detergent, in which the spray-dried granular material is sprayed simultaneously or in succession in a mixing unit with a liquid nonionic surfactant and an aqueous solution of an alkali silicate.
  • This method is preferably carried out in a mixing unit which has a horizontally arranged cylindrical mixing drum in which mixing tools rotate on a horizontally running axis.
  • the new process is distinguished from the previously known ones by the fact that a further increase in the bulk density can be achieved by using silicate solution without the grains being sticky.
  • the granular detergent is surprisingly free-flowing immediately after leaving the mixing unit without the need for a separate drying step.
  • the method is suitable for spray-dried detergents of any composition, but is preferably carried out with detergent tower powders which already have a relatively high bulk density. It is particularly preferably applied to those detergent tower powders which contain little or no phosphate and in which as essential builder component sodium aluminum silicate is contained in the form of zeolite.
  • the tower powder preferably consists of 4 to 20% by weight of at least one anionic surfactant, 15 to 70% by weight of at least one builder substance, 0 to 10% by weight of nonionic surfactants and 0 to 60% by weight. % from other detergent components accessible by hot spray drying.
  • the anionic surfactants contained in the tower powder are preferably anionic surfactants from the classes of soaps, sulfonates and sulfates.
  • Suitable soaps are derived from natural or synthetic, saturated or monounsaturated fatty acids with 12 to 22 carbon atoms. Are particularly suitable from natural fatty acids such. B. coconut, palm kernel or tallow fatty acid derived soap mixtures. Preferred are those which are composed of 50 to 100% of saturated C12 ⁇ 18 fatty acid soaps and 0 to 50% of oleic acid soap. Their proportion is preferably 0.5 to 5% by weight, based on the tower powder.
  • Usable surfactants of the sulfonate type are linear alkylbenzenesulfonates (C9-13-alkyl) and olefin sulfonates, i.e. H. Mixtures of alkene and hydroxylalkanesulfonates and disulfonates, such as those obtained, for example, from C12 ⁇ 18 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline hydrolysis of the sulfonation products.
  • alkanesulfonates which are obtainable from G12 ⁇ 18 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization, and also alpha-sulfonated hydrogenated coconut, palm kernel or tallow fatty acids and their methyl or ethyl esters and mixtures thereof.
  • the sulfosuccinic acid esters with preferably 8 to 16 carbon atoms in the alcohol groups are also suitable.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters long-chain alcohols of natural and synthetic origin, ie from fatty alcohols, such as. B. coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C10 ⁇ 18 oxo alcohols and the sulfuric acid esters of secondary alcohols of this chain length.
  • the sulfuric acid monoesters of the primary alcohols or alkylphenols ethoxylated with 1 to 3 mol of ethylene oxide are also suitable.
  • Sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides are also suitable.
  • Preferred anionic surfactants are the alkylbenzenesulfonates and the fatty alcohol sulfates.
  • the anionic surfactants are usually in the form of their sodium salts.
  • Their proportion, based on the tower powder, is preferably 5 to 15% by weight.
  • Non-ionic surfactants can be completely absent in the tower powder and can only be added to the finished detergent in the subsequent mixing process.
  • the tower powder preferably also already contains a small proportion of these surfactants, in particular 0.5 to 5% by weight.
  • Suitable nonionic surfactants are derived in particular from primary alcohols, e.g. B. coconut or tallow fatty alcohol, oleyl alcohol, or of secondary alcohols with 8 to 18, preferably 12 to 18 carbon atoms.
  • Combinations of water-soluble nonionic surfactants and water-insoluble or water-dispersible nonionic surfactants are preferably used.
  • the nonionic surfactants can also have propylene glycol ether groups (PO). These can be arranged at the end or distributed statistically with the EO groups.
  • Preferred compounds of this class are those of the type R- (PO) x - (EO) y , in which R is the hydrophobic radical, x are numbers from 0.5 to 3 and y numbers from 3 to 20.
  • nonionic surfactants are ethoxylates of alkylphenols, 1,2-diols, fatty acids and fatty acid amides, and block polymers made of polypropylene glycol and polyethylene glycol or alkoxylated alkylenediamines (Pluronics and Tetronics type). Furthermore, the above-described nonionic surfactants of the EO type can be partially replaced by alkyl polyglycosides. Suitable alkyl polyglycosides have, for example, a C8 ⁇ 16 alkyl radical and an oligomeric glycoside radical with 1 to 6 glucose groups. Alkyl glycoside type surfactants are preferably incorporated in the spray dried powder.
