WO2000027962A1 - Granulats antimoussants contenant des cetones - Google Patents

Granulats antimoussants contenant des cetones Download PDF

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Publication number
WO2000027962A1
WO2000027962A1 PCT/EP1999/008290 EP9908290W WO0027962A1 WO 2000027962 A1 WO2000027962 A1 WO 2000027962A1 EP 9908290 W EP9908290 W EP 9908290W WO 0027962 A1 WO0027962 A1 WO 0027962A1
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WIPO (PCT)
Prior art keywords
weight
defoamer
silicones
contain
carrier materials
Prior art date
Application number
PCT/EP1999/008290
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German (de)
English (en)
Inventor
Karl-Heinz Schmid
Detlev Stanislowski
Andrea Bornträger
Michael Neuss
Original Assignee
Cognis Deutschland Gmbh
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Application filed by Cognis Deutschland Gmbh filed Critical Cognis Deutschland Gmbh
Priority to EP99955926A priority Critical patent/EP1129162A1/fr
Publication of WO2000027962A1 publication Critical patent/WO2000027962A1/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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2072—Aldehydes-ketones
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones

Definitions

  • the present invention relates to defoamer granules containing ketones and to processes for producing such defoamer granules by means of simultaneous granulation and drying, in particular by the SKET process, or in a thin-film evaporator or in a fluidized bed process, and to the use of the defoamer granules for the production of solid detergents.
  • Household and industrial laundry detergents generally contain organic surfactants, builders and numerous organic and inorganic additives.
  • the surfactants used to clean the laundry usually tend to develop foam during the washing cycle, which has a negative effect on the washing result. There is therefore a practical need to control the foam development during the washing process and in particular to minimize it.
  • defoamers or so-called anti-foaming agents are used, which on the one hand are intended to reduce the development of foam and on the other hand to reduce foam that has already formed.
  • Silicones have proven to be particularly suitable defoamers, as a rule applied to carrier materials and optionally coated with other defoaming substances and used in solid detergents.
  • defoamers containing silicone are known from European patent application EP-AI-0 496 510, a mixture of silicones and fatty alcohols, fatty acids or glycerol monoesters with special melting points being applied to starch as the carrier material.
  • EP-AI-0 496 510 a mixture of silicones and fatty alcohols, fatty acids or glycerol monoesters with special melting points being applied to starch as the carrier material.
  • the silicones and the other organic constituents are mixed with the starch in liquid form or granulated in a fluidized bed process. Spraying the silicones and the organic materials onto the carrier during the granulation proves problematic according to this method. Because of their viscosity and sticky, oily consistency, the silicones on the one hand show problems with pumpability and on the other hand Stringing and sticking in the spray nozzle, making the desired finely divided spraying hardly possible.
  • the silicones are relatively expensive defoamers, so that there continues to be a need to at least partially replace the silicones with
  • the object of the present invention was to provide defoamer granules which are free-flowing and do not dust. Furthermore, the defoamer granules should have a good defoaming effect, the silicones being at least partially replaced by other defoaming compounds. Of course, the silicones and the other defoaming compounds had to be compatible with one another and, if possible, have the maximum defoaming effect at different temperatures. Furthermore, a process had to be developed which made it possible to produce defoamer granules with silicones without the disadvantages known from the prior art, such as thread tension and sticking in the spray nozzle, being introduced when the silicones were introduced.
  • One object of the present invention relates to defoamer granules for solid detergents containing silicones as defoamers and carrier materials, characterized in that they additionally contain fatty ketones of the formula (I),
  • R and R independently of one another represent linear or branched hydrocarbon radicals having 11 to 25 carbon atoms and 0 or 1 double bond, as defoamers.
  • ketones of the general formula (I) are known substances that can be obtained by the relevant methods of preparative organic chemistry.
  • carboxylic acid magnesium salts are used to prepare them. which are pyrolyzed at temperatures above 300 ° C with elimination of CC and water, for example according to the German
  • Suitable fatty ketones are those obtained by pyrolysis of the magnesium salts of lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, Oleic acid, elaidic acid, petroselinic acid, arachic acid, gadoleic acid, behenic acid or erucic acid can be produced.
  • fatty ketones of the formula (I) preference is given to fatty ketones of the formula (I) in which R and R represent alkyl radicals having 15 to 21 carbon atoms.
