EP1076685A1 - Procede pour la production de granules actifs detergents - Google Patents

Procede pour la production de granules actifs detergents

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Publication number
EP1076685A1
EP1076685A1 EP99917991A EP99917991A EP1076685A1 EP 1076685 A1 EP1076685 A1 EP 1076685A1 EP 99917991 A EP99917991 A EP 99917991A EP 99917991 A EP99917991 A EP 99917991A EP 1076685 A1 EP1076685 A1 EP 1076685A1
Authority
EP
European Patent Office
Prior art keywords
mixing zone
weight
solids
aqueous
mixer
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
EP99917991A
Other languages
German (de)
English (en)
Other versions
EP1076685B1 (fr
Inventor
Hubert Harth
Petra-Stefanie Madle
Gisela Nitsch
Franz Pfeifer
Johann Seif
Herbert Senger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1076685A1 publication Critical patent/EP1076685A1/fr
Application granted granted Critical
Publication of EP1076685B1 publication Critical patent/EP1076685B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • 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

Definitions

  • the invention relates to a process for producing washable or cleaning-active granules with bulk densities below the value which is determined by the normal calculation method, the granules having a free-flowing and homogeneous structure, by mixing and agglomerating and, if appropriate, subsequent processing.
  • a modern washing or cleaning-active granulate is usually required to have sufficient storage stability with regard to the flowability of the granular products.
  • This requirement is normally met today with the help of so-called surface modifiers, which cover the surface of the granules and prevent the granules from sticking to one another.
  • Another requirement namely to produce a macroscopically homogeneous product, which shows no segregation during production and filling as well as no separation of specifically different powder qualities, by mixing and granulating in order to prevent the segregation of the individual components during transport or storage, can
  • experts today still face problems depending on the raw materials used and the equipment available. Then comes as a further requirement the specification of a specific bulk density with high formulation variability In addition, it is necessary, under the possibilities given so far, for the expert to make compromises.
  • a high bulk density is achieved (roughly the bulk density is achieved, which is calculated using the normal calculation method "sum of the weight percentages of the individual solid raw materials multiplied by their bulk weights and the liquid percentages multiplied by their density" is predicted or the bulk densities are only slightly less when the mixer is operating efficiently), but normally there is not sufficient agglomeration and therefore inhomogeneous granules and a relatively broad grain spectrum with coarse and fine-grain fractions are obtained. In addition, at least some of the coarser solids are destroyed These products tend to segregate.
  • mixers and granulators such as the ploughshare mixer can be characterized by rotating tools
  • the so-called free-fall mixers are characterized in that they contain no tools and are among the mixers with rotating containers. In them, the mix is lifted by friction on the wall or internals and trickles over the bed surface under the influence of gravity.
  • pulp-like starting materials are granulated
  • one or more solids are usually processed with the aid of granulating liquids during mixing and agglomeration.
  • a process for the production of washing or cleaning-active granules is described, the addition of water or aqueous solutions and / or aqueous dispersions taking place only in such amounts that the water-binding capacity of the finished stable granules is not exceeded .
  • the bulk weights of the embodiments mentioned in the examples are between 650 g / 1 and 780 g / 1.
  • Another problem is the homogeneous incorporation of small components, which are only used in minor amounts, for example up to about 10% by weight, in a washing or cleaning agent. These include cobuilders, optical brighteners, sequestering agents, graying inhibitors, soap, colorants and fragrances, etc.
  • the German patent application DE-A-196 51 072 suggests that small components of this type be accommodated in a separate additive, with the use of this additive being a more precise one Dosage and a more homogeneous distribution of the small components in the entire detergent or cleaning agent is sought.
  • mixed products usually contain a basic granulate, to which several other constituents are subsequently added, or that several compounds (each with at least two washing or cleaning-active ingredients) are prepared separately and subsequently, if necessary, with the addition of other ingredients
  • Raw materials are mixed.
  • Typical admixing components are, for example, peroxy bleaching agents such as perborate and / or percarbonate, which can have bulk densities between 800 and 1000 g / 1, or sodium sulfate, which has a bulk density of up to 1500 g / 1 and still in some amounts in amounts can contain up to 45 wt .-%.
