EP0663005B1 - Procede de fabrication de granules tensioactifs - Google Patents

Procede de fabrication de granules tensioactifs Download PDF

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Publication number
EP0663005B1
EP0663005B1 EP93920800A EP93920800A EP0663005B1 EP 0663005 B1 EP0663005 B1 EP 0663005B1 EP 93920800 A EP93920800 A EP 93920800A EP 93920800 A EP93920800 A EP 93920800A EP 0663005 B1 EP0663005 B1 EP 0663005B1
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EP
European Patent Office
Prior art keywords
granules
acid form
anionic
anionic surfactants
surfactants
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German (de)
English (en)
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EP0663005A1 (fr
Inventor
Volker Bauer
Ditmar Kischkel
Andreas Syldath
Joachim Peters
Peter Kraeplin
Jochen Jacobs
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Cognis IP Management GmbH
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
    • C11D11/04—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions 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 into their acid form in wash and cleaning active anionic surfactant granules.
  • the economical synthesis of light colored surfactant powders in particular of anionic surfactants based on fatty alkyl sulfates (FAS) and alkyl benzene sulfonates (ABS), is today a reliable state of technical knowledge.
  • the corresponding surfactant salts fall into aqueous preparation forms at, water contents in the range of about 20 to 80 wt .-% and in particular are adjustable from about 35 to 60 wt .-%.
  • anionic oleochemical surfactant compounds are the known sulfofatty acid methyl esters (fatty acid methyl ester sulfonates, MES) to name, by ⁇ -sulfonation of the methyl ester of fatty acids of vegetable or animal origin with predominantly 10 to 20 carbon atoms in the fatty acid molecule and subsequent ones Neutralization to water-soluble mono-salts, especially the corresponding ones Alkali salts can be produced.
  • MES fatty acid methyl ester sulfonates
  • Such aqueous alkyl glycoside pastes are, for example, by hydrolysis or microbial Contamination is more at risk than corresponding dry products. Also Here, simple drying is prepared using previously common technologies considerable difficulties. After all, drying can do the trick an aqueous paste of the alkali salts of detergent soaps and / or ABS pastes pose considerable problems.
  • Granulation is an alternative to spray drying surfactant pastes
  • European patent application EP 403 148 describes this Process for the production of FAS granules that are dispersible in cold water are.
  • a highly concentrated aqueous FAS paste is used less than 14% by weight of water and less than 20% by weight of other additives contains, mechanically processed at temperatures between 10 and 45 ° C, until granules form.
  • FAS granules are indeed obtained, which is already dispersed at washing temperatures between 4 and 30 ° C. become; the process temperature to be observed and the relatively low however, maximum water content of the surfactant paste are critical process parameters It is also not disclosed which bulk weights have the granules produced by this process.
  • a process for the production is known from the European patent application EP 402 112 of FAS and / or ABS granules known, the neutralization the anionic surfactants in acid form to a paste with a maximum of 12% by weight Water with the addition of auxiliaries such as polyethylene glycols, ethoxylated Alcohols or alkylphenols, which have a melting point above 48 ° C have, and the granulation take place in a high-speed mixer. Again, the amount of water to be maintained is a critical process parameter It is also not disclosed which bulk weights the have surfactant granules obtained by this process.
  • a process for the production is known from the European patent application EP 402 111 wash and cleaning active surfactant granules with a bulk density known between 500 and 1200 g / l, a surfactant preparation form, which contains water as a liquid component and also organic May contain polymers and builder substances with a fine particle size Solid added and granulated in a high-speed mixer becomes.
  • the water content of the surfactant paste is critical Process parameters. If the water content of the surfactant paste is too high the solid is dispersed so that it is no longer used as a deagglomeration agent can work. On the other hand, the solids content exceeds a certain value, the mass does not have that for the granulation necessary consistency.
  • European patent application 353 976 discloses an anhydrous manufacturing process for surfactant granules, with anionic surfactants in their acid form on granular or powdery carriers such as phosphate, carbonate, Adsorbed bicarbonate or silicate and then in a fluidized bed be agglomerated.