  • the defoamer granules according to the invention particularly preferably contain palmitone (hentriacontanone-16; R 3 and R 4 stands for an alkyl radical with 15 carbon atoms), tritriacontanone-17 (R 3 and R 4 stands for an alkyl radical with 16 carbon atoms), stearone (pentatriacontanone-18; R 3 and R 4 represents an alkyl radical with 17 carbon atoms) heptatriacontanone-19 (R 3 and R 4 stands for an alkyl radical with 18 carbon atoms), arachinone (nonatriacontanone-20; R 3 and R 4 stands for an alkyl radical with 19 carbon atoms), Hentetracontanone-21 (R 3 and R 4 stands for an alkyl radical with 20 carbon atoms) and
  • ketones are preferably contained in the defoamer granules according to the invention in amounts of 3 to 30% by weight, in particular 5 to 20% by weight, based on defoamer granules.
  • the defoamer granules according to the invention further contain silicones.
  • suitable silicones are conventional organopolysiloxanes which can have a content of finely divided silica, which in turn can also be silanated.
  • organopolysiloxanes are described, for example, in European patent application EP-A1-0 496 510.
  • Polydiorganosiloxanes which are known from the prior art are particularly preferred.
  • Suitable polydiorganosiloxanes can have an almost linear chain and are identified by the following formula (II),
  • R can independently represent an alkyl or an aryl radical and n can stand for numbers in the range from 40 to 1500.
  • suitable substituents R are methyl, ethyl, propyl, isobutyl, tert. Butyl and phenyl.
  • siloxane compounds crosslinked via siloxane can also be used, as are known to the person skilled in the art under the name silicone resins.
  • the polydiorganosiloxanes contain finely divided silica, which can also be silanized.
  • Silicic acid-containing dimethylpolysiloxanes are particularly suitable for the purposes of the present invention.
  • the polydiorganosiloxanes advantageously have a Brookfield viscosity at 25 ° C. in the range from 5000 mPas to 30,000 mPas, in particular from 15,000 to 25,000 mPas.
  • the silicones are preferably used to produce the defoamer granules according to the invention in the form of their aqueous emulsions.
  • the aqueous emulsions are produced by stirring the silicones into the water provided.
  • so-called thickeners can be added to increase the viscosity of the aqueous silicone emulsions.
  • the thickeners can be inorganic and / or organic in nature.
  • Nonionic cellulose ethers such as methyl cellulose, ethyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl hydroxybutyl cellulose and anionic carboxy cellulose types such as the carboxymethyl cellulose sodium salt (abbreviation CMC) are particularly preferred as thickeners.
  • Particularly suitable thickeners are mixtures of CMC to nonionic cellulose ethers in a weight ratio of 80:20 to 40:60, in particular 75:25 to 60:40.
  • concentrations of approximately 0.5 to 10, in particular 2.0 to 6,% by weight, calculated as a thickener mixture and based on aqueous silicone emulsion, are recommended.
  • the content of silicones of the type described in the aqueous emulsions is advantageously in the range from 5 to 50% by weight, in particular from 15 to 35% by weight, calculated as silicones and based on the aqueous silicone emulsion.
  • the aqueous silicone solutions contain starch as a thickener, which is accessible from natural sources, for example from rice, potatoes, corn and wheat.
  • the starch is advantageously present in amounts of 0.1 to 50% by weight, based on the silicone emulsion, and in particular in a mixture with the already described thickener mixtures of sodium carboxymethyl cellulose and a nonionic cellulose ether in the amounts already mentioned.
  • the procedure is expediently such that the thickeners which may be present are allowed to swell in water before the silicones are added.
  • the silicones are expediently incorporated using effective stirring and mixing devices.
  • the defoamer granules according to the invention generally contain 0.5 to 30% by weight, preferably 5 to 20% by weight, of silicones of the type already described.
  • the defoamer granules according to the invention contain carrier materials for the silicones as a further constituent.
  • carrier materials for the silicones as a further constituent.
  • all known inorganic and / or organic carrier materials can be used as carrier materials.
  • typical inorganic carrier materials are alkali carbonates, aluminosilicates, water-soluble sheet silicates, alkali silicates, alkali sulfates, for example sodium sulfate and alkali phosphates.
  • the alkali silicates are preferably a compound with a molar ratio of alkali oxide to SiO " 2 of 1: 1.5 to 1:
  • the use of such silicates results in particularly good grain properties, in particular high abrasion stability and nevertheless high dissolution rate in water.