  • Heavy sodium carbonates or bleach activators are also suitable as admixing components.
  • the admixing components mentioned with bulk weights above 700 g / 1 can be incorporated relatively easily into heavy detergents or cleaning agents;
  • detergents or cleaning agents which should have bulk densities below 650 g / l, not only do the other components have a correspondingly lower bulk density, there is also the great risk of segregation due to the bulk density differences of the individual granular components.
  • heavy sodium sulfate there is also the fact that sodium sulfate is relatively fine-grained and tends to settle in the packaged package during storage and especially during transport on the bottom of the package.
  • Tetraacetylethylenediamine which is still the most frequently used bleach activator, only has bulk densities between 500 and 600 g / 1; In washing or cleaning agents, which should only have a bulk density of, for example, 400 g / 1, TAED is also to be regarded as a heavy and therefore problematic raw material to handle.
  • the object of the invention was to produce washing or cleaning-active granules with bulk densities below the theoretical liter weight, which is determined according to the normal calculation method, by mixing and agglomerating, the finished granules, in addition to having a sufficient storage stability (pourability), being above all homogeneous and the bulk density should be variable at least to a certain extent with a constant recipe.
  • heavy ingredients with bulk densities that are above the desired bulk density of the end product should be able to be processed without the finished products tending to separate.
  • a solid or several solids and a granulating liquid or several granulating liquids in a rotatable container without mixing tools (13), which is divided into a mixing zone (1) and a post-mixing zone (2) and a knock-off bar (5) has, which is attached to an end plate (4) and from there crosses the entire mixing zone (1) and, if necessary, extends into the post-mixing zone (2), agglomerates and, if necessary, is subsequently processed, a bulk density being set which does not exceed 85% of the theoretical liter weight, which is determined according to the normal calculation method.
  • the normal calculation method is understood to be the method in which the bulk density of the finished solid product, as already stated above, is weighted by adding up the individual bulk weights of a respective solid raw material or compound with its weight fraction in the finished solid product.
  • the liquid constituents that is to say the granulating liquid or the granulating liquids, go into their density analogously.
  • Bulk weights are preferably set which only make up a maximum of 80% and in particular only a maximum of 75% of the theoretical liter weight calculated as indicated above. Process end products with bulk densities below 650 g / l are particularly preferred.
  • Raw materials and / or compounds can be used as solids, the latter in the context of this invention having at least two different ingredients usually contained in washing or cleaning agents and have been prefabricated by conventional techniques such as spray drying, granulation, roller compaction or extrusion.
  • the raw materials used can be finely divided, but also of a coarser nature, the process according to the invention having the advantage that relatively fine-grained material can also be processed without problems. Since the production and subsequent further processing of compounds can be economically unfavorable, it is preferred in one embodiment of the invention to use only 1 to 3 different compounds as solids. It is particularly preferred to use at least one further solid raw material as a solid admixture component in addition to the compounds. In a particularly advantageous embodiment, no spray-dried compounds are introduced into the process.
  • the method according to the invention has the advantage that so-called solid small components can also be mixed directly.
  • the procedure can be such that the solids are weighed together on a conveyor belt, a so-called component collection belt, and the addition of the solid small components, in particular those which are only used in amounts of at most 2% by weight, as the last solid or the last solids are carried out directly before the solids are fed into the mixer.
  • a separate premixing of the solids in a separate mixer ie the production of a so-called premix, which is quite common in other processes, is therefore not necessary in the process according to the invention.
  • a drying step either to the agglomeration process or to the treatment which may have been carried out, but water can be added in the agglomeration phase and the end products of the process should not tend to stick
  • the aqueous granulating liquid is used only in such an amount that the water-binding capacity of the agglomerates is not exceeded.
  • At least one granulating liquid but preferably at least two different granulating liquids are introduced into the process.
  • the granulating liquids can be non-aqueous or aqueous in nature.
  • water, an aqueous solution or an aqueous dispersion is used as the only granulating liquid.
  • a non-aqueous granulating liquid is used.
