WO1994007990A1 - Procede de fabrication de granules tensioactifs - Google Patents

Procede de fabrication de granules tensioactifs Download PDF

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Publication number
WO1994007990A1
WO1994007990A1 PCT/EP1993/002567 EP9302567W WO9407990A1 WO 1994007990 A1 WO1994007990 A1 WO 1994007990A1 EP 9302567 W EP9302567 W EP 9302567W WO 9407990 A1 WO9407990 A1 WO 9407990A1
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Prior art keywords
granules
surfactant
surfactants
anionic
weight
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PCT/EP1993/002567
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German (de)
English (en)
Inventor
Volker Bauer
Ditmar Kischkel
Andreas Syldath
Joachim Peters
Peter Kraeplin
Jochen Jacobs
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to DE59309891T priority Critical patent/DE59309891D1/de
Priority to EP93920800A priority patent/EP0663005B1/fr
Publication of WO1994007990A1 publication Critical patent/WO1994007990A1/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
    • C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
    • 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

Definitions

  • the invention relates to a process for converting anionic surfactants in their acid form into washable and cleaning-active surfactant compounds and storage-stable and dust-free granules with preferably increased bulk density.
  • anionic oleochemical surfactant compounds are the known sulfofatty acid ethyl esters (fatty acid methyl ester sulfonates, ES), which by ⁇ -sulfonation of the methyl esters of fatty acids of vegetable 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.
  • ES fatty acid methyl ester sulfonates
  • ester cleavage gives rise to the corresponding sulfo fatty acids or their disalts, which, like mixtures of disalts and sulfo fatty acid methyl ester mono salts, have important washing and cleaning properties.
  • comparable problems also occur in other surfactant classes when trying to display the corresponding surfactant raw materials in dry form.
  • a final bleaching for example with aqueous hydrogen peroxide, is generally required in their synthesis, so that here, too, today's technology leads to aqueous paste form.
  • APG pastes Such aqueous alkyl glycoside pastes (APG pastes) are more at risk from hydrolysis or microbial contamination, for example, than corresponding dry products.
  • simple drying according to the technologies customary to date presents considerable difficulties.
  • drying an aqueous paste of the alkali salts of detergent soaps and / or ABS pastes can also cause considerable problems.
  • Granulation is an alternative to spray drying of surfactant pastes.
  • European patent application EP 403 148 describes a process for producing FAS granules which can be dispersed in cold water.
  • a highly concentrated aqueous FAS paste is used contains less than 14% by weight of water and less than 20% by weight of further additives, mechanically processed at temperatures between 10 and 45 ° C. until granules form.
  • FAS granules are obtained which are already dispersed at washing temperatures between 4 and 30 ° C; however, the process temperature to be observed and the relatively low maximum water content of the surfactant paste represent critical process parameters.
  • a process for the production of FAS and / or ABS granules is known from European patent application EP 402112, the neutralization of the anionic surfactants in acid form to give a paste with a maximum of 12% by weight of water with the addition of auxiliaries such as polyethylene glycols , ethoxylated alcohols or alkylphenols, which have a melting point above 48 ° C, and the granulation is carried out in a tendon-running mixer.
  • auxiliaries such as polyethylene glycols , ethoxylated alcohols or alkylphenols, which have a melting point above 48 ° C
  • the amount of water to be maintained represents a critical process parameter.
  • European patent application 353 976 discloses an anhydrous production process for surfactant granules, anionic surfactants in their acid form on granular or powdery carriers such as phosphate, arbonate, Bicarbonate or silicate are adsorbed and then agglomerated in a fluidized bed.
  • the object of the invention was to provide a process for the production of concentrated surfactant granules, in which the content of a non-surfactant liquid component, in particular water, is not a critical process parameter.
  • the invention accordingly relates to a process for the preparation of washable and cleaning-active anionic surfactant granules by neutralizing anionic surfactants in their acid form, characterized in that the anionic surfactants are neutralized in their acidic form with a powdery neutralizing agent, at the same time being granulated and the resulting granules if desired, be dried simultaneously.
  • Suitable anionic surfactants in their acid form are either an anionic surfactant in its acid form or a surfactant from the group of the anionic surfactants in their acid form, preferably in combination with anionic, nonionic, amphoteric and / or cationic surfactants.
  • Preferred anionic surfactants in their acid form are C8-C22-alkylsulfonic acids, Cg-Ci ⁇ -alkylbenzenesulfonic acids, usually called dodecylbenzenesulfonic acid, and ⁇ -sulfofatty acid methyl esters in their acid form.
