EP0541608B1 - Procede de production de granules actifs de lavage et de nettoyage - Google Patents

Procede de production de granules actifs de lavage et de nettoyage Download PDF

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Publication number
EP0541608B1
EP0541608B1 EP91913378A EP91913378A EP0541608B1 EP 0541608 B1 EP0541608 B1 EP 0541608B1 EP 91913378 A EP91913378 A EP 91913378A EP 91913378 A EP91913378 A EP 91913378A EP 0541608 B1 EP0541608 B1 EP 0541608B1
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EP
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Prior art keywords
surfactant
granules
water
weight
solids
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EP91913378A
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German (de)
English (en)
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EP0541608A1 (fr
Inventor
Volker Bauer
Wilfried Rähse
Andreas Syldath
Ditmar Kischkel
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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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions 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
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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

Definitions

  • the invention relates to a process for converting aqueous preparation forms of detergent active in washing and cleaning into storage-stable surfactant granules and into storage-stable detergents and cleaning agents in granular form.
  • oleochemical surfactant compounds in detergents and cleaning agents is of great and increasing importance.
  • the considerations in the foreground are based on the one hand on the fact that surfactant compounds of this type are obtained from renewable vegetable and / or animal raw materials, but on the other hand it is the high ecological compatibility of selected components of this type which is of crucial importance.
  • Examples of such a class of oleochemical surfactant compounds are the known fatty alcohol sulfates, which are produced by sulfating fatty alcohols of vegetable and / or animal origin with predominantly 10 to 20 carbon atoms in the fatty alcohol molecule and subsequent neutralization to form water-soluble salts, in particular the corresponding alkali metal salts.
  • Tallow alcohol sulfates with predominantly saturated C16-C18 residues in fatty alcohol are already of considerable importance for the production of laundry detergents, particularly in solid form, but also fatty alcohol sulfates (FAS) with a further range in the C chain number are important washing properties .
  • fatty alcohol sulfates of the C12-C18 range with a high proportion of the lower fatty alcohols in this range can be important anionic surfactants for use in detergents and cleaning agents.
  • anionic surfactants for use in detergents and cleaning agents.
  • European patent application 342 917 also describes detergents in which the anionic surfactants consist predominantly of C12-C18 alkyl sulfates.
  • anionic oleochemical surfactant compounds are the known sulfofatty acid methyl esters (fatty acid methyl ester sulfonates, MES), which by ⁇ -sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin with predominantly 10 to 20 carbon atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono Salts, in particular the corresponding alkali salts, are prepared.
  • MES fatty acid methyl ester sulfonates
  • ester splitting arise from the corresponding ⁇ -sulfofatty acids or their di-salts, which, like mixtures of di-salts and sulfofatty acid methyl ester mono-salts, have important washing and cleaning properties specific to the substance. Comparable problems also occur in other surfactant classes when trying to manufacture the corresponding surfactant raw materials in solid or granular form. Reference is made to washing and cleaning-active alkyl glycoside compounds. In order to obtain light-colored reaction products, a final bleaching, for example with aqueous hydrogen peroxide, is generally required in their synthesis, so that here, too, today's technology leads to the aqueous paste form of the surfactant.
  • APG pastes aqueous alkyl glycoside pastes
  • ABS pastes alkylbenzenesulfonates
  • paste viscosity of such aqueous substance mixtures is strongly temperature-dependent, so that pastes of the type mentioned are practically not problem-free in the region of room temperature can work, the use of elevated temperatures of, for example, 50 to 70 ° C is required.
  • EP-A-0 116 905 (Henkel) describes the use of alcohols having 8 to 40 carbon atoms which are substituted by 1 to 5 hydroxyl groups and / or to which up to 15 moles of ethylene oxide and per mole of alcohol / or propylene oxide are added as a viscosity regulator for highly viscous technical surfactant concentrates of the synthetic anionic surfactant type.
  • Corresponding aqueous pastes of alkyl sulfates, alkylaryl sulfates and ⁇ -sulfofatty acid esters with a surfactant content of at least 30% by weight are mentioned in detail.
  • viscosity regulators in amounts of 1 to 15% by weight, based on the amount of surfactant, leads, according to this teaching, to viscosities of the respective surfactant concentrate of at most 1000 mPas at 70 ° C (Höppler falling ball viscometer). Mixtures of saturated and unsaturated fatty alcohols with up to 8 mol EO and / or PO units are particularly preferred as viscosity regulators.
  • the viscosity behavior of aqueous pastes of mixed surfactants and in particular the unusual increase in viscosity when mixing aqueous ABS and TAS pastes is not addressed in this document.