  • a non-aqueous granulating liquid is understood to mean, in particular, an auxiliary which is a customary ingredient - optionally in aqueous solution or dispersion - of detergents or cleaning agents and is present as a liquid or melt at the process temperature.
  • At least two different granulating liquids are used. It is particularly advantageous that at least one of them is one of the above-mentioned non-aqueous granulating liquids, while at least one further granulating liquid is water, an aqueous solution or an aqueous dispersion. In a further advantageous embodiment, the invention provides that 0.5 to 15% by weight and in particular 1 to 10% by weight, with a particularly advantageous 1.5 to 7% by weight, of granulating liquid are introduced into the process.
  • Suitable non-aqueous granulating liquids are, in particular, liquid or liquefied or melted nonionic surfactants, paraffins, silicone oils, fragrances, fatty acids, meltable polyesters and known soil release ingredients from detergents.
  • the liquid or liquefied nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 20 moles of ethylene oxide (EO) per mole of alcohol, in particular up to an average of 14 EO per mole of alcohol, in of which the alcohol residue may be methyl-branched linearly or preferably in the 2-position or may contain linear and methyl-branched residues in the mixture, as is usually present in oxo alcohol residues.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, palm kernel, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 4 alcohols or C 12 -C 15 alcohols with 3 EO or 4 EO, C 9 -C n alcohols with 7 EO, C 3 -C 15 alcohols with 3 EO , 5 EO, 7 EO or 8 EO, C ⁇ 2 -C ⁇ 8 - alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ⁇ 2 -C 1 alcohol or C 12 -C 15 alcohol with 3 EO and C 12 -Ci 8 - alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
  • Suitable fatty acids are in particular saturated fatty acids, such as lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. coconut, palm kernel or tallow fatty acids, derived mixtures.
  • the amount of water introduced as the granulating liquid is 0.5 to 10% by weight and in particular 1 to 7% by weight, in each case based on the entire mixture. It is irrelevant whether the water is introduced into the process as the sole raw material or in the form of an aqueous solution or in the form of an aqueous dispersion. However, since preferably no drying step is connected to the agglomeration process, in a preferred embodiment of the invention water is not used as the sole agglomeration aid in order to keep the amount of water introduced as low as possible.
  • aqueous solutions are those of inorganic and / or organic builder substances.
  • Solutions of alkali silicates, alkali carbonates, but also of polycarboxylates, for example citrates, (co) polymeric polycarboxylates and cellulose ethers such as carboxymethyl celluloses or methyl celluloses, are particularly suitable here.
  • aqueous surfactant pastes of anionic and / or nonionic surfactants also represent suitable granulating liquids.
  • highly concentrated pastes of alkylbenzenesulfonates and alkyl sulfates can be used.
  • the use of nonionic surfactant pastes such as pastes of alkyl glycosides, polyhydroxy fatty acid amides or the fatty acid methyl ester ethoxylates already mentioned above is particularly preferred at this point.
  • Alkyl glycosides are surfactants of the general formula RO (G) x , in which R denotes a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.1 to 1.4. - 9 -
  • R CO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R ⁇ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups .
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
  • the agents produced according to the invention are colored.
  • aqueous dye solutions or combinations of such dye solutions and a non-aqueous granulating liquid, in particular nonionic surfactant are advantageously used.
  • Nonionic surfactants Mixtures of dye solutions and nonionic surfactants can also be used. In a preferred embodiment, however, no aqueous dispersions of nonionic surfactants are used. Rather, it is preferred to use at least one further aqueous granulating liquid in addition to at least one non-aqueous granulating liquid.
  • nonionic surfactants, fragrances and / or paraffins which are liquid at the process temperature, preferably at temperatures around room temperature to 60 ° C., is particularly preferred.
  • Aqueous liquids and non-aqueous liquids are advantageously used in weight ratios of 1.5: 1 to 1: 1.5 and in particular 1.2: 1 to 1: 1.2.
  • the rotatable container to be used according to the invention without internal mixing tools (13) is preferably a conical mixing drum, which is arranged in a lying position, but can advantageously be inclined against the horizontal.
  • the angle of inclination ⁇ is preferably less than 45 °, angle of inclination of less than 20 ° having proven particularly useful.