  • Patent application GB 2 209 172 discloses a process for the production of surfactant granules, in which a builder granulate, preferably sodium carbonate, in a fluidized bed is presented, onto which a concentrated aqueous solution of a surfactant is sprayed.
  • a preferred embodiment of the invention is the neutralization of the acid form of the Anionic surfactants associated with this agglomeration. It’s not the water content of the products, nor their bulk weights or the temperatures during process control revealed.
  • the object of the invention was to provide a method for manufacturing to provide concentrated surfactant granules in which the content of a non-surfactant liquid component, especially water, none represents critical process parameters.
  • the invention accordingly relates to a process for the production of washing and cleaning-active anionic surfactant granules by neutralizing anionic surfactants in their Acid form, characterized in that the liquid phase of the anionic surfactants in their acid form simultaneously with and in addition to a liquid component that is under normal pressure at temperatures between 20 and 70 ° C in liquid to pasty form and one aqueous zeolite suspension contains with a powdered neutralizing agent a fluidized bed batchwise or continuously, preferably continuously, neutralized, granulated at the same time and the resulting granules if desired be dried at the same time.
  • Suitable anionic surfactants in their acid form are either an anionic surfactant in its acid form or a surfactant mixture from the group of 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 C 8 -C 22 alkyl sulfonic acids, C 9 -C 13 alkyl benzene sulfonic acids, mostly called dodecyl benzene sulfonic acid, and methyl ⁇ -sulfofatty acid ester in their acid form.
  • alkyl sulfonic 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, palmityl or stearyl alcohol, or the C 10 -C 20 oxo alcohols, and those secondary Alcohols of this chain length.
  • the sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 mol of ethylene oxide, are also suitable.
  • esters of ⁇ -sulfofatty acids which, by ⁇ -sulfonation of the methyl esters of fatty acids of plant and / or animal origin with 10 to 20 C atoms in the fatty acid molecule, are, for example, the ⁇ -sulfonated methyl esters of the hydrogenated coconut -, Palm kernel or tallow fatty acids, and the ⁇ -sulfofatty acids (diacids) obtainable by ester cleavage are used.
  • alkanesulfonic acids which can be obtained from C 12 -C 18 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.
  • the pulverulent neutralizing agent is preferably pulverized Alkali hydroxide or alkali carbonate used, the use of Sodium salts and potassium salts, especially sodium carbonate and potassium carbonate, is preferred.
  • the neutralizing agent is advantageous at least in stoichiometric amounts, for example in molar ratios Neutralizing agent for 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 used. If other solids are used, can also 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 be preferred.
  • the neutralizing agent in substoichiometric amounts to use is even possible.
  • the non-neutralized portions of the liquid anionic surfactants in their acid form then remain fluid in the fluidized bed, agglomerate itself not, but can be a valuable binder in granulation Represent excipient and are at the exit from the fluidized bed firmly.
  • 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.
  • tallow fatty sulfonic acids and / or alkylbenzenesulfonic acids in combination with tallow fatty alkyl sulfate and / or alkylbenzenesulfonate or ⁇ -sulfofatty acid esters in their acid form in combination with ⁇ -sulfofatty acid ester mono salts and / or alkylbenzenesulfonates in the process.
  • suitable 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. Preference is given to those which are composed of 50 to 100% of saturated C 12 -C 18 fatty acid soaps and 0 to 50% of oleic acid soaps.
  • the anionic surfactants can be 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 can be used.
  • 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 linear and May contain methyl-branched radicals in the mixture, as they are usually present in oxo alcohol radicals.
  • the alcohol radical can be linear or methyl-branched in the 2-position, or linear and May contain methyl-branched radicals in the mixture, as they 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 oil or oleyl alcohol, are particularly preferred.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, nre).
  • alcohol ethoxylates are preferred which have an average of 2 to 8 ethylene oxide groups.