  • alkylsulfonic acids are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, in particular from fatty alcohols, for example from coconut oil alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, pal ityl or stearyl alcohol, or the C ⁇ o-C20 ⁇ O ⁇ oa alcohols and those secondary alcohols of this chain length.
  • the sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 moles of ethylene oxide, are also suitable.
  • esters of ⁇ -sulfofatty acids which, for example, the ⁇ -sulfonated by ⁇ -sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin with 10 to 20 C atoms in the fatty acid molecule
  • Methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids and the ⁇ -sulfofatty acids (diacids) obtainable by ester cleavage.
  • mixtures of mono acids and Diacids with other anionic surfactants in their acid form for example with alkylbenzenesulfonic acids and / or fatty alkylsulfonic acids, are preferred.
  • alkanesulfonic acids which are obtainable from Ci2-Ci8-alkanes by sulfochlorination or sulfoxidation.
  • the content of neutralized anionic surfactants in the finished granules is generally 0.5 to 60% by weight, preferably 0.5 to 30% by weight and in particular 1 to 10% by weight.
  • Powdered alkali metal hydroxide or alkali metal carbonate is preferably used as the powdered neutralizing agent, the use of the sodium salts and potassium salts, in particular sodium carbonate and potassium carbonate, being preferred.
  • the neutralizing agent is advantageously used at least in stoichiometric amounts, for example in molar ratios of neutralizing agent to anionic surfactant in acid form from 0.5: 1 to 120: 1, preferably from at least 10: 1 and in particular from 20: 1 to 110: 1. If further solids are used, molar ratios of the neutralizing agent to anionic surfactant in acid form from 0.5: 1 to 10: 1 and in particular from 1: 1 to 5: 1 may also be preferred.
  • the neutralizing agent in a substoichiometric amount. This can even be advantageous from a procedural point of view.
  • the non-neutralized portions of the liquid anionic surfactants in their acid form then remain liquid in the fluidized bed, do not agglomerate themselves, but can be a valuable auxiliary as a binder in the granulation and become solid when they emerge from the fluidized bed.
  • the anionic surfactants are used in their acid form in combination with anionic, nonionic, amphoteric and / or cationic surfactants.
  • the alkylbenzenesulfonates, fatty alkyl sulfates and methyl ⁇ -sulfofatty acid esters already described are preferred as anionic surfactants.
  • anionic surfactants include, for example, alkanesulfonates and the salts of sulfosuccinic acid or soaps made from natural or synthetic, preferably saturated or ethylenically unsaturated, fatty acids. Soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids, are particularly suitable. Preferred in this context are those which are 50 to 100% saturated Ci2-CI8 fatty acid soaps un - z - - soaps are composed to 50% of oleic acid.
  • the anionic surfactants can be used in the form of their sodium, potassium, calcium and ammonium salts and as water-soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • Preferred nonionic surfactants are derived from liquid ethoxylated, in particular primary alcohols with preferably 9 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide per mole of alcohol, in which the alcohol radical can be linear or methyl-branched in the 2-position, or li ⁇ may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • linear residues of alcohols of native origin with 12 to 18 carbon atoms such as, for example, coconut oil, tallow fat or oleyl alcohol, are preferred.
  • the degrees of ethoxylation given represent statistical mean values which can be an integer or a fractional number for a special product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow ranks ethoxylates, nre).
  • alcohol ethoxylates are preferred which have an average of 2 to 8 ethylene oxide groups.
  • the preferred ethoxylated alcohols include, for example, Cg-Cu oxo alcohol with 7 E0, Ci3-Ci5-0xo alcohol with 3 E0, 5 E0 or 7 E0 and in particular Ci2-Ci4 alcohol with 3 E0 or 4 E0, Ci2-Ci8- Alcohols with 3 E0, 5 E0 or 7 E0 and mixtures of these, such as mixtures of Ci2-Ci4 alcohol with 3 E0 and Ci2 ⁇ Ci8 alcohol with 5 E0.
  • alkyl glycosides of the general formula R-0- (G) x in which R is a primary straight-chain or aliphatic radical which is methyl-branched in the 2-position and has 8 to 22, preferably 12 to 18, carbon atoms, G is furthermore a symbol , which stands for a glycose unit with 5 or 6 carbon atoms, and the oligomer Degree of fixation x is between 1 and 10, preferably between 1 and 2 and in particular is significantly less than 1.4.
  • the anionic surfactants in their acid form can be introduced into the process either separately or in a mixture with these other surfactants.
  • at least one further liquid component which is present in liquid to pasty form under normal pressure at temperatures between 20 and 70 ° C., is simultaneously introduced in its acid form.
  • one of these additional liquid components contains anionic and / or nonionic surfactants, but especially anionic surfactants that are present as a water-containing paste.
  • Anion surfactant pastes in the form of about 30 to 60% by weight aqueous preparations in which the anionic surfactants are obtained by neutralizing the corresponding acids when they are not prepared according to the invention are particularly preferred.