  • the mixing drum (13) is divided into two parts, creating an actual mixing zone (1) and a post-mixing zone (2). In an advantageous embodiment of the invention, the ratio of the length of the mixing zone (1): length of the secondary - 10 -
  • the mixing drum (13) has at least one possibility for adding solids (6), these being supplied in particular on the larger circular area.
  • the mixing drum (13) also has at least one possibility for adding liquids (7), in particular nozzles, advantageously 1 to 5 nozzles, different granulating liquids being introduced via different nozzles, but one and the same granulating liquid can also be added via different nozzles.
  • Single-substance nozzles are just as suitable here as multi-substance nozzles and / or spraying with gases, in particular air or water vapor, as aids.
  • two different nonionic surfactants such as -C 18 alcohol with 7 EO and C ] 2 -C 4 alcohol or C 12 -C ! 5 alcohol with 3 EO are used as granulating liquids, these can either be used as a mixture, via a Two-substance nozzle or two nozzles are introduced into the process.
  • the mixing drum (13) has the solid feed (6) on the larger circular area of the mixing drum (13), around which the various nozzle lances (7) are then attached.
  • the mixing drum (13) is preferably divided into the mixing zone (1) and the post-mixing zone (2) by the drive (3), for example by a toothed ring.
  • the part of the mixing drum (13) essential for the method according to the invention consists of a knock-over bar (5) which is attached to the end plate (4) of the first mixer part and from there crosses the entire mixing zone (1) and preferably into the post-mixing zone (2 ) extends into, but advantageously does not go beyond half the length of the post-mixing zone (2).
  • the knock-over bar (5) only extends into the first third of the length of the post-mixing zone (2).
  • the tee bar (5) itself can have a width of, for example, 50 to 150 mm, preferably 75 to 130 mm.
  • the upper edge of the knock-over bar (5) is at a distance from the inner mixer wall (14) which is preferably a maximum of 10% of the smallest drum diameter in the mixing zone (1), preferably a maximum of 5% of the smallest drum diameter of the mixing zone (1) and in particular 5 to 25 mm, advantageously less than 20 mm, for example 5 to 15 mm.
  • the distance to the nearest inner mixer wall can be greater than in the mixing zone (1); Values between 100 and 300 mm are quite common. - 11 -
  • the finished product can either be discharged directly via the discharge unit (8) and the discharge (9) or can be further processed via the conveyor device (10), with further powders, in particular surface modifiers of the well-known type can be added via the solids feed (11).
  • this conveying and metering screw (10) extends into the post-mixing zone (2) (it is also possible to connect the conveying device (10) directly to the discharge unit (8)), it is preferred that the screw (10) is only maximal in the second half of the length of the post-mixing zone (2) and thus does not protrude into the part of the post-mixing zone (2) that still contains the tee (5).
  • the tee bar (5) is mounted on the screw (10).
  • Amorphous and / or crystalline aluminosilicates such as zeolite A, X and / or P, various types of silicas, calcium stearate, carbonates, sulfates, but also finely divided compounds, for example made of amorphous silicates and carbonates, are preferred.
  • All raw materials and / or compounds usually used in solid or solidified form in detergents or cleaning agents in particular from the range of anionic, nonionic, cationic and / or amphoteric surfactants, inorganic and organic builder substances and organic builder acids, can be used as solid starting materials.
  • inorganic salts which react alkaline in water such as sodium or potassium (bi) carbonate, amorphous or crystalline sodium silicates, neutral reacting salts such as sodium or potassium sulfate and the acidic salts such as sodium or potassium bisulfate, enzymes, discoloration inhibitors, Graying inhibitors, soil repellents, foam inhibitors, complexing agents, for example phosphonates, and optionally optical brighteners and pH regulators are used.
  • heavy solids which are often added subsequently for a variety of reasons, are introduced into the agglomeration process.
  • These include sodium sulfate, which still contains up to 45% by weight in detergents in some countries, but also sodium carbonate and sodium bicarbonate as well as peroxy bleaching agents such as perborate monohydrate, perborate tetrahydrate and / or percarbonate.
