EP1117759B1 - Procede de granulation - Google Patents

Procede de granulation Download PDF

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Publication number
EP1117759B1
EP1117759B1 EP99969733A EP99969733A EP1117759B1 EP 1117759 B1 EP1117759 B1 EP 1117759B1 EP 99969733 A EP99969733 A EP 99969733A EP 99969733 A EP99969733 A EP 99969733A EP 1117759 B1 EP1117759 B1 EP 1117759B1
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EP
European Patent Office
Prior art keywords
surfactant
weight
foam
mixer
granules
Prior art date
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Expired - Lifetime
Application number
EP99969733A
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German (de)
English (en)
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EP1117759A1 (fr
Inventor
Wilfried Rähse
Matthias Sunder
Markus Semrau
Bernd Larson
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP1117759A1 publication Critical patent/EP1117759A1/fr
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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
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes

Definitions

  • the present invention relates to a process for the preparation of surfactant granules. It relates in particular to a process which allows surfactant granules or surfactant-containing Components of detergent and cleaner compositions or complete Detergent and detergent compositions with no or reduced use to prepare spray drying steps.
  • Granular detergent compositions or components thereof are produced to a large extent by spray drying.
  • the ingredients such as surfactants, builders, etc. with about 35 to 50 wt .-% of water an aqueous slurry, the so-called slurry, mixed and in spray towers sputtered in a hot gas stream, wherein the detergent particles and detergent form.
  • Both the equipment for this process and the implementation of the process are costly because most of the slurry water is evaporated in order to obtain particles with residual water contents around 5 to 10% by weight.
  • the granules produced by spray-drying usually have an excellent Solubility, but have only low bulk densities, resulting in higher packaging volumes as well as transport and storage capacities.
  • Spray drying method exhibit Another number of disadvantages, so that there was no lack of attempts, the Manufacture of detergents and cleaners completely without spray drying or at least the lowest possible levels of spray-drying products in the finished product to have.
  • European Patent EP 642 576 (Henkel) describes a two-stage granulation in two successive mixers / granulators, wherein in a first, low-speed granulator 40-100 wt .-%, based on the total amount of the ingredients used, the solid and liquid components vorgranuliert and in a second, high-speed granulator, the pregranulate optionally mixed with the remaining ingredients and transferred into a granulate the following process parameters are met: granulation in the first mixer at peripheral speeds of the tools of 2-7 m / s over 0.5-10 min, in the second mixer at peripheral speeds of 8-35 m / s over 0.1-30 (0.5-2) s; Pre-granulate temperature when entering the second granulation stage 30-60 ° C.
  • surfactant-containing zeolite granules having bulk densities of 750 to 1000 g / l can be prepared by using as granulating a mixture of water, surfactants and (co) polymeric carboxylates, wherein the content the granulating liquid to surfactants at least 10 wt .-% is.
  • the feeding of the granulation takes place according to the teaching of this document by a spray nozzle.
  • European patent application EP-A-0 402 111 discloses a granulation process for the preparation of surfactant granules in which surfactants, water and optionally fine powders are mixed to form a dough which is prepared by adding a deagglomerating agent Powder) is granulated in a high speed mixer.
  • European Patent Application EP-A-0 508 543 discloses a process in which a surfactant acid is neutralized with an excess of alkali to form an at least 40 wt% surfactant paste, which is subsequently conditioned and granulated, with a Direct cooling with dry ice or liquid nitrogen takes place.
  • the liquid surfactant mixtures disclosed in this document contain sodium or potassium salts of alkylbenzenesulfonic acids or alkylsulfuric acids in amounts of up to 80% by weight, ethoxylated nonionic surfactants in amounts of up to 80% by weight and at most 10% by weight of water.
  • the surfactant mixtures to be sprayed contain between 40 and 92% by weight of a surfactant mixture and more than 8 to at most 60% by weight of water.
  • the surfactant mixture is in turn at least 50% of polyalkoxylated nonionic surfactants and ionic surfactants.
  • German patent application DE-A-4304062 (Henkel KGaA) discloses a granulation process in which an anionic surfactant in its acid form or a mixture of several anionic surfactants in acid form in which an aqueous alkaline solution separately with a gaseous medium are applied. Subsequently, these preparation forms are sprayed into a granulation and granulated with a solid.
  • the procedure to be provided should be universally applicable and regarding the usable solids and Granulicrillonkeiten be subject to no restrictions, the disadvantage of energy-consuming evaporation of water but largely avoided.
  • the solution of these different tasks succeeds in a mixing and granulation process, in which a surfactant-containing flowable component by application of a gaseous medium is foamed to a foam, which as Granuliertosmittel serves.
  • the invention thus relates to a process for the preparation of surfactant granules, in which a surfactant-containing flowable component with a gaseous Medium is applied, wherein the surfactant-containing flowable component through the foamed gaseous medium and the resulting surfactant-containing foam below is added to a charged in a mixer solid bed.
  • the process of the invention has compared to the use of conventional Granulating liquids considerable advantages.
  • a "granulating foam” Instead of conventional Granulier crampkeiten is a much more homogeneous Liquid distribution on the solid bed reached.
  • the particles of the bed of solids become wets better and it is less granulating liquid to form the total Granules needed, so that can be dispensed with subsequent drying steps.
  • Another advantage is the more homogeneous particle size distribution of the resulting granules, because of the use of granulating foam overagglomeration and training is avoided by lumps.
  • foam used in the context of the present invention denotes Structures of gas-filled, spherical or polyhedron-shaped cells (pores), which by liquid, semi-liquid or highly viscous cell webs are limited.
  • the volume concentration of the gas forming the foam is more homodisperse Distribution is less than 74%, so are the gas bubbles because of the surface-reducing Effect of interfacial tension spherical.
  • the bubbles are deformed into polyhedral lamellae of about 4-600 be limited to thin skins.