  • the content of the finished granules in additionally used surfactants, in particular in anionic surfactants, which are introduced into the process in aqueous, pasty form or as powder, is preferably 10 to about 99.5% by weight, in particular 30 to 80% by weight. and advantageously 40 to 70% by weight, so that the finished granules contain a total of preferably 10 to 100% by weight, in particular 30 to 80% by weight and advantageously 40 to 70% by weight of surfactants, in particular anionic surfactants .
  • the liquid component or the liquid components can also contain further ingredients of detergents and cleaning agents.
  • a liquid component contains silicates, for example crystalline sheet silicates of the general formula NaMSi x 02 ⁇ + i ⁇ H20, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, or contains amorphous alkali silicates with a molar ratio M2 ⁇ : Si ⁇ 2 of 1: 1 to 1: 4, preferably from 1: 2 to 1: 3.3, or aluminosilicates in detergent quality.
  • silicates for example crystalline sheet silicates of the general formula NaMSi x 02 ⁇ + i ⁇ H20, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, or contains amorphous alkali silicates with a molar ratio M2 ⁇ : Si ⁇ 2 of 1: 1 to 1: 4, preferably from 1: 2 to 1: 3.3,
  • aqueous zeolite suspensions for example an aqueous suspension of zeolite NaA and of mixtures of NaA and NaX, is preferred.
  • the suspension can make small additions of nonionic surfactants contain as stabilizers, for example 1 to 3% by weight, based on
  • a non-surfactant liquid component is introduced into the process which contains constituents of organic and / or inorganic nature and preferably under normal pressure below 250 ° C., advantageously below 200 ° C. and in particular between 60 and 180 ° C is boiling.
  • Mono- and / or polyfunctional alcohols for example methanol, ethanol, propanol, isopropanol, butanol, secondary and tertiary butanol, pentanol, ethylene glycol, 1,2-, are preferably used as the optional organic constituent of the non-surfactant liquid component.
  • Propanediol, glycerin and mixtures of these are used.
  • water is preferred to use water as the inorganic constituent, preferably together with ethanol, 1,2-propanediol or glycerol.
  • further solids which are preferably the usual ingredients of detergents and cleaners, can be introduced into the process.
  • the zeolite can also be used as a spray-dried powder.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 20 to 22% by weight of bound water.
  • the content of zeolite and / or layered silicates and / or amorphous silicates in the finished granules is preferably 15 to 70% by weight and in particular 20 to 60% by weight, in each case calculated as water-containing substance.
  • bleaching agents chlorine bleaching agents, but preferably peroxy bleaching agents
  • peroxy bleaching agents are introduced into the process.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching itte! are, for example, peroxy carbonate, peroxypyrophosphates, citrate perhydrates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • hydrogen peroxide as the bleaching agent in one of the liquid components.
  • the content of peroxy bleaching agents, in particular hydrogen peroxide, in the finished granules is preferably 0.5 to 10% by weight and in particular 1 to 5% by weight.
  • bleach activators can also be incorporated into the granules.
  • these are N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N.N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
  • the bleach activators contain bleach activators in the usual range, preferably between 1 and 8% by weight and in particular between 2 and 5% by weight.
  • Particularly preferred bleach activators are N, N, N '.N'-tetraacetylethylene diamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.
  • Additives for example neutral salts, in particular alkali sulfates, salts of polycarboxylic acids, in particular salts of citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid or mixtures of these, dyes, foam inhibitors and / or the other, can be used as further liquid, pasty or solid constituents Solubility-improving ingredients are introduced into the process.
  • Suitable foam inhibitors are, for example, soaps of natural and synthetic origin, which have a high proportion of Ci8 ⁇ C24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of different foam inhibitors are also advantageously used, for example those made from silicone and paraffins or waxes.
  • the foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • the foam inhibitor content of the surfactant preparation form is preferably 0.01 to 0.5% by weight.
  • Components that improve solubility include liquid, pasty and solid compounds.
  • the use of polyethylene glycols with a relative molecular weight between 200 and 600 is particularly preferred. These polyethylene glycols are advantageously used as part of one of the additional liquid components.
  • solid polyethylene glycols with a relative molecular weight greater than or equal to 2000, in particular between 4000 and 20,000 can also be used.
  • the content of the finished granules in these constituents improving the solubility of the finished granules is preferably 0.5 to 15% by weight and in particular 1 to 10% by weight, for example between 2 and 7% by weight.
  • the anionic surfactants in their acid form are simultaneously neutralized, granulated and the resulting granules are dried.
  • "Drying” is understood to mean the partial or complete removal of the non-surfactant liquid components.
  • the process according to the invention has the advantage that the heat generated during neutralization can be used simultaneously for drying the resulting granules.