  • European patent application EP-A-0 349 201 describes a granulation process in which it is essential that the temperatures do not exceed 20 ° C. If the temperatures in the mixing process should be higher than 20 ° C, the mixture must be cooled accordingly so that a Formation of granules can take place. This cooling process is usually carried out with dry ice.
  • the invention is based on the object of demonstrating a simple alternative processing option for the aqueous, in particular paste-like, surfactant preparations to give dry, in particular free-flowing and concentrated surfactant granules.
  • the invention is based on the knowledge gained from the European patent application EP 116 905, but extends the principles described there beyond the knowledge known to date.
  • the invention relates to a process for producing granules which are active in washing and cleaning by granulating a mixture of an aqueous surfactant preparation form and one or more water-soluble and / or water-insoluble solids, so that free-flowing granules are formed.
  • the concentrated surfactant preparation forms contain anionic and nonionic surfactants and, as viscosity regulators, alkoxylates of mono- and / or polyhydric alcohols with 8 to 40 carbon atoms, which have up to 20 ethylene oxide and / or propylene oxide groups.
  • the granulation is carried out at temperatures from 25 ° C.
  • the free-flowing granules are preferably at least partially freed of their water content by drying.
  • the process according to the invention is particularly suitable for the granulation of surfactant pastes, the surfactant components of which are solids in the range up to at least about 40 ° C. and which have a high viscosity per se , the viscosity being reduced according to the invention by using the viscosity regulator. At the same time, this results in the possibility of lowering the processing temperature and / or increasing the surfactant solids content in the aqueous paste material.
  • the new process can be particularly suitable for the use of anionic surfactant pastes based on alkyl sulfates, alkyl sulfonates, alkylarylsulfonates, ⁇ -sulfofatty acid esters, ⁇ -sulfofatty acid disalts and / or soaps. It has surprisingly been found, in particular, that mixed pastes here The type mentioned, which, for example, contain any quantity of mixtures of surfactant compounds based on ABS and TAS, can be converted into comparatively free-flowing and pumpable pastes by adding comparatively limited quantities of fatty alcohol alkoxylates.
  • Suitable viscosity regulators in the context of the teaching according to the invention are, in particular, those alkoxylates of synthetic and / or fatty alcohols of natural origin, as are common in today's technology of detergents and cleaning agents - especially textile detergents - as so-called nonionic surfactant components and are generally used here in a mixture with anionic surfactants of the type described above.
  • the process according to the invention is also suitable for the use of aqueous pastes of wash-active alkylglycoside compounds.
  • the invention thus enables the economical production of virtually any mixtures of, for example, anionic surfactants and selected nonionic surfactants in dry form, which can be controlled and optimized in terms of their composition and type and / or amount by the intended use.
  • the invention relates to a process for the production of highly concentrated surfactant granules using the granulation process described above, which can be used as a surfactant-rich compound for the production of detergents and cleaning agents.
  • the invention relates to a method for producing storage-stable and free-flowing detergents and cleaning agents, in particular textile detergents, which are also suitable for subsequent blending with particularly temperature-sensitive components of detergents and cleaning agents.
  • the compounds preferred according to the invention as viscosity regulators are derived from monohydric alcohols in the C number range mentioned, it being possible for these alcohols to be of natural or synthetic origin. Aliphatic alcohols of this type are known to be derived from natural fats and oils and are obtained, for example, by reducing the corresponding fatty acid esters. These so-called fatty alcohols are straight-chain and can be saturated or unsaturated. In the context of the action according to the invention, viscosity regulators based on alkoxylated fatty alcohol mixtures of the type used in the production of detergents and cleaning agents as nonionic surfactant components are particularly suitable.
  • Suitable viscosity regulators are therefore, in particular, ethoxylates of straight-chain and / or branched monofunctional fatty alcohols having about 10 to 20 carbon atoms, the range from 12 to 18 carbon atoms in the alcohol residues being of particular importance in the fatty alcohol or fatty alcohol mixture.
  • these fatty alcohols are alkoxylated with an average of about 2 to 10 EO groups, the range of about 3 to 8 EO groups being particularly important here.
  • a commercially available nonionic surfactant component of this type is, for example, the product sold by the applicant under the name "Dehydol LST 80:20", which is a mixture of 80 parts by weight of C12 ⁇ 18 fatty alcohols and on average 5 EO units and 20 parts by weight of a C 12 / 14 represents fatty alcohol with 3 EO units.
  • This nonionic surfactant which is used in numerous textile detergents, is a very useful viscosity regulator in the sense of the action according to the invention. Aliphatic alcohols or addition products suitable as viscosity regulators can, however, also be used alcohol components with a branched carbon chain.