  • Granulated bleach activators which often have a bulk density of 500 to 600 g / 1, are also heavy ingredients in detergents which, as desired, should have a bulk density below 500 g / 1, which can also be used in the process according to the invention.
  • the bleaching agent and bleach activator can be introduced together into the process without fear of a loss in bleaching activity despite the use of water as the agglomerating or granulating liquid.
  • the compounds preferably used include those containing 10 to 75% by weight of organic constituents such as surfactants, cosurfactants, which are also referred to as detergency boosters, and in particular organic builders and cobuilders, in particular polymers and / or copolymeric salts, for example acrylic acid and / or maleic acid.
  • organic constituents such as surfactants, cosurfactants, which are also referred to as detergency boosters, and in particular organic builders and cobuilders, in particular polymers and / or copolymeric salts, for example acrylic acid and / or maleic acid.
  • So-called highly concentrated surfactant compounds with surfactant fractions of at least 30% by weight, preferably at least 50% by weight, each based on the compound, which can be granulated in the fluidized bed, for example, are advantageously used.
  • Another advantageous compound is a so-called builder compound, which contains predominantly inorganic constituents and accordingly inorganic builders. They can be made alkaline by the choice of builder substances as desired.
  • builder compounds are used which have a maximum of 30% by weight, preferably up to 20% by weight, of organic constituents, in particular anionic surfactants and / or nonionic surfactants.
  • embodiments can be preferred which contain only 2 to 15% by weight of organic constituents and here above all anionic surfactants.
  • builder compounds in particular those made of carbon - 13 -
  • silicates mentioned which may optionally have up to 30 wt .-%, preferably up to 20 wt .-%, surfactants, especially anionic surfactants, but also anionic surfactants and nonionic surfactants.
  • Particularly preferred builder compounds have between 40 and 70% by weight sodium carbonate, 20 to 50% by weight sodium silicate of the module 2.0 to 3.3 and optionally about 2 to 18% by weight anionic surfactant, in particular alkylbenzenesulfonate.
  • Another interesting compound essentially contains zeolite, crystalline layered sodium disilicate and polymeric polycarboxylate or crystalline layered sodium disilicate and citric acid.
  • a compound with high organic fractions such as surfactants and optionally organic cobuilders and a builder compound which is intended to adjust the washing alkalinity of the finished product are combined with one another.
  • These two compounds are preferably used in weight ratios of 5: 1 to 1: 3 and in particular 3: 1 to 1: 1.
  • fragrances can be introduced into the process in liquid form as a granulating liquid, as described.
  • the process is also suitable for processing fragrances in the form of solid compounds.
  • concentrated fragrance compounds can be produced separately, for example, by granulation, compacting, extrusion, pelleting or using other agglomeration processes.
  • Cyclodextrins for example, have proven themselves as carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
  • fragrance foic bodies are described, for example, in the older German patent application DE-A-197 46 780.6, in which a method is disclosed in which a solid and essentially water-free premix comprising a) 65 to 95% by weight of carrier (en), b) 0 to 10% by weight of excipient (s) and c) 5 to 25% by weight of perfume are subjected to granulation or press agglomeration.
  • Preferred carriers are selected from the group of surfactants, surfactant compounds, di- and polysaccharides, silicates, zeolites, carbonates, sulfates and citrates and are used in amounts between 65 and 95% by weight, preferably from 70 to 90% by weight, each based on the weight of the fragrance moldings formed.
  • the total content of the surfactants in the finished composition can vary within a wide range and for example between 5 and 40% by weight, based on the finished composition, - 14 -
  • anionic surfactants are preferably added as solids to the mixture to be agglomerated, while nonionic surfactants can be added both as a constituent of the solids (compounds) and as agglomerating aids.
  • the weight ratio of the anionic surfactants to the nonionic surfactants in the finished compositions can be 10: 1 to 1:10. In preferred embodiments, however, it is above 1, in particular even above 1.5: 1, for example 5: 1 or 8: 1.
  • the agglomeration effect according to the invention is supported by the special mode of action of the mixer (13) used according to the invention.