  • residual values of free that is to say unbound water and / or mono- and / or polyfunctional alcohols can be present as long as the finished granules are free-flowing and non-sticky.
  • a free water content of 10% by weight and in particular 0.1 to 2% by weight, based in each case on the finished granules is preferably not exceeded.
  • the granules can be produced in all devices in which neutralization with simultaneous granulation and with simultaneous drying can be carried out.
  • examples of this are heatable mixers and granulators, in particular granulators of the Turbo dryer ( R ) type (device from Vomm, Italy).
  • the invention provides that the combination of these process steps in a batch or continuous the current fluidized bed is carried out. It is particularly preferred to carry out the process continuously in the fluidized bed.
  • the liquid anionic surfactants in their acid form or the various liquid components can be introduced into the fluidized bed simultaneously or in succession via one, for example via a nozzle with several openings, or via several nozzles.
  • the nozzle or the nozzles and the direction of spraying of the products to be sprayed can be arranged as desired.
  • the solid carriers which are the neutralizing agent and, if appropriate, further solids, can be dusted in via one or more lines simultaneously (continuous process) or in succession (batch process), preferably pneumatically via blowing lines, the neutralizing agent in batch process is dusted as the first solid.
  • Fluidized bed apparatuses which are preferably used have base plates with dimensions of at least 0.4 m.
  • fluidized bed apparatuses are preferred which have a base plate with a diameter between 0.4 and 5 m, for example 1.2 m or 2.5 m.
  • fluidized bed apparatuses are also suitable which have a base plate with a diameter greater than 5 m.
  • a perforated floor plate or a Conidur plate (commercial product from Hein & Leh ⁇ mann, Federal Republic of Germany) is preferably used as the base plate.
  • the method according to the invention is preferably carried out at fluidizing air speeds between 1 and 8 m / s and in particular between 1.5 and 5.5 m / s, for example up to 3.5 m / s.
  • the granules are discharged from the fluidized bed advantageously by means of a size classification of the granules.
  • This classification can be carried out, for example, by means of a sieve device or by an opposed air flow (classifier air) which is regulated in such a way that only particles of a certain particle size are removed from the fluidized bed and smaller particles are retained in the fluidized bed.
  • the inflowing air is composed of the heated or unheated classifier air and the heated soil air.
  • the soil air temperature is preferably between 80 and 400 ° C, in particular between 90 and 350 ° C. Temperatures between 200 and 300 ° C. are particularly advantageous.
  • the fluidizing air is generally cooled by heat losses and possibly by the evaporation heat the components of the non-surfactant liquid component. This
  • the air outlet temperature exceeds the temperature of the vortex air about 5 cm above the base plate.
  • the temperature of the fluidizing air is approximately 5 cm above the base plate 60 to 120 ° C., preferably 65 to 100 ° C. and in particular 70 to 90 ° C.
  • the air outlet temperature is preferably between 60 and 120 ° C, in particular below 100 ° C and particularly advantageously between 70 and 90 ° C.
  • Ingredients of detergents and cleaning agents are particularly suitable as starting mass, in particular those which can also be used as solids in the process according to the invention and which have a particle size distribution which corresponds approximately to the particle size distribution of the finished granules.
  • surfactant granules as starting mass which have already been obtained in a previous process.
  • non-surfactant liquid component evaporate partially or completely in the fluidized bed. Dried to dried germs are formed, which are coated with further amounts of introduced anionic surfactants in their acid form and, if appropriate, additionally introduced anionic surfactant pastes, optionally neutralized with neutralizing agent, granulated and again dried at the same time.
  • a particularly important embodiment provides that the anionic surfactants are granulated in their acid form with the addition of an inorganic and optionally an organic solid, at least one of which has neutralizing properties, and the resulting granules are dried simultaneously, if necessary.
  • Suitable organic solids are, for example, surfactants or surfactant mixtures which have been produced by granulation, by spray drying or by the process according to the invention and which are recycled after grinding in order to increase the surfactant concentration in the finished granulate.
  • the use of spray-dried and / or surfactant granules obtained by the process according to the invention is preferred.
  • Highly ethoxylated fatty alcohols with, for example, 20 to 80 EO, preferably 20 to 60 E0 and in particular tallow fatty alcohol with 30 or 40 E0, can also advantageously be used as solids.
  • the solids are preferably used as finely divided materials, which can either be produced directly in this state, are commercially available, or are converted into this finely divided state by conventional comminution methods, for example by grinding with conventional mills.