  • the preferred ethoxylated alcohols include, for example, C 9 -C 11 oxo alcohol with 7 EO, C 13 -C 15 oxo alcohol with 3 EO, 5 EO or 7 EO and in particular C 12 -C 14 alcohol with 3 EO or 4 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 5 EO.
  • nonionic surfactants which can be used are alkyl glycosides of the general formula RO- (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 a symbol which represents a glycose unit with 5 or 6 carbon atoms, and the degree of oligomerization x is between 1 and 10, preferably between 1 and 2 and in particular is significantly less than 1.4.
  • 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 a symbol which represents a glycose unit with 5 or 6 carbon atoms
  • the degree of oligomerization x is between 1 and 10, preferably between 1 and 2 and in particular is significantly less than 1.4.
  • the anionic surfactant in its acid form becomes at least one further liquid component, which under normal pressure at temperatures between 20 and 70 ° C in liquid to pasty form, entered at the same time. It is it prefers that one of these additional liquid components be anionic and / or nonionic surfactants, but especially anionic surfactants, which are present as a water-containing paste.
  • anionic surfactant pastes in the form of about 30 to 60% by weight aqueous preparations, in which the anionic surfactants in when they are not produced according to the invention Neutralization of the corresponding acids occur, particularly preferred.
  • the content of the finished granules in additionally used tensides, especially on anionic surfactants, which are in aqueous, pasty form or as Powder introduced into the process is preferably 10 to about 99.5% by weight, in particular 30 to 80% by weight and advantageously 40 to 70 wt .-%, so that the finished granules in total preferably 10 to 100% by weight, in particular 30 to 80% by weight and advantageously 40 to Contain 70% by weight of surfactants, especially anionic surfactants.
  • the liquid component or the liquid components also contain further ingredients of detergents and cleaning agents.
  • aqueous zeolite suspensions are included.
  • aqueous suspensions of zeolite NaA and mixtures of NaA and NaX are preferred.
  • the suspension can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups.
  • a liquid component contains silicates, for example crystalline sheet silicates of the general formula NaMSi x O 2x + 1 .yH 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, or contains amorphous alkali silicates with a molar ratio M 2 O: SiO 2 of 1: 1 to 1: 4, preferably of 1: 2 to 1: 3.3.
  • silicates for example crystalline sheet silicates of the general formula NaMSi x O 2x + 1 .yH 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, or contains amorphous alkali silicates with a molar ratio M 2 O: SiO 2 of 1: 1 to 1: 4, preferably of 1: 2 to 1: 3.3.
  • a non-surfactant liquid component introduced into the process which contains components of organic and / or inorganic nature and preferably under normal pressure below 250 ° C, advantageously below 200 ° C and in particular boils between 60 and 180 ° C.
  • organic component of the non-surfactant liquid component are preferably mono- and / or polyfunctional alcohols, for example Methanol, ethanol, propanol, isopropanol, butanol, secondary and tertiary butanol, pentanol, ethylene glycol, 1,2-propanediol, glycerin and Mixtures of these are used.
  • inorganic component water, preferably together with ethanol, 1,2-propanediol or use glycerin.
  • Solids which are preferred ingredients of detergents and cleaning agents are brought into the process.
  • crystalline layered silicates already mentioned above, layered silicates like smectite or bentonite, amorphous silicates and above all Zeolite, especially NaA zeolite.
  • the zeolite can also can be used as 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 zeolite content of the finished granules and / or layered silicates and / or amorphous silicates is preferably 15 to 70 wt .-% and in particular 20 to 60 wt .-%, each calculated as hydrous 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 agents are, for example, peroxy carbonate, peroxypyrophosphate, citrate perhydrate, peroxophthalate, 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 H 2 O 2 , preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
  • the bleach activator content of the bleach-containing granules is 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'-tetraacetylethylenediamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.
  • additives for example neutral salts, especially 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 solubility improving ingredients in the procedure be introduced.
  • neutral salts especially 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 solubility improving ingredients in the procedure be introduced.
  • Suitable foam inhibitors are, for example, soaps of natural and synthetic origin, which have a high proportion of C 18 -C 24 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 is preferably 0.01 to 0.5% by weight.