  • the cell bridges connected via so-called nodal points, form a coherent framework. Between the cell ridges tension the Foam lamellae (closed-cell foam). Are the foam lamellae destroyed or If they flow back into the cell ridges at the end of foaming, you get an open-celled one Foam.
  • Foams are thermodynamically unstable, because by reduction of the surface Surface energy can be recovered. The stability and thus the existence The foams of the invention is thus dependent on how far they succeed in their self-destruction to prevent.
  • the gaseous medium in the surfactant-containing flowable Component is blown in, or the foaming is achieved by intensive beating, Shaking, splashing or stirring the liquid in the gas atmosphere concerned. Due to the lighter and better controllable and feasible foaming is in According to the present invention, the generation of foam by the injection of the gaseous Medium ("fumigation") over the other variants clearly preferred.
  • the gassing takes place depending on the desired process variant continuously or discontinuously over perforated plates, sintered disks, sieve inserts, Venturi nozzles or others usual systems.
  • any gases or gas mixtures be used.
  • gases used in the art are nitrogen, oxygen, Noble gases and noble gas mixtures such as helium, neon, argon and their Mixtures, carbon dioxide, etc.
  • the inventive method preferably carried out with air as the gaseous medium.
  • the gaseous medium can also be wholly or partially made of ozone, causing oxidatively destructible impurities or discoloration eliminated in the foaming surfactant-containing flowable components or a germ attack of these components can be prevented.
  • the inventive method includes the independent sub-steps of Production of foam from a surfactant-containing flowable component and the subsequent Addition to a moving in a mixer solid bed, the foam as Granulation aid is used.
  • the ingredients of the surfactant-containing produced in the first sub-step Foams are described below.
  • the surfactant-containing flowable component contains surfactants from the Group of anionic, nonionic, zwitterionic or cationic surfactants, wherein anionic surfactants for economic reasons and because of their power spectrum are clearly preferred.
  • the content of the flowable surfactant-containing component Surfactant (s) can vary within wide limits.
  • the surfactant-containing flowable component one or more surfactants from the group of anionic and / or nonionic and / or cationic and / or amphoteric surfactants in amounts of 20 to 100 wt .-%, preferably from 50 to 95 wt .-% and in particular from 60 to 90 wt .-%, each based on the surfactant-containing Component containing.
  • surfactant-containing flowable component anionic (s) surfactant (s) in amounts of 10 to 90 wt .-%, preferably from 20 to 85 wt .-% and in particular from 30 to 80 wt .-%, each based on the surfactant-containing component.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
  • alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids estersulfonatec
  • ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are also suitable.
  • the surfactant-containing flowable component comprises alkali metal salts of alkylbenzenesulfonic acids in amounts of from 20 to 90% by weight, preferably from 30 to 85% by weight and in particular from 40 to 80% by weight, based in each case on the surfactant Component containing.
  • sulfated fatty acid glycerol esters are sulfated fatty acid glycerol esters.
  • fatty acid glycerol esters are the mono-, di- and triesters and their mixtures to understand, as with the preparation by esterification of a monoglycerol with 1 to 3 mol fatty acid or obtained in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • preferred Sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, Myristic, lauric, palmitic, stearic or behenic acid.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analog environmental compatibility as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates which are prepared, for example, according to US Pat . Nos . 3,234,258 or 5,075,041 and can be obtained as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants.
  • EO ethylene oxide
  • Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • anionic surfactants are particularly soaps into consideration.
  • suitable saturated fatty acid soaps such as the salts of 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 soap mixtures.
  • the anionic surfactants including soaps may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or Triethanolamine.
  • the anionic surfactants are in the form of their Sodium or potassium salts, especially in the form of the sodium salts.
  • the surfactant-containing component has a soap content of 0.2% by weight on the total weight of the resulting granules.
  • the surfactant-containing flowable component in addition soaps in quantities from 1 to 30 wt .-%, preferably from 2 to 25 wt .-% and in particular from 5 to 20 Wt .-%, each based on the surfactant-containing component.
  • Preferred anionic surfactants are generally the alkylbenzenesulfonates and Fatty alcohol sulfates, with preferred surfactant granules more than 5 wt .-%, preferably more than 15% by weight and in particular more than 25% by weight of alkylbenzenesulfonate (s) and / or fatty alcohol sulfate (s), in each case based on the granule weight
  • nonionic surfactants are the most important surfactants Links.
  • surfactant-containing flowable component nonionic (s) surfactant (s) wherein method are preferred in which the surfactant-containing flowable component nonionic (s) Surfactant (s) in amounts of 1 to 100 wt .-%, preferably from 2 to 70 wt .-% and in particular from 5 to 30 wt .-%, each based on the surfactant-containing component.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • alkoxylated nonionic surfactants are preferred in the context of the present invention.
  • Process variants in which the surfactant-containing flowable component alkoxylated, preferably ethoxylated nonionic surfactants in amounts of 20 to 90 wt .-%, preferably from 30 to 85 wt .-% and in particular from 40 to 80 wt .-%, each based on the surfactant-containing Component contains, in this case have advantages, wherein processes are particularly preferred in which the surfactant-containing flowable component as ethoxylated nonionic surfactants, the reaction products of C 8-22 fatty alcohols, preferably C 12-20 fatty alcohols and in particular C 14-18 fatty alcohols with from 1 to 30 mol of ethylene oxide, preferably from 2 to 20 mol of ethylene oxide and in particular from 5 to 10 mol of ethylene oxide, in amounts of from 10 to 80% by weight, preferably from 20 to 75% by weight and in particular from 30 to 70% by weight. %, in each
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters as they are for example, in Japanese Patent Application JP 58/217598 , or which are preferably prepared according to the method described in International Patent Application WO-A-90/13533 .
  • alkyl polyglycosides Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG).