  • Preferred solids have, for example, no more than 5% by weight of particles with a diameter above 2 mm and preferably no more than 5% by weight of particles with a diameter above 1.6 mm.
  • solids are preferred which consist of at least 90% by weight of particles with a diameter below 1.0 mm, in particular below 0.6 mm.
  • Solids are particularly preferred which consist of at least 40% of particles with a diameter below 0.1 mm. Examples of this are alkali carbonates with more than 90 parts by weight of particles with a diameter of less than or equal to 0.5 mm and zeolite NaA powder in detergent quality, which contains at least 90 parts by weight with a diameter below 0.03 mm contains.
  • the surfactant granules which can be produced by the process according to the invention are claimed.
  • Preferred surfactant granules have a surfactant content of 10 to 100% by weight, in particular 30 to 80% by weight and with particular advantage between 40 and 70% by weight, based in each case on the finished granules.
  • Pure surfactant granules are obtained when sodium carbonate is used as the neutralizing agent in stoichiometric amounts, the neutralization has passed 100%, the non-surfactant liquid component of the anionic surfactant paste optionally used is completely evaporated and the granules are thus completely dried and the any added solids consist of a pure surfactant material.
  • surfactant granules which have been produced by the process according to the invention and now serve as a solid in the process according to the invention are optionally comminuted to the desired particle size distribution and recycled.
  • the content of surfactants in the granules can be set to any of the desired values.
  • preferred granules contain 20 to 70% by weight, in particular 40 to 60% by weight, sodium and / or potassium carbonate.
  • granular washing and cleaning agents are claimed which can be produced by the process according to the invention.
  • Preferred granular washing and cleaning agents contain 30 to 80% by weight of surfactants, 20 to 60% by weight of zeolite and / or crystalline layered silicates, smectite, bentonite or mixtures of zeolite, crystalline layered silicates and / or smectite and / or bentonite and / or amorphous silicates, and 0.5 to 10% by weight of peroxy bleach and, if appropriate, further ingredients of washing and cleaning agents.
  • Granular detergents and cleaning agents are particularly preferred which additionally contain 0.5 to 10% by weight, preferably 1 to 8% by weight, sodium and / or potassium carbonate.
  • the surfactant granules or granular detergents and cleaning agents obtained by the process according to the invention generally have a bulk density of 350 to 1000 g / 1, preferably between 450 and 850 g / 1 and in particular between 500 and 800 g / 1 dust-free, ie in particular they do not contain any particles with a particle size below 50 ⁇ m. Otherwise the particle size distribution of the granules corresponds to the usual particle size distribution of a heavy detergent of the prior art.
  • the granules have a particle size distribution in which a maximum of 5% by weight, particularly advantageously a maximum of 3% by weight, of the particles have a diameter below 0.1 mm, in particular below 0.2 mm.
  • the particle size distribution can be influenced by the nozzle positioning in the fluidized bed system.
  • the granules are characterized by their light color and their flowability. A further measure to prevent the granules produced according to the invention from sticking together is not necessary.
  • a process step can be followed, the granules being powdered in a known manner with finely divided materials, for example with zeolite NaA, sodium carbonate, silica or calcium stearate, in order to further increase the bulk density. This powdering can for example during a rounding step.
  • preferred granules already have such a regular, in particular approximately spherical, structure that a rounding step is generally not necessary and is therefore not preferred.
  • the granules have an improved dissolving behavior. This is due to the fact that when alkali carbonate is used as the neutralizing agent, carbon dioxide is produced in the neutralization reaction, which escapes during the granulation and drying process, whereby granules with a pronounced pore structure can be obtained under certain circumstances.
  • Examples 1 and 2 used alkylbenzenesulfonic acid (Marlon (R) AS3, a commercial product from Huls AG, Federal Republic of Germany) and a tallow alcohol sulfate paste containing 54% by weight tallow alcohol sulfate and 41% water (sulfopone ( R. ) T55, commercial product of the applicant) through a 3-component nozzle into a plant for granulation drying (AGT; Glatt, Federal Republic of Germany).
  • sodium carbonate bulk density approx. 550 g / l; commercial product from Matthes & Weber, Federal Republic of Germany
  • a surfactant granulate was used as the starting mass, which had been produced in a previous batch (under the same process conditions) and had approximately the same composition as the finished granules of Examples 1 and 2.
  • the process conditions can be found in Table 1. Through simultaneous drying neutralization, granulation and drying, dust-free, non-sticky granules with high surfactant contents were produced (see Table 2).
  • ABS acid anionic surfactant acid
  • Example 1 In a repeat experiment of Example 1, the position of the granules with a grain size above 2.5 mm was reduced to a value below 5% by weight by another positioning of the nozzle for the liquid components.