  • relatively smaller particles and in particular the fine-grained fractions with particle diameters smaller than 100 ⁇ m are moved up by the movement of the mixer (13), while relatively coarser and smaller numbers are included in the rotating movement of the mixer (13) and instead in the direction of the Post-mixing zone (2) and then to be discharged from the mixer (13) into the discharge unit (8) or the conveying device (10), whereby the rolling movement of the individual particle causes the individual particle to compress.
  • Such a process is also called roll agglomeration or roll granulation.
  • the knock-over bar (5) prevents the highly moved particles and in particular the fines from being "driven in a circle", since as soon as they hit the knock-over bar (5) they are stripped off and fall vertically again.
  • the geometry of the mixer (13) allows the sprayed liquid mist not only to be sprayed onto the freshly added solids, but also directly into this curtain of relatively fine particles which are moving up and down again, and the beating bar (5) prevents the powder is pressed and glued to the mixer wall (14) when the mixer (13) rotates If the build-up should still occur - which, depending on the type of granulation liquids added and their quantity, cannot always be excluded - this is how the knock-off bar works as a scraper and prevents the adhesive layer from growing further and further. - 15 -
  • the agglomeration effect takes place in the mixing zone ( 1) between the moistened powder on the one hand and the smaller particles and fine fractions on the other hand, while an over-agglomeration by bringing the moistened powder or the remaining quantities of liquid fractions into contact with the already further agglomerated and therefore coarser particles can be almost ruled out.
  • finer particles are agglomerated into coarser particles which, depending on their size, are then swirled up less and less or no longer by the rotary movement of the mixer (13).
  • the mixer (13) used according to the invention, coarser particles can be moved up and agglomerated, and this happens all the more, the flatter the angle of inclination ⁇ , the longer the residence time of the material to be mixed in the mixer (13) and - as already mentioned above - The higher the speed of the mixer.
  • the angle of inclination ⁇ can be set from 0 to approximately 30 ° and up to approximately 70 revolutions per minute
  • the mixer (13) is inclined from 10 to 20 °, in particular from 12 to 15 °, in a preferred embodiment of the invention for the reasons mentioned with simultaneous movement of the mixer (13) via the drive (3) from 20 to 70 revolutions per minute and in particular from 30 to 60 revolutions per minute.
  • the agents produced by the process according to the invention usually have bulk densities between about 350 and 750 g / 1, preferably between 400 and 720 g / 1, in particular above 450 g / 1, but advantageously not above 700 g / 1. - 16 -
  • the bulk density is below 700 g / 1, in particular below 650 g / 1, even if a bulk density of significantly above 800 g / 1 would have been expected according to the normal calculation method given above.
  • Such agents can serve excellently as detergents, but also as a compound for a processed detergent.
  • the invention thus relates to detergents which consist of approximately 50 to 100% by weight of a compound or product produced according to the invention.
  • the detergents or compounds produced according to the invention therefore not only have a relatively variable bulk density, they are also to be regarded as highly stable in storage both with regard to the flowability and the reduced to nonexistent tendency to segregate. This also applies to the bleaching and enzyme stability, because during storage, due to the corresponding preferred control of the addition of water during the manufacturing process, there is no uncontrolled water absorption later during storage.
  • the particle size distributions of the finished products can, for example, be adjusted so that they are roughly comparable to those of an essentially spray-dried product to which the hydrolysis and temperature-sensitive ingredients were subsequently added.
  • the agents produced according to the invention have lower proportions of fine and coarse grain, so that the end result is a higher product yield. Any fine and coarse particles still present can be screened as before, if desired. Fine particles can be returned directly to the agglomeration process, while coarse particles due to the missing tools in the mixer (13) must first be broken up separately before they can be recycled.
  • the products thus produced according to the invention also have application-technical advantages over products of the same composition, but which were produced by conventional granulation processes. These advantages relate in particular to the washing-in behavior in automatic washing machines and / or the residue behavior on dark textiles.
  • fillers or fillers are probably the sodium sulfate. Removing the sodium sulfate from the slurry to be spray-dried would mean increasing the organic content in the slurry and thus a high level of process uncertainty. Replacing the sulfate with other inorganic salts such as soda would ensure process reliability, but would produce very alkaline products that are often not usable for the desired application.