  • the aluminosilicates referred to as carrier material include, in particular, the zeolites, for example zeolite NaA and NaX.
  • the compounds referred to as water-soluble layered silicates include, for example, amorphous or crystalline water glass.
  • suitable organic carrier materials are film-forming polymers, for example polyvinyl alcohols, polyvinyl pyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and starch.
  • Usable cellulose ethers are, in particular, alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and so-called cellulose mixed ethers, such as, for example, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose, and mixtures thereof.
  • Particularly suitable mixtures are composed of sodium carboxymethyl cellulose and methyl cellulose, the carboxymethyl cellulose usually having a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methyl cellulose having a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit.
  • the mixtures preferably contain alkali carboxymethyl cellulose and nonionic cellulose ethers in weight ratios of from 80:20 to 40:60, in particular from 75:25 to 50:50.
  • Such cellulose ether mixtures can be used in solid form or as aqueous solutions which are pre-swollen in the customary manner can.
  • the native starch which is composed of amylose and amylopectin is particularly preferred as the carrier.
  • Starch is referred to as native starch as it is available as an extract from natural sources, for example from rice, potatoes, corn and wheat.
  • Native starch is a commercially available product and is therefore easily accessible.
  • Carrier materials which can be used are one or more of the abovementioned compounds, in particular selected from the group of alkali metal carbonates, alkali metal sulfates, alkali metal phosphates, zeolites, water-soluble sheet silicates, alkali metal silicates, polycarboxylates, cellulose ethers, polyacrylate / polymethacrylate and starch.
  • alkali carbonates in particular sodium carbonate
  • alkali silicates in particular sodium silicate
  • alkali sulfates in particular sodium sulfate
  • zeolites zeolites
  • polycarboxylates in particular poly (meth) acrylate
  • cellulose ether and native starch are particularly suitable.
  • the carrier materials can be composed as follows:
  • alkali silicate 0 to 30% by weight alkali silicate
  • alkali sulfate 0 to 75% by weight alkali sulfate
  • polycarboxylates 0 to 5% by weight of polycarboxylates, the sum having to add up to 100% by weight.
  • the carrier materials are generally present in amounts of 40 to 90% by weight, preferably in amounts of 45 to 75% by weight, based on the defoamer granulate.
  • the defoamer granules according to the invention can contain further water-insoluble wax-like defoamer substances.
  • Compounds which have a melting point at atmospheric pressure above 25 ° C. (room temperature), preferably above 50 ° C. and in particular above 70 ° C. are understood as “wax-like”.
  • the wax-like defoamer substances which may be present according to the invention are practically insoluble in water, ie at 20 ° C they have a solubility of less than 0.1% by weight in 100 g of water.
  • wax-like defoamer substances known from the prior art can additionally be contained.
  • Suitable waxy compounds are, for example, bisamides, fatty alcohols, fatty acids, carboxylic acid esters of mono- and polyhydric alcohols, and paraffin waxes or mixtures thereof.
  • Bisamides are suitable which are derived from saturated fatty acids with 12 to 22, preferably 14 to 18, carbon atoms and from alkylenediamines with 2 to 7 carbon atoms.
  • Suitable fatty acids are lauric acid, myristic acid, stearic acid, arachic acid and behenic acid and mixtures thereof, as can be obtained from natural fats or hydrogenated oils, such as tallow or hydrogenated palm oil.
  • diamines are ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine.
  • Preferred diamines are ethylenediamine and hexamethylenediamine.
  • Particularly preferred bisamides are bis-myristoyl-ethylenediamine, bis-palmitoyl-ethylenediamine, bis-stearoylethylenediamine and mixtures thereof, and the corresponding derivatives of hexamethylenediamine.
  • Suitable carboxylic acid esters are derived from carboxylic acids with 12 to 28 carbon atoms. In particular, these are esters of behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid and / or lauric acid.
  • the alcohol part of the carboxylic acid ester contains a mono- or polyhydric alcohol with 1 to 28 carbon atoms in the hydrocarbon chain.
  • suitable alcohols are behenyl alcohol, arachidyl alcohol, coconut alcohol, 12-hydroxystearyl alcohol, oleyl alcohol and lauryl alcohol as well as ethylene glycol, glycerin, polyvinyl alcohol, sucrose, erythritol, pentaerythritol, sorbitan and / or sorbitol.
  • Preferred esters are those of ethylene glycol, glycerol and sorbitan, the acid part of the ester being selected in particular from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.