  • the content of the ready-made detergents in nonionic surfactants or nonionic surfactant mixtures is 2 to 15% by weight, preferably 3 to 12% by weight and in particular 4 to 10% by weight.
  • the builder portion of the tower powder preferably consists predominantly of finely crystalline, synthetic, water-containing zeolites of the NaA type, which have a calcium binding capacity in the range from 100 to 200 mg CaO / g (according to the information in DE 22 24 837). Their particle size is usually in the range from 1 to 10 »m.
  • the content of these zeolites in the tower powders is preferably 10 to 50, in particular 15 to 35,% by weight.
  • the zeolite is preferably used together with polyanionic co-builders. These include compounds from the class of polyphosphonic acids and homo- or copolymeric polycarboxylic acids, derived from acrylic acid, methacrylic acid, maleic acid and olefinically unsaturated copolymerizable compounds.
  • Preferred phosphonic acids or phosphonic acid salts are 1-hydroxyethane-1,1-diphosphonate, ethylenediaminetetramethylenephosphonate (EDTMP) and Diethylene triamine pentamethylene phosphonate, mostly used in the form of their sodium salts and their mixtures.
  • the amounts used, calculated as free acid, are usually up to 1.5% by weight, based on the tower powder, preferably 0.1 to 0.8% by weight.
  • Suitable co-builders are aminopolycarboxylic acids, in particular nitrilotriacetic acid, also ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and their higher homologues. They are generally in the form of the sodium salts. Their proportion can be up to 2% by weight, in the case of nitrilotriacetic acid up to 10% by weight.
  • co-builders are homopolymers of acrylic acid and methacrylic acid, copolymers of acrylic acid with methacrylic acid and copolymers of acrylic acid, methacrylic acid or maleic acid with 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.
  • vinyl ethers such as vinyl methyl ether or vinyl ethyl ether
  • vinyl esters such as vinyl acetate or vinyl propionate
  • acrylamide, methacrylamide and with ethylene, Propylene or styrene is not more than 70 mole percent, preferably less than 60 mole percent.
  • Copolymers of acrylic acid or methacrylic acid with maleic acid as are characterized, for example, in EP 25 551, have proven to be particularly suitable. These are copolymers which contain 50 to 90 percent by weight of (meth) acrylic acid. Copolymers in which 60 to 85 percent by weight acrylic acid and 40 to 15 percent by weight maleic acid are present and which have a molecular weight between 30,000 and 120,000 are particularly preferred.
  • polyacetal carboxylic acids as described, for example, in US Pat. Nos. 4,144,226 and 4,146,495, which are obtained by polymerizing esters of glycolic acid, introducing stable terminal end groups and saponifying to give the sodium or potassium salts.
  • polymeric acids which are obtained by polymerizing acrolein and disproportionating the polymer according to Canizzaro using strong alkalis. They are essentially made up of acrylic acid units and vinyl alcohol units or acrolein units.
  • the proportion of the (co) polymeric carboxylic acids or their salts, based on acid can be up to 8% by weight, preferably 1 to 8% by weight.
  • the co-builders mentioned prevent the formation of fiber incrustations and improve the dirt-dissolving and dirt-dispersing properties of the detergents.
  • the agents are preferably phosphate-free.
  • the builder portion of the detergent may also consist of polyphosphates, in particular pentasodium triphosphate (Na-TPP).
  • Na-TPP pentasodium triphosphate
  • the content of Na-TPP should not be more than 25% by weight, preferably less than 20% by weight and in particular 0 to at most 5% by weight in the tower powder.
  • washing alkalis can also be counted among the builder substances as co-builders.
  • Their proportion in the tower powder is preferably not more than 5% by weight, in particular 1 to 3% by weight.
  • the proportion in the finished detergent can be higher, for example 1 to 15% by weight.
  • the sodium silicate improves the grain stability and the grain structure of the powdery or granular agents and has a favorable effect on the washing-in and dissolving behavior of the agents when they are entered in washing machines. It also has an anti-corrosive effect and improves washability.
  • the alkali silicate is added entirely or preferably predominantly to the tower powder only in the subsequent mixing process, this agglomeration of the zeolite particles and thus the deposition on the textiles is surprisingly avoided even in the absence of polymeric carboxylic acids and polyphosphonic or polyamino acids.