  • Components that improve solubility include liquid, pasty and solid compounds.
  • Preferred solubility-improving constituents are polyethylene glycols with a relative molecular weight between 200 and 20,000 and highly ethoxylated fatty alcohols with 14 to 80 ethylene oxide groups per mole of alcohol, in particular C 12 -C 18 fatty alcohols with 20 to 60 ethylene oxide groups, for example tallow fatty alcohol with 30 EO or 40 EO used.
  • 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 which improve 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 neutralized at the same time, granulated and the resulting granules dried. It is under "Drying” means the partial or complete removal of the non-surfactant Understand liquid components.
  • the method according to the invention has the advantage that the heat generated during neutralization can also be used to dry the resulting granules can. If desired, residual values of free, i.e. unbound, can be used Water and / or mono- and / or polyfunctional alcohols available as long as the finished granules are free-flowing and non-sticky. However, a free water content of 10% by weight and in particular from 0.1 to 2% by weight, based in each case on the finished granules, not exceeded.
  • the granules are produced according to the invention in a batch or continuously ongoing fluidized bed. 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 simultaneously or in succession via a for example via a nozzle with several openings, or via several Nozzles are introduced into the fluidized bed.
  • the nozzle or nozzles and the spray direction of the products to be sprayed can be arranged as desired be.
  • the solid carriers which are the neutralizing agent and optionally can represent further solids, via one or more lines simultaneously (continuous process) or successively (batch process), preferably dusted pneumatically via blow lines, the neutralizing agent being the first solid in the batch process is dusted.
  • Fluidized bed apparatuses used with preference have base plates with dimensions of at least 0.4 m.
  • fluidized bed apparatus preferred, which is a base plate with a diameter between 0.4 and 5 m, for example 1.2 m or 2.5 m.
  • they are also fluidized bed devices suitable a bottom plate with a larger diameter than 5 m.
  • a perforated base plate is preferably used as the base plate or a Conidur plate (commercial product from Hein & Lehmann, Federal Republic of Germany).
  • the invention Swirl air velocities 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 carried out.
  • the granules are advantageously discharged from the fluidized bed about a size classification of the granules.
  • This classification can for example by means of a screening device or by a reverse air flow (classifier air), which is regulated so that only particles from a certain particle size out of the fluidized bed removed and smaller particles are retained in the fluidized bed.
  • the inflowing air is exposed the heated or unheated classifier air and the heated bottom air together.
  • the soil air temperature is preferably between 80 and 400 ° C, especially between 90 and 350 ° C. Are particularly advantageous temperatures between 200 and 300 ° C.
  • the vortex air cools in the generally by heat loss and possibly by the heat of vaporization the components of the non-surfactant liquid component.
  • the air outlet temperature is about 5 cm above the base plate.
  • the temperature of the vortex air is about 5 cm above the Base plate 60 to 120 ° C, preferably 65 to 100 ° C and especially 70 up to 90 ° C.
  • the air outlet temperature is preferably between 60 and 120 ° C, especially below 100 ° C and with particular advantage between 70 and 90 ° C.
  • Ingredients are particularly suitable as starting mass of detergents and cleaning agents, especially those that can also be used as solids in the process according to the invention can and have a grain size distribution, which is approximately the Grain size distribution of the finished granules corresponds.
  • a grain size distribution which is approximately the Grain size distribution of the finished granules corresponds.
  • surfactant granules as starting mass that already have were obtained in a previous process.
  • the components of the non-surfactant evaporate in the fluidized bed Partial or complete liquid component. There are dried ones to dried germs, with additional quantities of anionic surfactants in their acid form and, if necessary, additionally introduced anionic surfactant pastes enveloped, if necessary neutralized with neutralizing agent, granulated and again dried at the same time.
  • a particularly important embodiment provides that the anionic surfactants in its acid form with the addition of an inorganic and optionally an organic solid, at least one of which has neutralizing properties, granulated and the resulting Granules - if necessary - are dried at the same time.