  • Suitable esters of polyvalent alcohols include xylitol monopalmitate, penta rythritmonostearat, glycerol, ethylene glycol and sorbitan, sorbitan, sorbitan Sorbitandilaurat, sorbitan, sorbitan dibehenate, sorting bitandioleat and mixed tallowalkyl and diesters.
  • Glycerol esters which can be used are the mono-, di- or triesters of glycerol and the carboxylic acids mentioned, the mono- or diesters being preferred.
  • Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glycerol distearate are examples of this.
  • esters examples include beeswax, which mainly consists of the esters CH 3 (CH2) 24COO (CH 2 ) 27CH3 and ⁇ (C ⁇ COO ⁇ C ⁇ , and carnauba wax, which is a mixture of carnaubaic acid alkyl esters, often in combination with small proportions of free carnauba acid, other long-chain acids, high-molecular alcohols and hydrocarbons.
  • Suitable carboxylic acids as a further defoamer compound are, in particular, behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid and lauric acid and mixtures thereof, as can be obtained from natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil. Saturated fatty acids with 12 to 22, in particular 18 to 22, carbon atoms are preferred. Suitable fatty alcohols as a further defoamer compound are the hydrogenated products of the fatty acids described.
  • Suitable paraffin waxes as a further defoamer compound generally represent a complex mixture of substances without a sharp melting point. For characterization, its melting range is usually determined by differential thermal analysis (DTA), as described in "The Analyst” 87 (1962), 420, and / or its freezing point. This is the temperature at which the paraffin changes from the liquid to the solid state by slow cooling. Paraffins which are completely liquid at room temperature, that is to say those having a solidification point below 25 ° C., cannot be used according to the invention. For example, the paraffin wax mixtures known from EP 309 931 of, for example, 26% by weight to 49% by weight of microcrystalline paraffin wax with a solidification point of 62 ° C.
  • paraffin waxes which can be used according to the invention, this liquid fraction is as low as possible and is preferably absent entirely.
  • Particularly preferred paraffin wax mixtures at 30 ° C have a liquid content of less than 10% by weight, in particular from 2% by weight to 5% by weight, at 40 ° C a liquid content of less than 30% by weight, preferably 5 % By weight to 25% by weight and in particular from 5% by weight> to 15% by weight, at 60 ° C. a liquid fraction of 30% by weight to 60% by weight, in particular 40% by weight. -% to 55% by weight, at 80 ° C a liquid content of 80% by weight to 100% by weight>, and at 90 ° C a liquid content of 10% by weight.
  • the temperature at which a liquid content of 100% by weight of the paraffin wax is reached is still below 85 ° C. in particularly preferred paraffin wax mixtures, in particular at 75 ° C. to 82 ° C.
  • the further additional water-insoluble wax-like defoamers of the type described are present in amounts of 0 to 30% by weight, preferably 5 to 25% by weight, based on the defoamer granules.
  • Another object of the present invention relates to a process for the preparation of defoamer granules according to claim 1, characterized in that the silicones are sprayed in the form of aqueous emulsions onto a precursor from carrier materials and fat ketones of the formula (I) with simultaneous drying and granulation.
  • the process according to the invention is based on spraying the silicones in the form of aqueous emulsions onto an admixed precursor composed of carrier materials and ketones and, if appropriate, other wax-like defoamer substances which are insoluble in water, and a defoamer granulate is obtained with simultaneous drying and granulation.
  • the way of preparing the aqueous emulsions of the silicones has already been described.
  • the preliminary products can be prepared in various ways, depending on whether the preliminary products are used as a solid or as an aqueous solution or aqueous slurry.
  • the procedure is generally such that the carrier material is dissolved or slurried in water and the ketones and any wax-like defoamer substances present are dispersed therein.
  • a water-soluble, non-surfactant dispersion stabilizer in the form of a water-swellable polymer can be added to the dispersion.
  • examples include the cellulose ethers mentioned, homopolymers and copolymers of unsaturated carboxylic acids, such as acrylic acid, maleic acid and copolymerizable vinyl compounds, such as vinyl ether, acrylamide and ethylene.
  • aqueous slurry preferably not more than 5% by weight, in particular 1% by weight to 3% by weight, based on the resulting precursor.
  • the water content of the slurry can be 30% by weight to 60% by weight.
  • Such aqueous solutions or slurries of the preliminary products are injected via nozzles for the production of the defoamer granules.
  • the precursors as a solid.