  • Comparative Example VI contained the same compounds and raw materials as Ml, but was produced in a commercially available double cone mixer from Teltschik. Analogous results were achieved for VI when a ploughshare mixer from Lödige was used instead of the double cone mixer. In comparative example V2, which had the same composition as Ml or VI, instead of compounds 1 and 2, a spray-dried powder was prepared and prepared with the same raw materials, with the exception of the sulfate and other organic material.
  • Compound 1 contained 30% by weight of surfactant components, in particular 28% by weight of alkylbenzenesulfonate and / or alkylsulfate and 3% by weight of nonionic surfactants such as C] 2 -C 18 fatty alcohol with about 5 EO.
  • the composition of the surfactants can vary within a wide range without affecting the result. 25% by weight of alkylbenzenesulfonate, 2% by weight of alkylsulfate and 3% by weight of nonionic surfactant with different degrees of ethoxylation in the end product gave the same result.
  • Compound 1 additionally contained 50% by weight of inorganic builders, for example zeolite A, zeolite X, zeolite P, crystalline layered disilicates or any mixtures thereof, and 12% by weight of organic cobuilders such as citric acid, citrate, other polycarboxylic acids or polycarboxylates and or (co-) polymeric salts of acrylic acid and / or methacrylic acid and / or maleic acid with relative molecular weights between 3000 and 100000.
  • organic cobuilders such as citric acid, citrate, other polycarboxylic acids or polycarboxylates and or (co-) polymeric salts of acrylic acid and / or methacrylic acid and / or maleic acid with relative molecular weights between 3000 and 100000.
  • organic cobuilders such as citric acid, citrate, other polycarboxylic acids or polycarboxylates and or (co-) polymeric salts of acrylic acid and / or methacrylic acid and / or maleic
  • Compound 2 consisted of 50% by weight of sodium carbonate, 30% by weight of amorphous sodium disilicate, 8% by weight of alkylbenzenesulfonate and 12% by weight of water.
  • the theoretical liter weight of Ml calculated in advance according to the normal calculation method is 872 g / 1.
  • Table 1 shows the performance properties of the products Ml, VI and V2. It can be seen that Ml has advantages in solubility in spite of the higher bulk density than V2. In addition, it is proven that the significant reduction in the bulk density of Ml compared to the value determined by the normal calculation method (only 71% of the theoretical liter weight) and the value of VI (86% of the theoretical liter weight) brings about very clear application advantages. For VI, this was aggravated by the fact that the residue remaining in the induction chamber hardened.
  • the segregation tendencies were examined in three ways: 1. visually (when several visible layers appear, either recognizable by different particle sizes and / or in the case of partially stained products by concentration of a certain color in one layer), 2. analytically (samples from several layers were taken and analyzed for their composition) and 3. application technology (as in 2. samples were taken from several layers and examined for their flushing-in behavior and their residue behavior). 20th
  • the detergents were tested in household drum washing machines with a detergent drawer at a water pressure of 0.5 bar. Test machines were Miele W918 and Jo Privileg 1100. 5 determinations were carried out in each machine. The mean value given below was then formed from the 10 results. For this purpose, 100 g of the detergent were added to the induction chamber per wash. The tap water, with which the detergent was washed into the respective machine, which was loaded with 3.5 kg of dry laundry, had a water hardness of 16 ° d. After the wash-in was completed, the detergent residues from the wash-in drawer and the wash-in chamber were placed separately on a watch glass with a rubber wiper and weighed out. 30% moisture was subtracted from these moist residues. The "dry residues" from the drawer and chamber were added and the mean was calculated from the sum, which is given in Table 1. - 21 -
  • grade 1 perfect, no recognizable residues grade 2: tolerable, isolated, not yet disturbing residues grade 3: recognizable residues that were already annoying if critically assessed from grade 4: clearly recognizable and annoying residues in increasing number and quantity
  • Example 1 was repeated, but in addition to 2.5 parts by weight of nonionic surfactant, 2 parts by weight of an aqueous dye solution were now used as agglomerating liquids. A homogeneously colored product M2 was obtained which, despite the increased content of granulating liquid and here in particular water, did not tend to stick.