  • Suitable organic solids are, for example, surfactants or surfactant mixtures, by granulation, by spray drying or according to the invention Processes have been made and used to increase surfactant concentration can be recycled in the finished granulate after grinding.
  • surfactant granules preferred.
  • surfactant granules preferred.
  • With advantage can also be highly ethoxylated fatty alcohols, for example, as solids 20 to 80 EO, preferably 20 to 60 EO and especially tallow fatty alcohol with 30 or 40 EO.
  • the solids are preferably used as finely divided materials, which can either be produced directly in this condition, can be purchased or by conventional comminution methods, for example by grinding with conventional mills, converted into this finely divided state become.
  • preferred solids have no more than 5 % By weight of particles with a diameter above 2 mm and preferably not 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 Particles with a diameter below 1.0 mm, especially below of 0.6 mm.
  • Solids that are at least 40 % consist of particles with a diameter below 0.1 mm.
  • alkali carbonates with more than 90 wt .-% of particles with a Diameter less than or equal to 0.5 mm and zeolite NaA powder in detergent quality, which at least 90 wt .-% particles with a diameter contains less than 0.03 mm.
  • the surfactant granules produced by the process according to the invention have a content of 10 to 100 wt .-%, in particular of 30 to 80% by weight and with particular advantage between 40 and 70% by weight, each based on the finished granules, of surfactants.
  • Pure surfactant granules are obtained when sodium carbonate as neutralizing agent was used in stoichiometric amounts, the neutralization 100% has expired, the non-surfactant liquid component of the optionally used anionic surfactant paste completely evaporated and the granules is completely dried and any solid added consists of a pure surfactant material.
  • Surfactant granules produced by the process according to the invention were and now as a solid in the inventive method serve, optionally crushed to the desired particle size distribution and recycled.
  • the content of surfactants in the granules is on everyone the desired values can be set.
  • Preferred granules also contain the surfactants 20 to 70% by weight, in particular 40 to 60% by weight sodium and / or potassium carbonate.
  • the according to the inventive method manufacturable granular detergents and cleaning agents included 30 to 80 wt .-% surfactants, 20 to 60 wt .-% 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 wt .-% peroxy bleach and optionally other ingredients of detergents and cleaning agents.
  • Especially granular detergents and cleaning agents are preferred, which additionally 0.5 to 10 wt .-%, preferably 1 to 8 wt .-% sodium and / or Potassium carbonate included.
  • the surfactant granules obtained by the process according to the invention or Granular detergents and cleaning agents generally have a bulk density from 350 to 1000 g / l, preferably between 450 and 850 g / l and in particular between 500 and 800 g / l and are dust-free, i.e. they contain especially no particles with a particle size below 50 ⁇ m. Otherwise the particle size distribution of the granules corresponds to the usual one Particle size distribution of a heavy detergent the state of the art.
  • the granules have a grain size distribution, at a maximum of 5% by weight, with a particular advantage of a maximum of 3 % By weight of the particles have a diameter below 0.1 mm, in particular below 0.2 mm.
  • the grain size distribution is by Nozzle positioning in the fluidized bed system can be influenced.
  • the granules are characterized by their bright colors and their flowability out. Another measure to prevent the sticking is Granules produced according to the invention are not required.
  • a process step can be followed, whereby the granules in order to further increase the bulk density in known Way with finely divided materials, for example with zeolite NaA, soda, Silica or calcium stearate are powdered. This powdering can for example during a rounding step.
  • granules already have such a regular one, in particular approximately spherical structure that a rounding step in generally not necessary and therefore not preferred.
  • the Granules have an improved dissolving behavior. This is due to, that when using alkali carbonate as a neutralizing agent During the neutralization reaction, carbon dioxide is generated, which during of the granulation and drying process escapes, which may result in Granules with a pronounced pore structure can be obtained.