  • alcohols with a branched carbon chain examples include oxo alcohols and Guerbet alcohols, that is to say alcohols obtained by the oxo synthesis or by the so-called Guerbet reaction, each branched in the 2-position.
  • polyfunctional alcohols or their alkoxylates which are also suitable according to the invention, reference is made to the teaching of EP-A-0 116 905.
  • they are mentioned as basic alcohol components Compounds such as 12-hydroxystearyl alcohol, 9,10-dihydroxystearyl alcohol or their ethylene oxide products.
  • aqueous anionic surfactant pastes can be achieved not only with selected individual anionic surfactants or their aqueous pastes, but even with small amounts of the nonionic surfactant component in the sense of the teaching of EP-A-0 116 905 added a few percent of the non-ionic surfactant to a completely solidified ABS / TAS paste, which ensures the desired flow and pumpability.
  • the viscosity regulators in amounts of at least about 2% by weight, preferably in amounts of at least about 5% by weight, the weight% given here being based on the solids weight of the mostly anionic surfactant mixture component in the aqueous preparation form. Amounts of the nonionic viscosity regulators in the range up to about 15% by weight can be particularly suitable, so that the range from about 5 to 15% by weight can be of particular importance.
  • the aqueous FAS mixtures used in the flowable and pumpable surfactant preparation forms are the reaction products from the sulfation and the subsequent aqueous-alkaline neutralization of the particular fatty alcohol used. In general, these are mixtures of corresponding FAS types of different chain lengths with a preferably straight-chain fatty alcohol residue within the specified range of C12-C18.
  • the water content of these FAS mixtures is preferably in the range from approximately 20 to 80% by weight and in particular in the range from approximately 30 to 50% by weight.
  • the working temperature temperature of the surfactant paste
  • the working temperature is room temperature or moderately elevated temperatures, for example 40 ° C, preferred.
  • the granulation process is as follows:
  • a suitable mixing and granulating device for example in appropriate systems of the type of an Eirich mixer, a Lödige mixer, for example a ploughshare mixer from the Lödige company, or a mixer from the Schugi company, at peripheral speeds of the mixing elements, preferably between 2 and 7 m / s (ploughshare mixer) or 5 to 50 m / s (Eirich, Schugi), in particular between 15 and 40 m / s the aqueous FAS / nonionic surfactant mixture on the one hand and on the other hand water-soluble and / or water-insoluble solids, the temperature-dependent modifications of water-binding solids contain, fed in such proportions and mixed with each other so intensively that a free-flowing granulate is formed.
  • a predeterminable grain size of the granulate can be set in a manner known per se.
  • the mixing process takes only a very short period of time, for example about 0.5 to 10 minutes, in particular about 0.5 to 5 minutes (Eirich mixer, Lödige mixer) to homogenize the mixture to form the free-flowing granulate.
  • a residence time of 0.5 to 10 seconds is usually sufficient to obtain a free-flowing granulate.
  • the mixing ratios of the components and in particular the proportions of the added solid are to be matched to the water content entered via the FAS mixture in such a way that the homogenized mixture of aqueous surfactant preparation form and added solid can form the free-flowing granulate.
  • the still moist granulate is preferably transferred immediately after the granulation to the drying stage, which in the preferred embodiment is designed as a fluidized-bed dryer. In principle, however, no subsequent drying step is required to produce the free-flowing granules. Drying is, however, advantageous and therefore preferred, since this leads to surfactant granules with an increased surfactant content.
  • non-dried granules are mixed with partially or completely dried granules in any ratio.
  • “Completely dried” is understood to mean the state in which the unbound water and possibly portions of the bound water have been removed from the granules.
  • Fluidized bed drying is a preferred type of drying, since rapid drying of the outer surface of the granules occurs with simultaneous intensive movement and mixing of the granules, so that undesirable caking of the still moist granules is counteracted in this way.
  • the invention provides for the still moist granules to be powdered - expediently immediately after the granules are produced - with a dusty or pulverulent auxiliary and for the granules stabilized in this way to be added to the drying stage.
  • the state of the free-flowing granulate is then quickly reached there even under comparatively mild drying conditions.
  • the drying in particular the fluidized bed drying, is preferably carried out at temperatures of the gas phase below 200 ° C. and in particular at temperatures in the range from approximately 70 to 160 ° C., for example in the range from approximately 90 to 150 ° C. These temperatures relate primarily to the gas phase; in a preferred embodiment, the final temperature of the granules which is established is kept at comparatively low temperatures and here, for example, does not exceed 80 to 90 ° C., preferably it is not higher than 75 ° C.