  • Such solid precursors can be produced by various processes.
  • the carrier material is usually first prepared by spray drying an aqueous slurry of the carrier materials.
  • the molten ketones and any further molten wax-like defoamer substances, if any, are applied to the spray-dried, granular carrier materials, for example by successive mixing, in particular in the form of a spray.
  • the carrier material is preferably kept in motion by mixing elements or by fluidization in order to ensure a uniform loading of the carrier material.
  • the spray mixers used for this can be operated continuously or discontinuously.
  • the solid precursor is produced by spray drying an aqueous solution or slurry of carrier materials, ketones and any other wax-like defoamer substances that may be present.
  • the starting point is aqueous solutions or slurries which have already been described above in connection with the liquid precursors.
  • Spray drying of the same can be carried out in a known manner in systems provided for this purpose, so-called spray towers, using hot drying gases conducted in cocurrent or countercurrent. Drying by drying gases carried in cocurrent with the spray material is preferred, since the loss of activity due to the potential hot air volatility of some constituents of the paraffin can be reduced to a minimum, particularly in the case of paraffin-containing preliminary products.
  • solid precursors can be produced by simultaneous granulation and drying of an aqueous solution or slurry of carrier materials, ketones and any other wax-like defoamer substances which have already been described in connection with the liquid precursors.
  • the simultaneous drying and granulation is preferably carried out in the fluidized bed by the SKET process, for example in accordance with European Patent EP-B-603 207 or by the fluidized bed process, which will be explained in more detail below.
  • the defoamer granules are produced by granulation and simultaneous drying.
  • the aqueous silicone emulsions are sprayed onto the mixed solid precursor.
  • the aqueous silicone emulsions and the aqueous solutions or slurries of the preliminary products can be injected independently of one another.
  • the defoamer granules are preferably produced by spraying the silicone emulsion onto the solid preliminary product with simultaneous drying and granulation in a fluidized bed.
  • the granulation and simultaneous drying take place in a fluidized bed above a circular inflow floor provided with through-openings for the drying air, preferably according to the so-called SKET process.
  • the aqueous silicone emulsions are introduced into the fluidized bed via one or more nozzles.
  • the solid intermediate product from the carrier material, ketones and, if appropriate, further wax-like defoamer substances are mixed in, preferably via an automatically controlled solids metering.
  • the product streams of aqueous silicone emulsions and admixed preliminary product are controlled so that defoamer granules of those already mentioned Weight compositions result.
  • the aqueous silicone emulsion meets the mixed preliminary products with simultaneous evaporation of the water, whereby dried to dried germs are formed, which are coated with further introduced aqueous silicone emulsions or with the mixed preliminary products, granulated and again dried at the same time.
  • a particular advantage of the process is that the defoamer granules that are produced are classified or classified by the incoming drying air with regard to their particle size and thus also with regard to their weight, so that those granules which have reached the desired particle size or weight fall out of the fluidized bed the fluidized bed in a discharge lock.
  • Fluidized bed apparatuses which are preferably used have circular base plates (inflow base) with a diameter between 0.4 and 5 m, for example 1.2 m or 2.5 m.
  • Perforated floor slabs a Contidur slab (commercial product from Hein & Lehmann, Federal Republic of Germany) or perforated floor slabs can be used as the floor slab, the holes (passage openings) of which are covered by a grid with mesh sizes of less than 600 ⁇ m.
  • the grid can be arranged inside or above the passage openings. However, the grid preferably lies directly below the passage openings of the inflow floor. This is advantageously realized in such a way that a metal gauze with the appropriate mesh size is sintered on.
  • the metal gauze preferably consists of the same material as the inflow floor, in particular of stainless steel.
  • the mesh size of said grid is preferably between 200 and 400 ⁇ m.
  • the process is preferably carried out at swirl air speeds between 1 and 8 m / s and in particular between 1.5 and 5.5 m / s.
  • the granules are advantageously discharged via a size classification of the granules. This classification is preferably carried out by means of an opposite flow of drying air (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.
  • the vortex air cools down due to heat losses and the heat of vaporization and is preferably about 5 cm above the base plate 60 to 120 ° C, preferably 65 to 90 and in particular 70 to 85 ° C.
  • the air outlet temperature is preferably between 60 and 120 ° C, in particular below 80 ° C.
  • the residence time for the product to be dried, which remains stationary above the inflow floor, is preferably in the range from 5 to 60 minutes.