Claims (12)

  1. Procédé de production de granulés tensioactifs anioniques dotés d'un pouvoir lavant et nettoyant, par neutralisation de surfactifs anioniques sous leur forme acide, caractérisé en ce que la phase liquide des tensioactifs anioniques sous leur forme acide est présentée en même temps que et en plus d'un composant liquide, qui est présent sous forme liquide à pâteuse à la pression normale et à des températures comprises entre 20 et 70 °C et qui renferme une suspension aqueuse de zéolithe, et est neutralisée avec un neutralisant en poudre dans un lit fluidisé, de manière discontinue ou continue, de préférence continue, en étant simultanément granulée, les granulés obtenus étant séchés simultanément si on le souhaite.
  2. Procédé selon la revendication 1, caractérisé en ce que l'on met en oeuvre dans la pâte, un surfactif anionique sous sa forme acide ou un mélange de tensioactifs appartenant au groupe des surfactifs anioniques sous leur forme acide, de préférence des acides alkyl(en C8-C22)sulfoniques, en particulier des acides alkylsulfoniques gras, des acides alkyl(en C9-C13)benzènesulfoniques et des esters méthyliques d'acides gras sulfoniques sous leur forme acide, en association avec des tensioactifs anioniques, non ioniques, amphotères et/ou cationiques, en particulier des surfactifs anioniques et/ou des alcools gras éthoxylés liquides comportant 2 à 8 groupes d'oxyde d'éthylène par mol d'alcool.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que l'on met en oeuvre comme neutralisant pulvérulent, de l'hydroxyde ou du carbonate de métal alcalin pulvérisé, l'utilisation de sels de sodium et de potassium, en particulier de carbonate de sodium et de potassium étant préférée, et le neutralisant étant mis en oeuvre au moins en quantités stoechiométriques, par exemple en rapports molaire entre le neutralisant et le surfactif anionique sous forme acide de 0,5:1 à 120:1, de préférence d'au moins 10:1 et en particulier, de 20:1 à 110:1, en présence d'autres matières solides, de préférence de 0,5:1 à 10:1 et en particulier, de 1:1 à 5:1
  4. Procédé selon une des revendications 1 à 3, caractérisé en ce que le composant liquide introduit en plus des surfactifs anioniques sous forme acide, renferme des tensioactifs anioniques et/ou non ioniques, de préférence des tensioactifs anioniques, qui sont présents comme pâte aqueuse.
  5. Procédé selon une des revendications 1 à 4, caractérisé en ce qu'on introduit dans le procédé comme autres supports pulvérulents, des matières solides, qui sont de préférence des ingrédients usuels de produits de lavage et de nettoyage, en particulier des sulfates de métaux alcalins, des silicates de métaux alcalins cristallins et amorphes, des silicates lamellaires, tels que la zéolithe et des sels d'acides polycarboxyliques.
  6. Procédé selon une des revendications 1 à 5 caractérisé en ce qu'on introduit dans le procédé un composant liquide non tensioactif, qui renferme des constituants de nature organiques et/ou inorganique, et dont le point d'ébullition se situe de préférence sous pression normale en deçà de 250 °C, de préférence en deçà de 200 °C et en particulier, entre 60 et 180 °C.
  7. Procédé selon une des revendications 1 à 6 caractérisé en ce qu'on introduit dans le procédé un agent de blanchiment, de préférence un agent de blanchiment peroxydique, par exemple du perborate ou du percarbonate et en particulier de l'eau oxygénée, ainsi qu'éventuellement un activateur de blanchiment.
  8. Procédé selon une des revendications 1 à 7 caractérisé en ce qu'on introduit dans le procédé des constituants liquides, pâteux ou solides, qui améliorent la solubilité.
  9. Procédé selon une des revendications 1 à 8 caractérisé en ce que l'on utilise la chaleur de neutralisation pour le séchage.
  10. Procédé selon une des revendications 1 à 9 caractérisé en ce que les surfactifs anioniques sous leur forme acide et les autres composants sont introduits simultanément ou successivement dans le lit fluidisé via une ou plusieurs buses, tandis que les supports solides, que représentent le neutralisant et éventuellement d'autres matières solides, peuvent être saupoudrés via une ou plusieurs canalisations, simultanément ou successivement, de préférence par voie pneumatique, le neutralisant étant saupoudré comme première matière solide.