  • the amount of alkali silicate applied in the mixing process is preferably 0.5 to 5% by weight, preferably 1 to 3% by weight (calculated as anhydrous), based on tower powder.
  • Sodium carbonate for example, may also be used as a further washing alkaline, the proportion of which may be up to 20% by weight, preferably 2 to 12% by weight and in particular 5 to 10% by weight.
  • the other constituents in the tower powder include, for example, optical brighteners, graying inhibitors (dirt carriers), textile-softening substances, dyes, neutral salts, such as sodium sulfate, and water.
  • Graying inhibitors serve to keep the dirt detached from the fiber suspended in the liquor and thus prevent graying.
  • cellulose ethers such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose and methyl carboxymethyl cellulose are suitable.
  • Mixtures of various cellulose ethers are also suitable, in particular mixtures of carboxymethyl cellulose and methyl cellulose or methyl hydroxyethyl cellulose. Their proportion is preferably 0.3 to 3% by weight.
  • sheet silicates from the classes of bentonites and smectites for. B. those according to DE 23 34 899 and EP 26 529.
  • synthetic layered silicates as described in more detail in DE 35 26 405.
  • the layered silicate content can be, for example, 5 to 30% by weight.
  • plasticizing additives are long-chain fatty acid alkanolamides or dialkanolamides and reaction products of fatty acids or fatty acid diglycerides with 2-hydroxyethylethylenediamine and quaternary ammonium salts, the 1 to 2 alkyl chains with 12-18 C atoms and 2 short-chain alkyl radicals or hydroxyalkyl radicals, preferably methyl radicals , contain.
  • These softening additives are preferably added to the powder together with the nonionic surfactants in the mixer, for example in proportions of up to 10% by weight, preferably 0.5 to 3% by weight, based on the tower powder.
  • the spray drying of the powders to be processed is carried out in a manner known per se by spraying a slurry under high pressure by means of nozzles and counter-sliding hot combustion gases in a drying tower.
  • the spray-dried powder leaving the drying tower should have an initial density (liter weight) of at least 350 g / l.
  • the density of the tower powder is preferably at least 400 g / l and in particular at least 500 g / l.
  • Specifically light tower powders for example those with a high zeolite content, can be compressed more than those which already have a higher initial density.
  • the process can be used to process powders with a broad and narrow grain spectrum.
  • the tower powder should not be too fine, for example flour-like, but rather have a granular structure, so that preferably at least 20% by weight and in particular at least 50% by weight have an average Have a particle diameter of 0.4 mm (sieve analysis).
  • the process causes loose, voluminous components to be compacted, irregularly shaped components to be rounded off and very fine components to be compacted.
  • the powders leaving the tower can be processed immediately in the manner according to the invention.
  • the temperature of the powder is not critical per se, especially when it has dried thoroughly, i. H. if its water content corresponds to or is below the theoretical water connection capacity. In the case of plastic, in particular water-rich, powders, however, it should not exceed 50 ° C., preferably 40 ° C., as is generally the case when the powder is conveyed pneumatically.
  • the powder can also be stored for any length of time, but this generally only plays a role in the event of production interruptions. A continuous flow of material is always advantageous, for which the method according to the invention is particularly suitable.
  • all dry mixers are suitable for the process according to the invention, which allow the uniform application of liquids to the grain and do not have such a compacting effect that the grains are caked more strongly during the mixing process.
  • Fast-running mixers are preferred, the speed of the mixing tools should be such that comminution of the individual grains of the tower powder is largely avoided.
  • the exact conditions depend on the internal structure of the mixer and are adapted to the strength of the tower powder and its ability to absorb liquids quickly. Continuously operating mixing units are preferably used.
  • This mixing device consists of an elongated mixing drum of substantially cylindrical shape, which is mounted horizontally or moderately descending against the horizontal and is equipped with at least one filler neck or funnel and a discharge opening.
  • a central, rotatable shaft is arranged, which carries several radially aligned striking tools. When rotating, these should be at a certain distance from the smooth inner wall of the drum.
  • the length of the striking tools should be 80% to 98%, preferably 85% to 95% of the inner radius of the mixing drum.
  • the shape of the striking tools can be any, i. H. they can be straight or angled, of uniform cross-section or pointed, rounded or widened at their ends. Their cross-section can be circular or angular with rounded edges. Different shaped tools can also be combined. Those with a drop-shaped or wedge-shaped cross-section have proven themselves, a flat or rounded surface pointing in the direction of rotation, since with such tools the compaction effect outweighs the comminution effect.