  • APG alkyl polyglycosides
  • Usable Alkypolyglycoside meet the general formula RO (G) z , in which R is a linear or branched, especially in the 2-position methyl branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.5.
  • linear alkyl polyglucosides ie alkyl polyglycosides in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.
  • the surfactant granules according to the invention may preferably contain alkylpolyglycosides, wherein contents of the granules of APG exceed 0.2% by weight, based on the total granules, are preferred.
  • Particularly preferred surfactant granules contain APG in amounts of 0.2 to 10 wt .-%, preferably 0.2 to 5 wt .-% and in particular from 0.5 to 3 wt .-%.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamide may be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of ethoxylated fatty alcohols, in particular not more than half of it.
  • polyhydroxy fatty acid amides of the formula (I) wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
  • R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an aryl radical
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides, for example according to the teaching of the international application WO-A-95/07331, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • the surfactant-containing flowable component according to the invention completely from a or more surfactants and thus be free of non-surfactant compounds. It is according to the invention but also possible, other ingredients of detergents and cleaners to incorporate into the surfactant-containing component.
  • the surfactant-containing component may also contain water due to the production process, this water being used for setting advantageous viscosity values or for optimization the foaming process of the surfactant-containing component also be added can.
  • the surfactant-containing flowable component contains less than 20% by weight, preferably less than 15% by weight, and in particular less than 10 wt .-% water, in each case based on the surfactant-containing component.
  • the surfactant-containing flowable component further ingredients of detergents and cleaners, in particular substances from the group of complexing agents, polymers, optical brighteners, Dyes and fragrances and alkalis.
  • the surfactant-containing flowable component to be added small components are described below.
  • the foaming of the flowable surfactant-containing component can be as desired Properties of the foam at room temperature or under cooling or heating respectively. Preferred process variants are carried out so that the foamed surfactant-containing flowable component before foaming temperatures of 20 to 120 ° C, preferably from 30 to 90 ° C and in particular from 50 to 75 ° C, having.
  • the viscosity of the surfactant-containing component in wide limits are varied, with less liquid surfactant-containing components in the Usually deliver less stable foams.
  • a surfactant-containing liquid component foamed and this foam with that of another liquid component produced foam are combined, which then serves as granulating foam.
  • the second liquid component is surfactant, for the sake of However, foam stability may be preferred.
  • foam stability may be preferred.
  • the flowable surfactant-containing component is through the gaseous medium to a Foamed foam, wherein liquid and gaseous medium in varying amounts or ratios to each other can be used. From process engineering It is preferred, for the production of foam, the gaseous medium in each case in quantities of at least 20% by volume, based on the amount of liquid to be foamed.
  • gaseous medium in this case preferably used air.
  • gaseous medium in this case preferably used air.
  • gas mixtures which For example, 0.1 to 4 wt .-% ozone.
  • the ozone content of the foaming gas then leads to the oxidative destruction of undesirable components in the foaming Liquids.
  • the Blend of ozone can be achieved a significant brightening.
  • the above exemplarily quoted liter of the surfactant-containing component preferably 1 to 300 liters, preferably 5 to 200 liters and in particular 10 used up to 100 liters of air.
  • the temperature of the resulting foam can be controlled.
  • the resulting foam has temperatures below 115 ° C., preferably between 20 and 80 ° C. and in particular between 30 and 70 ° C.
  • the resulting foam, which is used in the next process step as Granulationsangesmittel can be characterized by other physical parameters.
  • the foam has a density below 0.80 gcm -3 , preferably from 0.10 to 0.6 gcm -3 and especially from 0.30 to 0.55 gcm -3 .
  • the foam has average pore sizes below 10 mm, preferably below 5 mm and in particular below 2 mm.
  • the mentioned physical parameters of temperature, density and mean pore size characterize the foam at the time of its formation.
  • the process is chosen so that the foam the criteria mentioned even when added to the mixer met.
  • the foam is after its formation on a submitted in a mixer solid bed given there and serves as Granulationsangesmittel.
  • This process step can be found in the a variety of mixing and granulating be performed, as farther is described in detail below.
  • the solid bed submitted in the mixer can thereby All substances used in detergents and cleaners contain. In this way can be prepared by the process according to the invention finished washing and cleaning agents become.
  • certain ingredients of detergents and cleaners not granulated to avoid unwanted reactions of these constituents under the mechanical action of the granulating tools.
  • Ingredients which are usually only subsequently added to the resulting surfactant granules, i. in the Following granulation are bleaches, Bleach activators, enzymes and foam inhibitors.
  • the surfactant granules prepared according to the invention are present in addition to the surfactant Contain substances which in the later detergents and cleaners as active substances act.
  • the solid bed provided in the mixer therefore contains one or more substances from the group of builders, in particular the alkali metal carbonates, sulfates and silicates, zeolites and polymers.
  • builders are the most important ingredients of Detergents and cleaners. In the process according to the invention, all can usually be used builders used in detergents and cleaners in a solid bed zeolites, silicates, carbonates, organic co-builders and if there are no environmental concerns about their use - even the phosphates.
  • Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + 1 .H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are.
  • Such crystalline sheet silicates are described, for example, in European Patent Application EP-A-0 164 514 .
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred, whereby ⁇ -sodium disilicate can be obtained, for example, by the process described in international patent application WO-A-91/08171 .
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties.
  • the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous” is also understood to mean "X-ray amorphous”.
  • the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray-amorphous silicates which likewise have a dissolution delay compared to the conventional water glasses, are described, for example, in German patent application DE-A-44 00 024 .
  • Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula n Na 2 O. (1-n) K 2 O. Al 2 O 3 .
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • phosphates as builders possible, unless such use is avoided for environmental reasons should be.
  • Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular the tripolyphosphates.
  • Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such an operation is not objectionable for ecological reasons, as well as Mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures from these.