  • the solids used in the granulation for the partial drying of the aqueous surfactant preparation form can be corresponding ingredients from conventional formulations of detergents and / or cleaning agents, but they can also be foreign substances as long as they are compatible with the intended use of the surfactants. It will generally be preferred to use ingredients from washing and / or cleaning agents here. It is a particular advantage of the process according to the invention that there is very great freedom in the selection of these solid mixture components. The reason for this is the fact that the granulation method according to the invention with the preferably connected drying provides such comparatively mild working conditions that undesired secondary reactions in the granulation and / or drying step are only to be feared in special cases. General technical knowledge applies here.
  • temperature-sensitive mixture constituents for example textile detergents, such as those used as bleaching agents of the perborate type
  • textile detergents such as those used as bleaching agents of the perborate type
  • water-soluble and / or water-insoluble solids which can be mixed with the water-containing surfactant preparation forms without hesitation under the working conditions, granulated and then dried under the specified working conditions.
  • suitable water-soluble solids are inorganic salts, for example soda, alkali silicates, in particular water glass powder, sodium sulfate and / or phosphate salts such as sodium pyrophosphate and sodium tripolyphosphate.
  • the teaching of the invention also provides for the use of corresponding insoluble, preferably finely divided materials.
  • the grain size of the preferred solids is less than 1 mm and in particular less than 100 »m, for example not more than 30» m.
  • Typical examples from the field of washing and / or cleaning agents are additives which are used as so-called builder substances to bind the alkaline earth metal ions and thus to remove the water hardness.
  • Examples include finely divided crystalline zeolites, in particular sodium zeolite NaA in detergent quality, which preferably consists of at least 80% of particles of a size of less than 10 »m (volume distribution; Coulter Counter).
  • Other examples of preferred solids are hydrotalcites, water-insoluble and crystalline phyllosilicates, abrasives such as stone powder and the like.
  • a special feature of the invention is the use of preferably dried and again finely divided granules from ongoing production as a solid component of the mixture for working up further amounts of the aqueous surfactant preparation forms.
  • This embodiment provides in particular a complete or partial circulation of the granules produced by the process according to the invention, in particular the dried granules, in the process cycle. Details of this particular embodiment are described below.
  • the mixing ratios of the surfactants on the one hand and of the solids to be used in the mixing and granulation stage it may be expedient to adapt these mixture components to the corresponding requirements of the components in the detergents and / or cleaning agents that are ultimately to be created.
  • the ratio of anionic surfactants to the finely divided solids that are used, for example, in textile detergents can provide clues for the composition of the mixture to be granulated.
  • the need to use various solid detergent constituents, advantageously also in coordinated proportions, can be derived from such considerations.
  • the water glass content of textile detergents in the overall formulation is comparatively low, for example it can be in the range from 2 to 5% by weight of the total formulation.
  • the desired percentage composition of the granules according to the invention can be combined with the proportional mixture prescribed by the full detergent formulation.
  • Typical examples of this are mixtures of the water-containing surfactant pastes with sodium zeolite, soda and / or sodium sulfate.
  • a particularly important embodiment of the invention provides for the already mentioned partial or complete circulation of the granules, preferably of the dried granules, back into the mixing and granulating stage.
  • the process in particular in a continuous process, can be carried out in such a way that the entire solid phase added in the mixing and granulating stage is formed from a recycled material of this type, which consists of granules which have already been dried and thus already has considerable proportions, namely preferably more than 25% by weight .-%, based on this dry granulate used as a solid, contains anionic surfactant.
  • the dried granulate used as a solid in the mixing and granulating stage is first crushed, for example under the action of the mixing tools or a conventional mill. This return can take place once, but also several times, for example 2 to 8 times.
  • the peculiarities of such a procedure are immediately apparent: in the sense of this inventive action, the surfactant can be accumulated in the granulate up to predetermined values. Due to the comparatively low melting points of detergents important for washing, e.g. B. FAS compounds and in particular corresponding FAS mixtures, the enrichment of the granules is approximately for practical work 100% surfactant mass (sum of anionic surfactant and nonionic surfactant) are of minor importance.
  • the grain size range of the resulting granulate and the average grain size are adjusted in a manner known per se by adapting the working conditions in the granulation stage.
  • granules with a grain size range of approximately 0.01 to 3 mm (sieve analysis) and in particular those with a range of approximately 0.05 to 2 mm can be produced with ease.
  • An important embodiment of the invention provides for the classification of the dried granules by separating undesired fine-grain and coarse-grain fractions in a manner known per se. In an important embodiment of the invention, these separated fractions can even be returned to the mixing and granulating stage and used as a solid if no recycling of the granulated and dried granules is otherwise provided.