  • the tools can be mounted diametrically in pairs or in a star shape on the shaft in order to avoid imbalances. A spiral arrangement has proven to be advantageous. The number of tools is not critical, but it is advisable to arrange them at a distance of 5 to 25 cm in the interest of high efficiency.
  • the conveying of the mixed material in the mixer can also be accomplished or accelerated by means of additional conveyor blades.
  • These conveyor blades can be arranged individually or in pairs between the mixing tools.
  • the degree of delivery can be regulated by the angle of attack of the blades.
  • the internal radius of the mixer is advantageously 10 to 60, preferably 15 to 50 cm, its internal length is 70 to 400 cm, preferably 80 to 300 cm, and the ratio from inner length to inner radius 4: 1 to 15: 1, preferably 5: 1 to 10: 1.
  • the number of striking tools is usually 10 to 100, usually 20 to 80.
  • the inner wall of the cylinder should be bare to avoid an undesired one Avoid sticking the powder.
  • the speed of rotation of the shaft, taking the Froude number into account is above 800 rpm (revolutions per minute), usually between 1,000 and 3,000 rpm. With larger mixers it can be reduced accordingly.
  • the residence time of the powder in this mixer depends on the performance of the system and the size of the desired effect. It should preferably be not less than 10 seconds and not more than 60 seconds, in particular it is 20 to 50 seconds. It can be adjusted to a certain extent by the inclination of the mixer, by the shape and arrangement of the striking and conveying tools also influence by the amount of powder supplied and removed. By reducing the initial cross section, a certain back pressure and thus an increase in the residence time in the mixer can be achieved.
  • the mixer should be operated so that a constant powder throughput takes place after the start-up time, i. H. that the amount of powder fed and taken out is the same and constant at all times.
  • the Froude number should be 50 to 1,200, preferably 100 to 800 and in particular 250 to 500.
  • the powder can heat up slightly.
  • additional cooling is generally unnecessary and is only required if the powder added tends to stick at elevated temperature.
  • this problem can advantageously be solved by cooling the tower powder sufficiently beforehand, for example in the case of pneumatic conveying.
  • the nonionic surfactant and the silicate solution are fed into the mixer in separate streams in the area in which intensive mechanical processing of the powder takes place. It has proven advantageous to arrange the feeds in the mixer wall.
  • the otherwise generally customary arrangement of short spray nozzles in the hollow rotating shaft makes it necessary to use spray nozzles at low rotational speeds which work with excess pressure or are operated according to the principle of the perfume atomizer with compressed air. This method of operation also requires expenditure for pressure pumps or dust extraction systems for the compressed air discharged from the mixer.
  • the arrangement in the mixer wall does not require comparable investments.
  • the liquids supplied can spread out on the inner wall and are constantly absorbed, distributed and adsorbed by the powder hitting the wall.
  • the outlet nozzles arranged on the hollow shaft are advantageously extended to such an extent that they protrude into the powder flow. Due to the increased centrifugal forces, this enables compressed air-free conveying and atomization of the liquids, which are then distributed and absorbed by the powder stream.
  • the number of feeds is expediently from 1 to 10, with an arrangement in the cylinder wall preferably being arranged laterally in the region of the ascending powder stream. If several feeds are arranged one behind the other, the last one should be installed far enough in front of the outlet opening that the escaping liquids are still distributed homogeneously.
  • the nonionic surfactant is fed to the mixers in liquid form.
  • High-melting compounds are melted beforehand and fed in at temperatures above the melting point.
  • the powder in motion also expediently has a minimum temperature which is in the region of the melting point of the nonionic surfactant or above. This temperature range can be easily adjusted by a suitable product guide after the spray drying.
  • the nonionic surfactant can be introduced into the powder in this way. It is also possible to spray part of it add and only enter the rest via the mixer. In principle, however, surfactants with a low degree of ethoxylation (low HLB value) should only be incorporated via the mixer.
  • the proportion which is introduced via the tower spray powder is preferably not more than 50% by weight, based on the total content of nonionic surfactant in the finished product. 0.5 to 10% by weight, in particular 1 to 7% by weight, of nonionic surfactant, based on tower powder, is preferably introduced into the mixer.
  • the solution of alkali silicate, which is applied to the powder separately from the nonionic surfactant in the mixer, should preferably be as concentrated as possible.