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Abstract

Les granulés tensioactifs anioniques à action détergente et lavante, à haute teneur en tensioactifs anioniques sont obtenus par neutralisation de tensioactifs anioniques sous leur forme acide avec un agent de neutralisation pulvérulent, effectuée en même temps que la granulation et éventuellement en même temps que la dessiccation. On procède de préférence à la neutralisation d'acides sulfoniques d'alcool gras, d'acides sulfoniques de benzène d'alkyle et/ou de mélanges acides-esters méthyliques d'acide sulfonique gras α avec un excédent de carbonate de sodium et à la granulation simultanée avec d'autres composants liquides, notamment avec des pâtes tensioactives anioniques, une solution d'eau oxygénée et/ou une suspension à zéolithe. La fabrication peut s'opérer dans tous les dispositifs permettant d'effectuer simultanément une neutralisation, une granulation et une dessiccation. La fabrication s'opère de préférence dans une installation à lit fluidisé.
PCT/EP1993/002567 1992-09-30 1993-09-22 Procede de fabrication de granules tensioactifs WO1994007990A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE59309891T DE59309891D1 (de) 1992-09-30 1993-09-22 Verfahren zur herstellung von tensidgranulaten
EP93920800A EP0663005B1 (fr) 1992-09-30 1993-09-22 Procede de fabrication de granules tensioactifs

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4232874.8 1992-09-30
DE4232874A DE4232874A1 (de) 1992-09-30 1992-09-30 Verfahren zur Herstellung von Tensidgranulaten

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WO1994007990A1 true WO1994007990A1 (fr) 1994-04-14