  • the physical properties of the granules can also be largely predetermined in another way.
  • the hardness of the granules and, in particular, its abrasion hardness can be modified and, for example, increased by using suitable auxiliaries.
  • suitable auxiliaries This is possible by using small amounts of polymer compounds, as are usually used in detergents and cleaning agents.
  • Examples include the polyacrylates and polyacrylate copolymers known as builder substances, which can be used, for example, with relative molecular weights in the range from 30,000 to 100,000.
  • Auxiliaries of this type can already be added to the mixture in the mixing and granulating stage, but it is also possible to apply them subsequently to the preformed granules before or during the drying process.
  • the method according to the invention can also be modified in a completely different form and used to facilitate the production of granules of the type described.
  • This modification can be understood from the following example:
  • zeolite NaA is produced as an aqueous suspension (masterbatch) which can contain more than 50% by weight of water and is usually worked up in the spray tower to give a powdery solid.
  • the zeolite can be introduced into the mixing and granulating stage at least in part in the form of this suspension or as a product which has not been completely dried, in order then to be dried up in the granulate in the mixture with the surfactant and the added dry solids.
  • Such an embodiment can be of particular interest if the dried granules are circulated and the portion required as a solid is introduced into the mixing and granulating stage via the desired end product.
  • Zeolite materials of the last-mentioned type but also other typical additives of detergents and cleaning agents, are in turn capable of partially binding water.
  • auxiliaries of this type are anhydrous soda and anhydrous sodium sulfate, which can bind considerable amounts of water in the form of water of crystallization.
  • the present invention uses this ability of internal water binding for additional drying (internal drying) of the granules formed in the process according to the invention.
  • the water content in the drying step is reduced to such an extent that the bound water present as crystal water is at least partially discharged.
  • the water contents of the dried granules preferred according to the invention are accordingly comparatively low.
  • the proportion of unbound water is preferably below 8% by weight, in particular below 5% by weight, based on the dried granules.
  • Water bound in crystal form or integrated into the molecular structure can be present in the substance mixture in limited amounts, but the storage stability of the granules becomes higher, the lower the proportion of crystal water in the end product in particular is reduced. It is understandable that this embodiment is of lesser importance if rapid further processing of the surfactant granules is intended. If these granules are to be used as a form of trading in raw materials trading, the considerations discussed last should be given greater importance.
  • nonionic surfactant component as a viscosity regulator of 2 to 15% by weight, based on the amount of solids of the mostly anionic surfactant in the surfactant paste, are used in the production of the free-flowing granules, then mixing ratios of anionic surfactant lie in the finished granulate to non-ionic surfactants, which - compared to conventional formulations of detergents and cleaning agents - are comparatively low in non-ionic surfactants.
  • This can be meaningless for the teaching according to the invention of the improved production of the surfactant granules concerned here, but this must then be taken into account when mixing these granules into the finished detergent or cleaning agent.
  • nonionic surfactant can even be preferred Embodiment of the action according to the invention.
  • this is the case if the processing conditions chosen for the granulation and preferably subsequent drying of the granules, on the one hand, and the volatility of the nonionic surfactants used as viscosity regulators, on the other hand, are suitable for triggering procedural concerns in the sense of so-called pluming, as is the case for spray drying of nonionic surfactant-containing active ingredient mixtures during drying in the tower is known.
  • the invention also opens up new work opportunities for the granulation process and in particular the subsequent drying stage: the effective viscosity reduction in the sense of the inventive action makes processing temperatures so low for the granulation stage in the range from 25 to 40 ° C. that concerns about potential volatility non-surfactant mixture components become irrelevant.
  • the preferably subsequent drying step can also be adapted to such a low or at least comparably low temperature level. This is made possible by the use of underpressures in the drying stage, it being possible for the working pressures to be used individually to be adapted to the respectively selected process parameters in a manner known per se.
  • the mixing ratio of anionic surfactants to the nonionic surfactants that is ultimately used is set in the preliminary stage of the granulation.
  • the total amount of nonionic surfactant required in the finished laundry detergent is entered in the granules together with the anionic surfactants as a viscosity regulator.
  • nonionic surfactant content for example to amounts of at most about 80% by weight and in particular to less than 50% by weight, based on the total amount of nonionic surfactants in the textile detergent. Nonetheless, in the embodiments shown last, a nonionic surfactant quantity is still used as the viscosity regulator which exceeds the range from EP-A-116 905 - and thus about 15% by weight (based on anionic surfactant).
  • the amount of nonionic surfactant to be selected will also be determined by the aim aimed at, either to produce anionic surfactant granules containing high surfactants or to use the process according to the invention for the preparation of the detergents in their entirety.