  • the solid bed submitted in the mixer may also contain compounded raw materials, i.e. Ingredients that themselves are process end product of previous process steps.
  • Next granulated, compacted or extruded raw materials are spray-dried Base powder as part of the submitted in the mixer bed of solids on.
  • This spray-dried Base powders may be surfactant-free (for example polymer compounds), but preferably contain surfactants. If such spray-dried base powder used be so contains the submitted in the mixer solid bed based on those in the mixer submitted solids in preferred process variants, the spray-dried Base powder, preferably the surfactant-containing spray-dried base powder, in quantities from 10 to 80% by weight, preferably from 15 to 70% by weight and especially from 20 to 60% by weight.
  • the Surfactant foam in the weight ratio foam: solid from 1: 100 to 9: 1, preferably from 1:30 to 2: 1 and especially from 1:20 to 1: 1, to the solid bed charged in the mixer is given.
  • the preferred amounts of granulation (surfactant) optimal granulation results are achieved.
  • Suitable mixers are, for example, Eirich® mixers of the R series or RV (trademark of Maschinenfabrik Gustav Eirich, Hardheim), the Schugi® Flexomix, the Fukae® FS-G blenders (trademarks of Fukae Powtech, Kogyo Co., Japan), the Lödige® FM, KM and CB mixers (trademark of Lödige Maschinenbau GmbH, Paderbom) or the Drais® series T or K-T (trademark of Drais-Werke GmbH, Mannheim).
  • the inventive method in a low-speed mixer / granulator at peripheral speeds of the tools of 2 m / s to 7 m / s, wherein the surfactant-containing foam in a time between 0.5 and 10 minutes, preferably between 1 and 7 minutes and especially between 2 and 5 minutes, is added to the solid bed provided in the mixer.
  • surfactant-containing foam in a high-speed mixer / granulator at peripheral speeds of 8 m / s to 35 m / s in a time between 0.1 and 30 seconds, preferably up to 10 seconds and in particular between 0.5 and 2 seconds, are added to the solid bed submitted in the mixer.
  • the two process variants described above use each describe a mixer, it is also possible according to the invention, two mixers with each other to combine.
  • methods are preferred in which the surfactant-containing Foam in a first, low-speed mixer / granulator on a moving solid bed is given, wherein 40 to 100 wt .-%, based on the total amount of the used Ingredients that pre-granulate solid and liquid ingredients and in one second, high-speed mixer / granulator the pregranulate from the first stage of the process optionally mixed with the remaining solid and / or liquid components and in a granulate is transferred.
  • the surfactant-containing foam in the first mixer / granulator placed on a solid bed and the mixture pre-granulated.
  • composition of the foam and the solid bed presented in the first mixer are chosen so that 40 to 100 wt .-%, preferably 50 to 90 wt .-% and in particular 60 to 80 wt .-%, of the solid and liquid components, based on the Total amount of ingredients used, are in the "pre-granules".
  • This "Vorgranulat” is now mixed in the second mixer with other solids and under Granulated addition of further liquid components to the finished surfactant granules. in this connection it is possible and preferred according to the invention, that in the second step, the Liquid ingredients are notviasüst as a liquid, but in the form of a Foam serve as Granulationsangesmittel ("granulation").
  • the composition that is added to the second mixer may depend on the composition of the foam used in the first mixer, so that above described method are preferred in which in the second, high-speed mixer / granulator the pregranulate from the first stage of the process also with addition a surfactant-containing foam, the composition of which in the first process stage used foam, is granulated to the finished granules.
  • the said order of low-speed high-speed mixer can according to the invention be reversed, so that a method according to the invention results, in which the surfactant-containing foam in a first, high-speed mixer / granulator aufein moved Solid bed is given, wherein 40 to 100 wt .-%, based on the total amount of ingredients that pre-granulate solid and liquid ingredients and all in one second, low-speed mixer / granulator the pregranulate from the first stage of the process optionally mixed with the remaining solid and / or liquid components and transferred to a granule.
  • All the above-described embodiment variants of the method according to the invention can be carried out batchwise or continuously.
  • a mixer as a high-speed mixer is having both a mixing and a crushing device, wherein the Mixing shaft at rotational speeds of 50 to 150 revolutions / minute, preferably from 60 to 80 revolutions / minute and the shaft of the comminution device at rotational speeds of 500 to 5000 revolutions / minute, preferably from 1000 to 300 revolutions / minute.
  • the method according to the invention is with regard to the selection of the ingredients to be used and their concentration can be varied over a wide range. Nevertheless, it is it is preferred, when according to the invention surfactant granules are prepared, the surfactant contents above 10% by weight, preferably above 15% by weight and in particular above 20 wt .-%, each based on the granules, and bulk densities above 600 g / l, preferably above 700 g / l and in particular above 800 g / l.
  • the granulation process according to the invention can be carried out in such a way that particles predetermined size distribution result.
  • the surfactant granules have a particle size distribution in which at least 50% by weight, preferably at least 60% by weight, in particular at least 70 wt .-% of the particles have sizes in the range of 400 to 1600 microns.
  • the Residual moisture content of the surfactant granules according to the invention can be determined by the Selection of raw materials are predetermined so that subsequent drying steps can be waived.
  • the surfactant granules have residual contents in free water from 2 to 15 wt .-%, preferably from 4 to 10 wt .-%, based on the surfactant granules, on.
  • the residual content of free water can, for example, by means of a modified UX method (Sartorius MA 30, program 120 ° C over 10 minutes) be determined.
  • surfactant granules produced by the process according to the invention can be described below with other ingredients of detergents and cleaners to the finished product be mixed. If appropriate, however, these ingredients can also be passed over the solid bed or be incorporated directly into the surfactant granules via the surfactant foam and are described below:
  • surfactant and builders especially in detergents and detergents conventional ingredients from the group of bleaches, bleach activators, Enzymes, pH adjusters, fragrances, perfume carriers, fluorescers, dyes, Foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, Color transfer inhibitors and corrosion inhibitors of importance.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldip
  • Chlorine or bromine releasing substances are used.