  • the solution can be fed in simultaneously with the nonionic surfactant, but also shortly before or after it.
  • the amount of silicate solution that is applied in the mixer is preferably in a weight ratio of 2: 1 to 1: 2 to the applied nonionic surfactant. In a particularly preferred embodiment, approximately equal amounts by weight of both liquids are applied in the mixer.
  • the products leaving the mixer are exceptionally free-flowing and do not require any post-treatment, especially no post-drying. This also applies if larger amounts of nonionic surfactants are applied, which would lead to poorly flowing to sticky grains on their own. For this reason, it is also not necessary to additionally incorporate dry, moisture-absorbing powders during the mixing process in order to reduce the stickiness by superficial deposition of the powder on the grains.
  • the addition of other solids, for example zeolite or finely powdered inorganic salts, which are to be combined with the tower powder is of course also possible in the process according to the invention if this is desired for other reasons.
  • the products obtained can be processed immediately after leaving the mixer, that is, filled into shipping containers or with other components of the finished detergent, such as bleach (e.g. sodium perborate as monohydrate or tetrahydrate), bleach activators (e.g. granulated tetraacetylethylenediamine), enzyme granules and defoamers (e.g. silicone or paraffin defoamers applied to the carrier material).
  • bleach e.g. sodium perborate as monohydrate or tetrahydrate
  • bleach activators e.g. granulated tetraacetylethylenediamine
  • enzyme granules and defoamers e.g. silicone or paraffin defoamers applied to the carrier material.
  • defoamers e.g. silicone or paraffin defoamers applied to the carrier material.
  • a detergent tower powder was produced by spray drying and this powder was conveyed directly with the aid of an airlift into a bunker of 2 m3 above the mixing unit.
  • the tower powder had the following composition (in% by weight): Sodium dodecylbenzenesulfonate 12.5 Oleyl / cetyl alcohol + 10 EO 2.5 Tallow soap 1.7 Zeolite NaA 25.5 Sodium silicate (1: 3.35) 3.9 Na2CO3 16.8 Brightener 0.3 Sodium sulfate + salts from raw materials 26.3 Maleic acid copolymer, sodium salt 3.5 water 7.0
  • the tower powder was fed from the bunker at a temperature of 40 ° C on average in a continuous flow of approx. 80 to 100 kg per minute to a Lödige mixer of the type CB 60, which was operated at a speed of 850 per minute.
  • Nonionic surfactant coconut alcohol + 3 EO
  • the water glass solution had a temperature of about 30 ° C, the nonionic surfactant of about 40 ° C.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP93908860A 1992-04-08 1993-03-31 Verfahren zur erhöhung des schüttgewichts sprühgetrockneter waschmittel Expired - Lifetime EP0635049B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4211699A DE4211699A1 (de) 1992-04-08 1992-04-08 Verfahren zur Erhöhung des Schüttgewichts sprühgetrockneter Waschmittel
DE4211699 1992-04-08
PCT/EP1993/000775 WO1993021300A1 (de) 1992-04-08 1993-03-31 Verfahren zur erhöhung des schüttgewichts sprühgetrockneter waschmittel

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Publication Number Publication Date
EP0635049A1 EP0635049A1 (de) 1995-01-25
EP0635049B1 true EP0635049B1 (de) 1995-12-20

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US (1) US5501810A (es)
EP (1) EP0635049B1 (es)
AT (1) ATE131866T1 (es)
DE (2) DE4211699A1 (es)
ES (1) ES2082642T3 (es)
WO (1) WO1993021300A1 (es)

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DE19702845A1 (de) * 1997-01-27 1998-07-30 Henkel Kgaa Verfahren zur Herstellung von Tensidgranulaten
DE19752388A1 (de) * 1997-11-26 1999-05-27 Henkel Kgaa Verfahren zur Herstellung von Wasch- und Reinigungsmitteln mit hoher Schüttdichte
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US6680290B1 (en) * 1999-07-02 2004-01-20 Dow Europe S.A. Clear softening formulations including alkoxylated additives

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DE59301220D1 (de) 1996-02-01
WO1993021300A1 (de) 1993-10-28
ATE131866T1 (de) 1996-01-15
EP0635049A1 (de) 1995-01-25
ES2082642T3 (es) 1996-03-16
DE4211699A1 (de) 1993-10-14
US5501810A (en) 1996-03-26

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