  • the teaching according to the invention makes it possible to carry out the granulation with pastes with a very limited water content at very low temperatures of 25 to 40 ° C.
  • Temperature-sensitive materials such as sodium perborate or enzymes or enzyme-containing preparations can now be used here as granulation aids in the solid phase.
  • certain temperature-dependent modifications of solid mixture components which bind water of crystallization are used according to the invention to facilitate the process.
  • soda forms the decahydrate in the temperature range up to about 32 ° C, which converts into water with the release of water into the heptahydrate, which is stable up to about 35 ° C and finally changes into the monohydrate when the temperature increases further.
  • the lower surfactant viscosity produces finer droplets when the surfactant pastes are sprayed into the mixing and granulation device. This results in a more even distribution of the flowable phase.
  • a fluidized product zone is built up in the mixing area, into which the surfactant paste is injected. The high shear forces result in a very fine distribution of the more flowable aqueous surfactant.
  • the granules according to the invention can have an increased bulk density, in particular in comparison with corresponding spray-dried materials.
  • Typical granules within the meaning of the invention normally have a bulk density of at least about 350 g / l, preferably of at least about 500 g / l. Bulk weights between 600 and 800 g / l are particularly preferred.
  • the process according to the invention can be used in a wide range with regard to the aqueous surfactant mixtures.
  • mixtures of surfactants which are present in the region of room temperature as sufficiently dimensionally stable solids and which are present in the course of their preparation and / or workup as aqueous pastes which contain the surfactants dispersed in the aqueous phase are recorded.
  • An important example of such surfactants are the ⁇ -sulfofatty acid methyl ester mono salts and / or the so-called di-salts.
  • the mono-salts of the sulfofatty acid methyl esters (MES) are obtained in their large-scale production as a mixture with limited amounts of di-salts, which are known to result from partial ester cleavage with the formation of the corresponding ⁇ -sulfo-fatty acids or their di-salts.
  • the di-salt content of such MES-based surfactants is usually below 50 mol% of the anionic surfactant mixture, for example in the range up to about 30 mol%.
  • the teaching according to the invention is suitable for its application to such MES-based surfactant mixtures as well as corresponding mixtures with higher di-salt contents up to the pure di-salts.
  • a preferred aqueous MES feedstock are the comparatively strongly water-containing reaction products from the sulfonation and the subsequent aqueous-alkaline neutralization of the respective fatty acid methyl ester.
  • these are mixtures of corresponding MES types of different chain lengths with preferably straight-chain fatty acid residues within the specified range of C12-C18.
  • the water content of these raw MES products can be in the range from about 20 to 80% by weight and in particular in the range from about 30 to 60% by weight.
  • Surfactant compounds based on alkyl glycosides and their preparation, in particular in the form of water-containing bleached pastes, are described in detail, for example, in international patent application WO 90/03977.
  • Surfactant reaction products of this type are a further example of the applicability of the process according to the invention for the production of dry granules based on surfactants. It is very general that the process according to the invention can be used for the preparation of aqueous preparation forms of surfactant compounds from the class of anionic, nonionic, zwitterionic and / or cationic surfactants which are at least largely solid at room temperature, the choice of appropriate surfactant compounds having high ecological compatibility being preferred.
  • a surfactant mixture of 95% by weight of Texin ES 68 (commercial product of the applicant, containing 53% by weight of sodium mono salt of the ⁇ -sulfotalg fatty acid methyl ester and 11% by weight of disodium salt of the sulfotalg fatty acid and 29% by weight of water) and 5 %
  • a C12-C18 fatty alcohol with 5 ethylene oxide groups (EO) (Dehydol LT5, commercial product of the applicant) were with 1.5 kg of soda for 3 minutes in a 10 liter Eirich mixer at a peripheral speed of 24 m / s, corresponding to 2500 Rotations per minute (rpm) (star vortex) granulated.
  • the granules were then dried in a fluidized bed (aeromatics) for 60 minutes at an air inlet temperature of 70 ° C.
  • the detergent content (WAS, anion surfactant content titrable according to Epton, here: sulph tallow fatty acid methyl ester and disalt content; accuracy ⁇ 2% by weight) was 34% by weight, the disalin content was 5.5% by weight.
  • 1.5 kg of the surfactant mixture mentioned in Example 1 were granulated at 25 ° C. with 750 g of soda for about 1 minute in an Eirich mixer (10 liters, star swirler, 2500 rpm, 24 m / s). The granules were then dried in a fluidized bed (aeromatics) for 60 minutes at 50 ° C. air inlet temperature. A free-flowing granulate with about 7% by weight of water and a bulk density of 590 g / l was obtained. The WAS content of the granules was 49% by weight.