  • chlorine or bromine-releasing materials include, for example, heterocyclic N-bromo and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or salts thereof with Cations such as potassium and sodium into consideration.
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
  • bleach activators can be incorporated.
  • Bleach activators may be compounds which are aliphatic under perhydrolysis conditions
  • Peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, can be used.
  • Suitable substances are the O- and / or N-acyl groups of said C atom number and / or optionally substituted benzoyl groups.
  • acylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated Glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular Phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
  • TAED tetraacetyl
  • bleach catalysts are incorporated. These substances are to bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes are useful as bleach catalysts.
  • Enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof in question. Particularly suitable are from bacterial strains or Fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus enzymatic agents. Preferably, subtilisin-type proteases and in particular Proteases derived from Bacillus lentus.
  • enzyme mixtures for example from protease and amylase or protease and lipase or Protease and cellulase or cellulase and lipase or protease, amylase and lipase or protease, lipase and cellulase, but especially cellulase-containing mixtures of special interest.
  • Peroxidases or oxidases have also been found in some Cases proved to be suitable.
  • the enzymes can be adsorbed to carriers and / or embedded in encapsulants to protect against premature decomposition.
  • nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and of hydroxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic Cellulose ethers
  • nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and of hydroxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic Cellulose ethers
  • the known from the prior art polymers of phthalic acid and / or terephthalic acid or its derivatives in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives of these.
  • sulfonated ones Derivatives of phthalic and terephthalic acid
  • the detergents and cleaning agents can be used as optical brighteners derivatives of Diaminostilbendisulfonklare or their alkali metal salts.
  • Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar compounds which, instead of the morpholino group, have a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group wear.
  • brighteners of the type of substituted Diphenylstyryle present be, e.g.
  • Dyes and fragrances are added to detergents and cleaners to enhance the aesthetic To enhance the impression of the products and the consumer in addition to the softness performance a visual and sensory "typical and unmistakable" product to deliver.
  • perfume oils or perfumes individual fragrance compounds, e.g. the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons are used. Fragrance compounds of the ester type are e.g.
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes e.g.
  • the linear alkanals with 8-18 C atoms citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the Jonone, ⁇ -isomethylionone and methyl cedryl ketone, to the alcohols anethole, citronellol, Eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons mainly include the terpenes such as limes and pinene.
  • perfume oils may also contain natural fragrance mixtures, as available from plant sources, e.g. Pine, Citrus, Jasmine, Patchouly, Rose or Ylang-Ylang oil. Also suitable are muscatel, sage oil, chamomile oil, Clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, Vetiver oil, Olibanum oil, Galbanum oil and Labdanum oil and Orange blossom oil, Neroliol, Orange peel oil and sandalwood oil.
  • the content of detergents and cleaning agents is usually less than that of dyes 0.01% by weight, while perfumes account for up to 2% by weight of the total formulation can.
  • the fragrances can be incorporated directly into the detergents and cleaners, it However, it may also be advantageous to apply the fragrances to carriers, the adhesion of the perfume on the lingerie and by a slower release of fragrance for long-lasting fragrance of the textiles.
  • carrier materials for example Cyclodextrins proven, the cyclodextrin-perfume complexes in addition can still be coated with other excipients.
  • Preferred dyes their selection the expert no difficulty, have a high storage stability and Insensitivity to the other ingredients of the agent and against light as well no pronounced substantivity to textile fibers so as not to stain them.
  • Another object of the present invention is the use of the surfactant foams according to the invention as granulation liquid in the production of Surfactant granules.
  • the mixer to be used and in the solid bed usable ingredients are here referred to the above statements.
  • a surfactant-containing, flowable component of the composition given in Table 1 was metered at a temperature of 80 ° C in a equipped with a check valve pipe section and foamed via sintered disks with compressed air (16 m 3 / h).
  • the resulting foam (density: 0.45 gcm -3 , pore size ⁇ 1 mm, temperature: 75 ° C) was in the ratio foam: solid of ⁇ 1: 4.7 in a plowshare mixer with 2 cutter heads (KM300-D, Gebrueder Lödige, Paderbom), the foam impinging on the moving solid bed (composition see Table 2) in the area of the first cutter head.

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Claims (34)

  1. Procédé pour la préparation de produits de granulation tensioactifs, dans lequel on sollicite avec un milieu gazeux un composant tensioactif apte à l'écoulement, caractérisé en ce que le composant tensioactif apte à l'écoulement est transformé en mousse par le milieu gazeux et la mousse tensioactive que l'on obtient est appliquée par la suite sur un lit de substances solides déposé au préalable dans un mélangeur.
  2. Procédé selon la revendication 1, caractérisé en ce que le composant tensioactif apte à l'écoulement contient un ou plusieurs agents tensioactifs choisis parmi le groupe comprenant des agents tensioactifs anioniques et/ou non ioniques et/ou cationiques et/ou amphotères dans des quantités de 20 à 100 % en poids, de préférence de 50 à 95 % en poids, et en particulier de 60 à 90 % en poids, chaque fois rapportés au composant tensioactif.
  3. Procédé selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que le composant tensioactif apte à l'écoulement contient un ou plusieurs agents tensioactifs anioniques dans des quantités de 10 à 90 % en poids, de préférence de 20 à 85 % en poids, et en particulier de 30 à 80 % en poids, chaque fois rapportés au composant tensioactif.