  11. Procédé selon une des revendications 1 à 10 caractérisé en ce que la vitesse de l'air turbulent est comprise entre 1 et 8 m/s, de préférence entre 1,5 et 5,5 m/s, la température de l'air du fond est comprise entre 80 et 400 °C, de préférence entre 90 et 350 °C, en particulier entre 200 et 300 °C, la température de l'air turbulent à environ 5 cm au-dessus de la plaque de fond atteint 60 à 120 °C, de préférence 65 à 100 °C et en particulier 70 à 90 °C, et la température de sortie de l'air est comprise entre 60 et 120 °C, de préférence inférieure à 100 °C et en particulier, comprise entre 70 et 90 °C.
  12. Procédé selon une des revendications 1 à 11, caractérisé en ce que le déchargement des granulés du lit fluidisé se déroule via un criblage.
EP93920800A 1992-09-30 1993-09-22 Procede de fabrication de granules tensioactifs Expired - Lifetime EP0663005B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4232874A DE4232874A1 (de) 1992-09-30 1992-09-30 Verfahren zur Herstellung von Tensidgranulaten
DE4232874 1992-09-30
PCT/EP1993/002567 WO1994007990A1 (fr) 1992-09-30 1993-09-22 Procede de fabrication de granules tensioactifs

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EP0663005A1 EP0663005A1 (fr) 1995-07-19
EP0663005B1 true EP0663005B1 (fr) 1999-12-01

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EP93920800A Expired - Lifetime EP0663005B1 (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)

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DE102005005499A1 (de) * 2005-02-04 2006-08-17 Henkel Kgaa Verfahren zur Herstellung von Wasch- oder Reinigungsmitteln

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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
GB9313878D0 (en) * 1993-07-05 1993-08-18 Unilever Plc Detergent composition or component containing anionic surfactant and process for its preparation
GB9415904D0 (en) * 1994-08-05 1994-09-28 Unilever Plc Process for the production of detergent composition
TW397862B (en) * 1996-09-06 2000-07-11 Kao Corp Detergent granules and method for producing the same, and high-bulk density detergent composition
GB9712580D0 (en) * 1997-06-16 1997-08-20 Unilever Plc Production of detergent granulates
GB9712583D0 (en) 1997-06-16 1997-08-20 Unilever Plc Production of detergent granulates
GB9713748D0 (en) * 1997-06-27 1997-09-03 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
GB9825563D0 (en) 1998-11-20 1999-01-13 Unilever Plc Particulate laundry detergent compositions containing anionic surfactant granules
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
WO2011061045A1 (fr) 2009-11-20 2011-05-26 Unilever Nv Granulé de détergent et son procédé de fabrication
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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ZA72295B (en) * 1971-02-01 1973-09-26 Colgate Palmolive Co Method for neutralization of detergent acid
JPS6187657A (ja) * 1984-10-05 1986-05-06 Kao Corp α−スルホ脂肪酸エステル塩の製造法
US4734224A (en) * 1986-09-15 1988-03-29 The Dial Corporation Dry neutralization process for detergent slurries
GB2209172A (en) * 1987-08-28 1989-05-04 Unilever Plc Preparation of solid particulate components for detergents
IN170991B (fr) * 1988-07-21 1992-06-27 Lever Hindustan Ltd
GB8818613D0 (en) * 1988-08-05 1988-09-07 Paterson Zochonis Uk Ltd Detergents

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DE102005005499A1 (de) * 2005-02-04 2006-08-17 Henkel Kgaa Verfahren zur Herstellung von Wasch- oder Reinigungsmitteln

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CN1087945A (zh) 1994-06-15
DE4232874A1 (de) 1994-03-31
ES2140467T3 (es) 2000-03-01
WO1994007990A1 (fr) 1994-04-14
EP0663005A1 (fr) 1995-07-19
ATE187200T1 (de) 1999-12-15
DE59309891D1 (de) 2000-01-05

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