  • 150 kg of the surfactant mixture mentioned in Example 1 were granulated with 150 kg of soda for 2 minutes in a 300 liter Eirich mixer (Sternwirbler, 700 rpm, 18 m / s). The granules were then in a fluidized bed (Heinen) at an air inlet temperature of 100 ° C and a residence time of 20 Dried for minutes. Free-flowing granules with about 1% by weight of water and a bulk density of 780 g / l were obtained.
  • Heinen fluidized bed
  • a surfactant mixture of 95% by weight of Texin ES 68 and 5% by weight of a fatty alcohol with 7 EO (Dehydol LT7, commercial product from the applicant) were mixed with 750 g of sodium sulfate and dried as in Example 1. After drying, the granules had a content of 0.7% by weight of water and 53% by weight of WAS, of which 8% by weight was disalt. The bulk weight was 650 g / l.
  • Example 4 1.5 kg of the surfactant mixture mentioned in Example 4 were granulated with 1.5 kg of dried sodium zeolite A as in Example 1 and dried for 60 minutes at an air inlet temperature of 90 ° C.
  • the product had a water content of less than 1% by weight and a bulk density which (depending on the proportion of fine and coarse grains) was between 600 and 700 g / l.
  • composition of the "surfactant-free" detergent (in% by weight): C12-C18 sodium fatty acid soap 2.3 Sodium silicate (Na2O: SiO2 1: 3.3) 4.7 Sokalan CP5 (R) (commercial product from BASF; copolymer of acrylic acid) 6.3 Zeolite (based on anhydrous substance) 32.7 Sodium carbonate, calcined 18.9 Sodium sulfate 28.1 Water and residual components 7.0

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Claims (11)

  1. Procédé d'obtention de granulés actifs pour le lavage et pour le nettoyage par granulation d'un mélange à base d'une forme de préparation aqueuse d'agent tensioactif et d'un ou plusieurs solides solubles et/ou insolubles dans l'eau, dans lequel la forme de préparation d'agent tensioactif aqueuse contient des agents tensioactifs anionique et non ioniques, caractérisé en ce que la forme aqueuse de préparation d'agent tensioactif renferme en tant que régulateur de viscosité des alcoxylates d'alcools uni- et/ou plurivalents ayant de 8 à 40 atomes de carbone, qui possèdent jusqu'à 20 groupes d'oxyde d'éthylène et/ou d'oxyde de propylène, et en ce que l'on effectue la granulation à des températures de 25 à 40°C et que l'on met en oeuvre des modifications dépendant de la température de solides qui se lient à l'eau de cristallisation en quantités telles qu'à ces températures, il se forme un granulé apte à l'écoulement.
  2. Procédé selon la revendication 1, caractérisé en ce que le granulé apte à l'écoulement est séché en lit fluidifié, dans lequel les granulés d'agent tensioactif sont formés avec au moins 20 % en poids d'agent tensioactifs.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que l'on façonne des formes de préparation d'agents tensioactifs aqueuses à base d'agents tensioactifs anioniques et/ou de dérivés d'alcoylglycosides actifs pour laver, en particulier à base d'alcoylsulfates, d'alcoylsulfonates, d'esters d'acide gras α-sulfonés, de di-sels d'acide gras α-sulfonés et/ou, de savons, auxquels on ajoute comme régulateurs de viscosité des éthoxylates d'alcools gras monofonctionnels à chaîne droite et/ou ramifiée ayant de 10 à 20 atomes de carbone, de préférence ayant de 12 à 18 atomes de carbone, dans le radical alcoolique et ayant en moyenne environ 2 à 10 groupes OE, de préférence de 3 à 8 groupes OE, dans lesquels les mélanges de tensioactifs non ioniques de plusieurs éthoxylates d'alcool gras correspondants sont préférés.
  4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que les régulateurs de viscosité sont mis en oeuvre en quantités d'au moins 2 % en poids, de préférence en quantités d'au moins 5 % en poids, rapporté au poids de solides, des composants de mélange pour la plupart tensioactifs anioniques, parmi lesquels en particulier on préfère des quantités de régulateurs de la viscosité non ioniques dans la zone de 5 à 15 % en poids.
  5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que l'on met en oeuvre dans l'étape de mélange et de granulation, des solides qui sont des ingrédients à base d'agents de lavage et de nettoyage, tandis qu'on met en oeuvre comme matière solide soluble dans l'eau, du carbonate de sodium, des silicates de métal alcalin, ou du sulfate de sodium et comme matière solide insoluble dans l'eau de la zéolite NaA, de l'hydrotalcite, ou des substances d'abrasion comme des poudres de friction ou des silicates lamellaires cristallins.