  4. Procédé selon la revendication 3, caractérisé en ce que le composant tensioactif apte à l'écoulement contient des sels de métaux alcalins d'acides alkylbenzènesulfoniques dans des quantités de 20 à 90 % en poids, de préférence de 30 à 85 % en poids, et en particulier de 40 à 80 % en poids, chaque fois rapportés au composant tensioactif.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le composant tensioactif apte à l'écoulement contient en outre des savons dans des quantités de 1 à 30 % en poids, de préférence de 2 à 25 % en poids, et en particulier de 5 à 20 % en poids, chaque fois rapportés au composant tensioactif.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le composant tensioactif apte à l'écoulement contient un ou plusieurs agents tensioactifs non ioniques dans des quantités de 1 à 100 % en poids, de préférence de 2 à 70 % en poids, et en particulier de 5 à 30 % en poids, chaque fois rapportés au composant tensioactif.
  7. Procédé selon la revendication 6, caractérisé en ce que le composant tensioactif apte à l'écoulement contient des agents tensioactifs non ioniques alcoxylés, de préférence éthoxylés dans des quantités de 20 à 90 % en poids, de préférence de 30 à 85 % en poids, et en particulier de 40 à 80 % en poids, chaque fois rapportés au composant tensioactif.
  8. Procédé selon la revendication 7, caractérisé en ce que le composant tensioactif apte à l'écoulement contient, à titre d'agents tensioactifs non ioniques éthoxylés, les produits réactionnels d'alcools gras en C8-C22, de préférence d'alcools gras en C12-C20, en particulier d'alcools gras en C14-C18, avec de 1 à 30 moles d'oxyde d'éthylène, de préférence de 2 à 20 moles d'oxyde d'éthylène, et en particulier de 5 à 10 moles d'oxyde d'éthylène, dans des quantités de 10 à 80 % en poids, de préférence de 20 à 75 % en poids, et en particulier de 30 à 70 % en poids, chaque fois rapportés au composant tensioactif.
  9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que le composant tensioactif apte à l'écoulement contient de l'eau à concurrence de moins de 20 % en poids, de préférence à concurrence de moins de 15 % en poids, et en particulier à concurrence de moins de 10 % en poids, chaque fois rapportés au composant tensioactif.
  10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que le composant tensioactif apte à l'écoulement contient d'autres constituants d'agents de lavage et de nettoyage, en particulier des substances choisies parmi le groupe comprenant des formateurs de complexes, des polymères, des agents de blanchiment optique, des colorants et des parfums, ainsi que des alcalis.
  11. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que la quantité de gaz mise en oeuvre pour la transformation en mousse représente un volume de cent à trois cents fois, de préférence de cinq à deux cents fois, et en particulier de dix à cent fois le volume de la quantité du composant tensioactif apte à l'écoulement qui doit être transformée en mousse.
  12. Procédé selon l'une quelconque des revendications 1 à 11, caractérisé en ce qu'on met en oeuvre de l'air à titre de milieu gazeux.
  13. Procédé selon l'une quelconque des revendications 1 à 12, caractérisé en ce que le composant tensioactif apte à l'écoulement, qui doit être transformé en mousse, présente, avant la transformation en mousse, des températures de 20 à 120 °C, de préférence de 30 à 90 °C, et en particulier de 50 à 75 °C.
  14. Procédé selon l'une quelconque des revendications 1 à 13, caractérisé en ce qu'on transforme en mousse un composant liquide tensioactif et on combine la mousse obtenue avec une mousse obtenue à partir d'un autre composant liquide qui fait alors office de mousse de granulation.
  15. Procédé selon la revendication 14, caractérisé en ce que le deuxième composant liquide qui doit être transformé en mousse est un composant tensioactif.
  16. Procédé selon l'une quelconque des revendications 1 à 15, caractérisé en ce que la mousse tensioactive présente des températures inférieures à 115 °C, de préférence entre 20 et 80 °C, et en particulier entre 30 et 70 °C.
  17. Procédé selon l'une quelconque des revendications 1 à 16, caractérisé en ce que la mousse tensioactive présente une densité inférieure à 0,80 gcm-3, de préférence de 0,10 à 0,60 gcm-3, et en particulier de 0,30 à 0,55 gcm-3.
  18. Procédé selon l'une quelconque des revendications 1 à 17, caractérisé en ce que la mousse tensioactive présente des grosseurs de pores moyennes inférieures à 10 mm, de préférence inférieures à 5 mm, et en particulier inférieures à 2 mm.
  19. Procédé selon l'une quelconque des revendications 14 à 18, caractérisé en ce que la mousse tensioactive répond aux critères mentionnés lors de son addition dans le mélangeur.
  20. Procédé selon l'une quelconque des revendications 1 à 19, caractérisé en ce que le lit de substances solides déposé au préalable dans le mélangeur contient une ou plusieurs substances choisies parmi le groupe comprenant des builders, en particulier des carbonates, des sulfates et des silicates de métaux alcalins, des zéolithes et des polymères.
  21. Procédé selon l'une quelconque des revendications 1 à 20, caractérisé en ce que le lit de substances solides déposé au préalable dans le mélangeur contient une poudre de base séchée par pulvérisation, de préférence une poudre de base tensioactive séchée par pulvérisation, dans des quantités de 10 à 80 % en poids, de préférence de 15 à 70 % en poids, et en particulier de 20 à 60 % en poids, rapportés aux substances solides déposées au préalable dans le mélangeur.
  22. Procédé selon l'une quelconque des revendications 1 à 21, caractérisé en ce que la mousse tensioactive est appliquée sur le lit de substances solides déposé au préalable dans le mélangeur dans le rapport pondéral mousse : substance solide de 1 : 100 à 9 : 1, de préférence de 1 : 30 à 2 : 1, et en particulier de 1 : 20 à 1 : 1.