  • Example 1 was repeated; However, in addition to the 3 parts by weight of nonionic surfactant, water was now added as a further granulating liquid in the amounts indicated in each case: with additions between 1 (M3) and 4.5 parts by weight of water, bulk densities between 620 and 640 g / l were obtained . However, the wash-in behavior deteriorated almost continuously. Through additional subsequent surface treatment with solid 22
  • Composition 100 ml 100 ml 100 ml in parts by weight 1 water 2 water 4.5 water

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Abstract

Des granulés homogènes stables au stockage, dotés de caractéristiques détergentes et présentant des masses volumiques apparentes représentant au maximum 85 % du poids au litre théorique et calculées préalablement avec la méthode de calcul normale, peuvent être obtenus par agglomération d'un ou plusieurs solides avec un ou plusieurs liquides de granulation dans un malaxeur à chute libre (13) divisé en une zone de malaxage (1) et en une zone de post-malaxage (2) et comportant une barre d'abaissement (5) qui est fixée sur une plaque frontale (4) et, de ce point, traverse toute la zone de malaxage (1) et passe éventuellement dans la zone de post-malaxage (2). Il est ainsi possible de préparer également des produits, notamment des détergents spéciaux, par exemple des produits pour laver de la lingerie fine, de la laine ou bien des rideaux, lesquels produits présentent certes des masses volumiques apparentes correspondant aux détergents normaux actuels et atteignant environ 500 g/l, mais d'après leur formulation constituent néanmoins des concentrés.
EP99917991A 1998-04-28 1999-04-17 Procede pour la production de granules actifs detergents Expired - Lifetime EP1076685B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19818966 1998-04-28
DE19818966A DE19818966A1 (de) 1998-04-28 1998-04-28 Verfahren zur Herstellung von wasch- oder reinigungsaktiver Granulate
PCT/EP1999/002595 WO1999055820A1 (fr) 1998-04-28 1999-04-17 Procede pour la production de granules actifs detergents

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EP1076685A1 true EP1076685A1 (fr) 2001-02-21
EP1076685B1 EP1076685B1 (fr) 2002-03-06

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AT (1) ATE214091T1 (fr)
CZ (1) CZ291944B6 (fr)
DE (2) DE19818966A1 (fr)
ES (1) ES2174602T3 (fr)
HU (1) HU229241B1 (fr)
PL (1) PL191245B1 (fr)
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DE19858859A1 (de) * 1998-12-19 2000-06-21 Henkel Kgaa Verfahren zur Herstellung wasch- oder reinigungsaktiver Granulate
DE10258006B4 (de) * 2002-12-12 2006-05-04 Henkel Kgaa Trockenneutralisationsverfahren II
DE10258011A1 (de) * 2002-12-12 2004-07-08 Henkel Kgaa Trockenneutralisationsverfahren

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US3515672A (en) * 1965-06-24 1970-06-02 Colgate Palmolive Co Apparatus and process for the preparation of detergent compositions
DE19546735A1 (de) * 1995-12-14 1997-06-19 Henkel Kgaa Verfahren zur Herstellung eines granularen Additivs
DE19548346A1 (de) * 1995-12-22 1997-06-26 Henkel Kgaa Verfahren zum Herstellen granularer Wasch- und/oder Reinigungsmittel und zur Durchführung geeignete Vorrichtung

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Title
See references of WO9955820A1 *

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EP1076685B1 (fr) 2002-03-06
ATE214091T1 (de) 2002-03-15
DE19818966A1 (de) 1999-11-04
SK16232000A3 (sk) 2001-04-09
HU229241B1 (en) 2013-10-28
SK287177B6 (sk) 2010-02-08
CZ20003996A3 (cs) 2002-01-16
PL343622A1 (en) 2001-08-27
CZ291944B6 (cs) 2003-06-18
PL191245B1 (pl) 2006-04-28
DE59900940D1 (de) 2002-04-11
WO1999055820A1 (fr) 1999-11-04
HUP0101618A3 (en) 2002-08-28
ES2174602T3 (es) 2002-11-01
HUP0101618A2 (hu) 2001-09-28

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