  6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que les rapports de mélange qui doivent être mis en oeuvre dans les étapes de mélange et de granulation, d'agents tensioactifs et de matières solides sont adaptés à la demande correspondante des composants dans les agents de lavage et de nettoyage qui sont à élaborer.
  7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce que le granulé, de préférence le granulé séché, est récupéré partiellement ou totalement en circuit dans les étapes de mélange et de granulation, procédé dans lequel les granulés sont en premier lieu broyés et, au moins partiellement introduits sous forme de matière solide pour un mélange ultérieur avec un mélange de tensioactifs aqueux.
  8. Procédé selon l'une des revendications 1 à 7, caractérisé en ce que le granulé séché est produit avec des teneurs en agents tensioactifs d'au moins 25 % en poids, de préférence de 30 à 75 % en poids, rapportées au granulé séché.
  9. Procédé selon l'une des revendications 1 à 8, caractérisé en ce que le contenu en tensioactif non ionique requis au total dans l'agent de lavage pour articles textiles terminé, est introduit dans sa quantité totale en tant que régulateur de viscosité conjointement avec d'autres agents tensioactifs dans les granulés d'agent de lavage, ou en ce que seulement une fraction, de préférence au maximum 80 % en poids, et en particulier moins de 50 % en poids respectivement rapportée à la quantité globale de tensioactif non ionique dans l'agent de lavage pour articles textiles, intervient comme régulateur de viscosité, pendant que le reste de la quantité globale de tensioactif non ionique est introduit séparément dans le grain de granulé.
  10. Procédé de production de granulés très concentrés de composés tensioactifs solides à température ambiante et de préférence jusqu'à au moins 40°C, en particulier de granulés d'agents tensioactifs anioniques, qui sont utilisés comme composés riches en agents tensioactifs pour la réalisation d'agents de lavage et de nettoyage, selon l'une des revendications 1 à 9.
  11. Procédé de production d'agents de lavage et de nettoyage stables au stockage et aptes à l'écoulement, en particulier agents de lavage pour articles textiles, qui conviennent également pour un mélange ultérieur avec des constituants en particulier sensibles à la chaleur des agents de lavage et de nettoyage, selon l'une des revendications 1 à 9.
EP91913378A 1990-08-03 1991-07-25 Procede de production de granules actifs de lavage et de nettoyage Expired - Lifetime EP0541608B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4024657 1990-08-03
DE4024657A DE4024657A1 (de) 1990-08-03 1990-08-03 Verfahren zur trocknung und granulierung waessriger pasten waschaktiver wirkstoffgemische
PCT/EP1991/001395 WO1992002609A1 (fr) 1990-08-03 1991-07-25 Procede de production de granules actifs de lavage et de nettoyage

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EP0541608A1 EP0541608A1 (fr) 1993-05-19
EP0541608B1 true EP0541608B1 (fr) 1995-06-28

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EP (1) EP0541608B1 (fr)
JP (1) JPH05509120A (fr)
CN (1) CN1058609A (fr)
AT (1) ATE124446T1 (fr)
DE (2) DE4024657A1 (fr)
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IL108500A (en) * 1994-01-31 1998-06-15 Zohar Detergent Factory Fatty alcohol sulphates in granular form and process for their preparation
DE4406592A1 (de) * 1994-03-01 1995-09-07 Henkel Kgaa Verbesserte Mehrstoffgemische auf Basis wasserlöslicher Alkalisilikatverbindungen und ihre Verwendung, insbesondere zum Einsatz als Builder in Wasch- und Reinigungsmitteln
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US6204208B1 (en) 1996-09-04 2001-03-20 Kimberly-Clark Worldwide, Inc. Method and composition for treating substrates for wettability and skin wellness
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CN1970084B (zh) * 2006-12-04 2010-08-25 山东大学 一种类水滑石-囊泡复合体及其制备方法
EP2614841B1 (fr) 2012-01-12 2014-09-10 Evonik Industries AG Procédé de séparation continue de polymères hygroscopiques
CN103487310B (zh) * 2013-09-10 2015-08-05 付茜 一种沉积岩中干酪根分离前岩石样品的处理方法
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ES2073764T3 (es) 1995-08-16
US5397507A (en) 1995-03-14
DE59105890D1 (de) 1995-08-03
CN1058609A (zh) 1992-02-12
DE4024657A1 (de) 1992-02-06
JPH05509120A (ja) 1993-12-16
WO1992002609A1 (fr) 1992-02-20
ATE124446T1 (de) 1995-07-15
EP0541608A1 (fr) 1993-05-19

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