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PCT/EP1993/002567 WO1994007990A1 (fr) 1992-09-30 1993-09-22 Procede de fabrication de granules tensioactifs

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EP (1) EP0663005B1 (fr)
CN (1) CN1087945A (fr)
AT (1) ATE187200T1 (fr)
DE (2) DE4232874A1 (fr)
ES (1) ES2140467T3 (fr)
WO (1) WO1994007990A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5490954A (en) * 1993-07-05 1996-02-13 Lever Brothers Company, Division Of Conopco, Inc. Detergent composition or component containing anionic surfactant and process for its preparation
US6133223A (en) * 1997-06-27 2000-10-17 Lever Brothers Company, Division Of Conopco, Inc. Production of detergent granulates
US6369015B1 (en) 1998-11-20 2002-04-09 Unilever Home & Personal Care, Usa Division Of Conopco, Inc. Particulate laundry detergent compositions containing anionic surfactant granules
US6992055B1 (en) * 1996-09-06 2006-01-31 Kao Corporation Process for preparing detergent compositions having high bulk density
WO2011061045A1 (fr) 2009-11-20 2011-05-26 Unilever Nv Granulé de détergent et son procédé de fabrication

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DE4304015A1 (de) * 1993-02-11 1994-08-18 Henkel Kgaa Verfahren zur Herstellung von Granulaten
DE4314885A1 (de) * 1993-05-05 1994-11-10 Sued Chemie Ag Verfahren zur Neutralisation der Säureform von anionischen Tensiden, danach erhaltene Agglomerate und Waschmittel
GB9415904D0 (en) * 1994-08-05 1994-09-28 Unilever Plc Process for the production of detergent composition
GB9712583D0 (en) 1997-06-16 1997-08-20 Unilever Plc Production of detergent granulates
GB9712580D0 (en) * 1997-06-16 1997-08-20 Unilever Plc Production of detergent granulates
DE19822943A1 (de) * 1998-05-22 1999-11-25 Henkel Kgaa Verfahren zur Herstellung von Wasch- und Reinigungsmitteln
DE19844523A1 (de) 1998-09-29 2000-03-30 Henkel Kgaa Granulationsverfahren
DE19851454B4 (de) * 1998-11-09 2010-11-04 Henkel Ag & Co. Kgaa Tensid-Granulate durch Wirbelschichtgranulation
DE10163603B4 (de) * 2001-12-21 2006-05-04 Henkel Kgaa Verfahren zur Herstellung builderhaltiger Tensidgranulate
DE10258011A1 (de) * 2002-12-12 2004-07-08 Henkel Kgaa Trockenneutralisationsverfahren
DE102005005499A1 (de) * 2005-02-04 2006-08-17 Henkel Kgaa Verfahren zur Herstellung von Wasch- oder Reinigungsmitteln
CN103820253B (zh) * 2014-02-12 2016-06-01 浙江赞宇科技股份有限公司 一种连续化制备粉状mes粒子的工艺及装置

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US4734224A (en) * 1986-09-15 1988-03-29 The Dial Corporation Dry neutralization process for detergent slurries
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5490954A (en) * 1993-07-05 1996-02-13 Lever Brothers Company, Division Of Conopco, Inc. Detergent composition or component containing anionic surfactant and process for its preparation
US6992055B1 (en) * 1996-09-06 2006-01-31 Kao Corporation Process for preparing detergent compositions having high bulk density
US6133223A (en) * 1997-06-27 2000-10-17 Lever Brothers Company, Division Of Conopco, Inc. Production of detergent granulates
US6369015B1 (en) 1998-11-20 2002-04-09 Unilever Home & Personal Care, Usa Division Of Conopco, Inc. Particulate laundry detergent compositions containing anionic surfactant granules
WO2011061045A1 (fr) 2009-11-20 2011-05-26 Unilever Nv Granulé de détergent et son procédé de fabrication

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ES2140467T3 (es) 2000-03-01
EP0663005B1 (fr) 1999-12-01
ATE187200T1 (de) 1999-12-15
EP0663005A1 (fr) 1995-07-19
CN1087945A (zh) 1994-06-15
DE4232874A1 (de) 1994-03-31
DE59309891D1 (de) 2000-01-05

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