  23. Procédé selon l'une quelconque des revendications 1 à 22, caractérisé en ce que la mousse tensioactive est appliquée sur le lit de substances solides déposé au préalable dans le mélangeur dans un mélangeur/granulateur tournant à petite vitesse à des vitesses périphériques de l'appareillage de 2 m/s à 7 m/s dans un laps de temps entre 0,5 et 10 minutes, de préférence entre 1 et 7 minutes, et en particulier entre 2 et 5 minutes.
  24. Procédé selon l'une quelconque des revendications 1 à 22, caractérisé en ce que la mousse tensioactive est appliquée sur le lit de substances solides déposé au préalable dans le mélangeur dans un mélangeur/granulateur tournant à grande vitesse à des vitesses périphériques de 8 m/s à 35 m/s dans un laps de temps entre 0,1 et 30 secondes, de préférence allant jusqu'à 10 secondes, et en particulier entre 0,5 et 2 secondes.
  25. Procédé selon l'une quelconque des revendications 1 à 22, caractérisé en ce que la mousse tensioactive est appliquée sur un lit de substances solides mobile dans un premier mélangeur/granulateur tournant à petite vitesse, les constituants solides et liquides étant soumis à une granulation préalable, à concurrence de 40 à 100 % en poids, rapportés à la quantité totale des constituants mis en oeuvre, le produit de prégranulation issu de la première étape opératoire étant, le cas échéant, mélangé, dans un deuxième mélangeur/granulateur tournant à grande vitesse, avec les constituants solides et/ou liquides restants et étant transformé en un produit de granulation.
  26. Procédé selon la revendication 25, caractérisé en ce que, dans le deuxième mélangeur/granulateur tournant à grande vitesse, le produit de prégranulation issu de la première étape opératoire est également soumis à une granulation complète avec addition d'une mousse tensioactive, dont la composition peut s'écarter de celle de la mousse mise en oeuvre dans la première étape opératoire, pour obtenir un produit de granulation prêt à l'emploi.
  27. Procédé selon l'une quelconque des revendications 1 à 22, caractérisé en ce que la mousse tensioactive est appliquée sur un lit de substances solides mobile dans un premier mélangeur/granulateur tournant à grande vitesse, les constituants solides et liquides étant soumis à une granulation préalable, à concurrence de 40 à 100 % en poids, rapportés à la quantité totale des constituants mis en oeuvre, le produit de prégranulation issu de la première étape opératoire étant, le cas échéant, mélangé, dans un deuxième mélangeur/granulateur tournant à petite vitesse, avec les constituants solides et/ou liquides restants et étant transformé en un produit de granulation.
  28. Procédé selon la revendication 27, caractérisé en ce que, dans le deuxième mélangeur/granulateur tournant à petite vitesse, le produit de prégranulation issu de la première étape opératoire est également soumis à une granulation complète avec addition d'une mousse tensioactive, dont la composition peut s'écarter de celle de la mousse mise en oeuvre dans la première étape opératoire, pour obtenir un produit de granulation prêt à l'emploi.
  29. Procédé selon l'une quelconque des revendications 23 à 28, caractérisé en ce qu'on met en oeuvre le procédé en discontinu ou en continu.
  30. Procédé selon l'une quelconque des revendications 24 à 29, caractérisé en ce qu'on utilise, à titre de mélangeur tournant à grande vitesse, un mélangeur qui présente aussi bien un dispositif de mélange qu'un dispositif de broyage, l'arbre de mélange étant actionné à des vitesses périphériques de 50 à 150 tours/minute, de préférence de 60 à 80 tours/minute et l'arbre du dispositif de broyage étant actionné à des vitesses périphériques de 500 à 5000 tours/minute, de préférence de 1000 à 3000 tours/minute.
  31. Procédé selon l'une quelconque des revendications 1 à 30, caractérisé en ce que les produits de granulation tensioactifs présentent des teneurs en agents tensioactifs supérieures à 10 % en poids, de préférence supérieures à 15 % en poids, et en particulier supérieures à 20 % en poids, chaque fois rapportés au produit de granulation, et des densités apparentes supérieures à 600 g/l, de préférence supérieures à 700 g/l, et en particulier supérieures à 800 g/l.
  32. Procédé selon l'une quelconque des revendications 1 à 31, caractérisé en ce que les produits de granulation tensioactifs présentent une distribution granulométrique dans laquelle au moins 50 % en poids, de préférence au moins 60 % en poids et en particulier au moins 70 % en poids des particules possèdent des dimensions dans la plage de 400 à 1600 µm.
  33. Procédé selon l'une quelconque des revendications 1 à 32, caractérisé en ce que les produits de granulation tensioactifs présentent des teneurs résiduelles en eau libre de 2 à 15 % en poids, de préférence de 4 à 10 % en poids, rapportés au produit de granulation tensioactif.
  34. Utilisation de mousses tensioactives, qui présentent des grosseurs de pores moyennes inférieures à 10 mm, de préférence inférieures à 5 mm, et en particulier inférieures à 2 mm, à titre de liquide de granulation lors de la préparation de produits de granulation tensioactifs.
EP99969733A 1998-09-29 1999-09-18 Procede de granulation Expired - Lifetime EP1117759B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19844522A DE19844522A1 (de) 1998-09-29 1998-09-29 Granulationsverfahren
DE19844522 1998-09-29
PCT/EP1999/006917 WO2000018871A1 (fr) 1998-09-29 1999-09-18 Procede de granulation

Publications (2)

Publication Number Publication Date
EP1117759A1 EP1117759A1 (fr) 2001-07-25
EP1117759B1 true EP1117759B1 (fr) 2005-08-24

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EP99969733A Expired - Lifetime EP1117759B1 (fr) 1998-09-29 1999-09-18 Procede de granulation

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US (1) US6683042B1 (fr)
EP (1) EP1117759B1 (fr)
JP (1) JP2002525420A (fr)
KR (1) KR20010075409A (fr)
AT (1) ATE302843T1 (fr)
DE (2) DE19844522A1 (fr)
ES (1) ES2245521T3 (fr)
WO (1) WO2000018871A1 (fr)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19910789A1 (de) * 1999-03-11 2000-09-14 Henkel Kgaa Granulationsverfahren
DE10124430B4 (de) * 2001-05-18 2011-04-28 Henkel Ag & Co. Kgaa Granulationsverfahren mit Schäumen
DE10163603B4 (de) * 2001-12-21 2006-05-04 Henkel Kgaa Verfahren zur Herstellung builderhaltiger Tensidgranulate
US20080188392A1 (en) * 2002-12-02 2008-08-07 Diamond Chemical Company, Inc. Laundry Compositions
US20050186271A1 (en) * 2004-02-24 2005-08-25 Sheskey Paul J. Process for dispersing a fluid in a mass of solid particles
EP2164474A2 (fr) * 2007-05-08 2010-03-24 Dow Global Technologies Inc. Compositions polymères dispersibles dans l'eau
DE102007026216A1 (de) * 2007-06-05 2008-12-11 Clariant International Ltd. Feste Partikel von hydrophoben Bleichaktivatoren
US9237972B2 (en) * 2008-12-16 2016-01-19 Kimberly-Clark Worldwide, Inc. Liquid surfactant compositions that adhere to surfaces and solidify and swell in the presence of water and articles using the same
EP3279319B1 (fr) * 2010-04-26 2020-06-10 Novozymes A/S Granules enzymatiques
US9512388B2 (en) 2015-02-18 2016-12-06 Henkel Ag & Co. Kgaa Solid state detergent in a transparent container
USD762486S1 (en) 2015-02-18 2016-08-02 Henkel Ag & Co. Kgaa Solid state detergent in a transparent container
USD784819S1 (en) 2015-02-18 2017-04-25 Henkel Us Iv Corporation Container for a solid state detergent
RU2615506C1 (ru) * 2015-10-13 2017-04-05 Александр Адольфович Ламберов Способ гранулирования цеолита в качестве компонента синтетических моющих средств
JP6350500B2 (ja) * 2015-12-04 2018-07-04 トヨタ自動車株式会社 造粒体の製造装置および製造方法

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3234258A (en) 1963-06-20 1966-02-08 Procter & Gamble Sulfation of alpha olefins
GB1151767A (en) 1965-06-24 1969-05-14 Colgate Palmolive Co Process for the preparation of Detergent Compositions
JPS58217598A (ja) 1982-06-10 1983-12-17 日本油脂株式会社 洗剤組成物
DE3413571A1 (de) 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt Verwendung von kristallinen schichtfoermigen natriumsilikaten zur wasserenthaertung und verfahren zur wasserenthaertung
CA1276852C (fr) 1985-06-21 1990-11-27 Francis John Leng Composition detersive liquide
GB8625104D0 (en) 1986-10-20 1986-11-26 Unilever Plc Detergent compositions
DE3741401A1 (de) 1987-12-07 1989-06-15 Henkel Kgaa Verfahren zur herstellung von festen oder pastenfoermigen produkten
US4919847A (en) * 1988-06-03 1990-04-24 Colgate Palmolive Co. Process for manufacturing particulate detergent composition directly from in situ produced anionic detergent salt
DE3914131A1 (de) 1989-04-28 1990-10-31 Henkel Kgaa Verwendung von calcinierten hydrotalciten als katalysatoren fuer die ethoxylierung bzw. propoxylierung von fettsaeureestern
CA2017921C (fr) 1989-06-09 1995-05-16 John Michael Jolicoeur Preparation de granules detergentes par voie de separation d'une pate detergente
YU221490A (sh) 1989-12-02 1993-10-20 Henkel Kg. Postupak za hidrotermalnu izradu kristalnog natrijum disilikata
US5075041A (en) 1990-06-28 1991-12-24 Shell Oil Company Process for the preparation of secondary alcohol sulfate-containing surfactant compositions
DE4038609A1 (de) 1990-12-04 1992-06-11 Henkel Kgaa Verfahren zur herstellung von zeolith-granulaten
EP0508543B1 (fr) 1991-04-12 1997-08-06 The Procter & Gamble Company Structuration chimique de pâtes tensio-actives pour former des granulés tensio-actifs avec haute activité
DE4216774A1 (de) 1992-05-21 1993-11-25 Henkel Kgaa Verfahren zur kontinuierlichen Herstellung eines granularen Wasch und/oder Reinigungsmittels
US5739097A (en) 1993-02-11 1998-04-14 Henkel Kommanditgesellschaft Auf Aktien Process for the production of surfactant granules
DE4304062A1 (de) 1993-02-11 1994-08-18 Henkel Kgaa Verfahren zur Herstellung von Tensidgranulaten
WO1995007331A1 (fr) 1993-09-09 1995-03-16 The Procter & Gamble Company Detergents liquides comportant des tensioactifs d'amides d'acides gras n-alcoxy ou n-aryloxy polyhydroxy
DE4400024A1 (de) 1994-01-03 1995-07-06 Henkel Kgaa Silikatische Builder und ihre Verwendung in Wasch- und Reinigungsmitteln sowie Mehrstoffgemische für den Einsatz auf diesem Sachgebiet
DE4425968A1 (de) 1994-07-25 1996-02-01 Henkel Kgaa Verfahren zur Herstellung von Tensidgranulaten

Also Published As

Publication number Publication date
US6683042B1 (en) 2004-01-27
EP1117759A1 (fr) 2001-07-25
ES2245521T3 (es) 2006-01-01
ATE302843T1 (de) 2005-09-15
DE59912472D1 (en) 2005-09-29
DE19844522A1 (de) 2000-03-30
JP2002525420A (ja) 2002-08-13
KR20010075409A (ko) 2001-08-09
WO2000018871A1 (fr) 2000-04-06

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