  • a starting mass is present at the beginning of the process, which serves as the initial carrier for the sprayed-in aqueous silicone emulsion.
  • Suitable starting materials are the admixed preliminary products or, in particular, the defoamer granules themselves, which have already been obtained in a previous process.
  • defoamer granules which have been ground over a roller mill preferably with a grain size in the range above 0.01 and below 0.2 mm, are used as starting mass and are fed in via a solids metering.
  • the defoamer granules obtained from the SKET fluidized bed are then subsequently cooled in a separate fluidized bed and classified by means of a sieve into granules with particle sizes between 0.9 and 5 mm as good grain fraction, into granules over 5 mm as oversize fraction and into granules below 0.9 mm as undersize fraction.
  • the granules of the undersize fraction are returned to the fluidized bed.
  • the oversize fraction is ground, preferably in particle sizes greater than 0.01 and less than 0.02 mm, and also returned to the fluidized bed.
  • the defoamer granules can be produced by the so-called fluid bed process.
  • the aqueous silicone emulsion is sprayed onto the preferably solid preliminary product with simultaneous drying and granulation in a fluidized bed above a rectangular inflow surface provided with through-openings for the drying air, the product to be dried preferably being pneumatically conveyed continuously during the drying phase.
  • Suitable devices for the fluidized bed process are offered, for example, by Sulzer, Heinen, Gea or Babcock in the market.
  • the dimensions of the inflow floor are not critical. Preferred inflow floors are approximately 1 m wide and 3 m long.
  • the inflowing air temperature is preferably between 80 ° C and 400 ° C.
  • the inflowing amount of air is preferably in the range from 10,000 to 100,000 m 3 / h, in particular about 15,000 to 50,000 m 3 / h.
  • the residence time for the product to be dried, which is continuously being used, is preferably in the range from 1 to 30 minutes, in particular in the range from 1 to 15 minutes.
  • the aqueous silicone emulsions and the preferably solid preliminary product are introduced analogously to the SKET process already described, ie the silicone emulsions are introduced via one or more nozzles and into the fluidized bed and the solid preliminary product is preferably introduced via an automatically controlled solids metering .
  • the product flows of aqueous silicone emulsions and admixed preliminary product are controlled analogously to the SKET fluidized bed.
  • the aqueous silicone emulsion meets the mixed preliminary products with simultaneous evaporation of the water, whereby dried to dried germs are formed, which are coated with further introduced aqueous silicone emulsions or with the mixed preliminary products, granulated and again dried at the same time.
  • the simultaneous drying and granulation takes place in a preferably horizontally arranged thin-film evaporator with rotating internals, as is sold, for example, by VRV under the name "Flashdryer” , around a pipe that can be heated to different temperatures across several zones
  • the primary product is metered in via one or more shafts, which are provided with blades or shares of flies as rotating internals, and sprayed with the aqueous silicone emulsion sprayed through one or more nozzles and hurled against the heated wall, on which the drying takes place in a thin layer, typically 1 to 10 mm thick.
  • the preliminary products are used as a slurry, metering is carried out by means of a pump.
  • a temperature gradient from 170 ° C (product inlet) to 20 ° C (product discharge) on the thin film evaporator.
  • the first two zones of the evaporator can be heated to 160 ° C and the last can be cooled to 20 ° C.
  • the thin film evaporator is operated at atmospheric pressure and gassed in countercurrent with air (throughput 50 to 150 m 3 / h).
  • the inlet temperature of the gas is usually 20 to 30 ° C, the outlet temperature 90 to 110 ° C.
  • the throughput is of course dependent on the size of the dryer, but is typically 5 to 15 kg / h. It is advisable to temper the aqueous slurry of the preliminary product (slurry) to 40 to 60 ° C. during the feed. Furthermore, it is particularly advantageous to temper the aqueous silicone emulsions to 45 to 65 ° C.
  • the product streams of aqueous silicone emulsions and metered in preliminary product are controlled in such a way that defoamer granules with the proportions already given result.
  • the granules After drying, it has also proven to be very advantageous to place the granules, which are still about 50 to 70 ° C., on a conveyor belt, preferably an oscillating shaft, and there quickly, ie cool within a dwell time of 20 to 60 s with ambient air to temperatures of around 30 to 40 ° C.
  • the granules can also subsequently be powdered by adding 0.5 to 2% by weight of silica.
  • the defoamer granules are regarded as dried if the free water content is below 10% by weight, preferably from 0.1 to 2% by weight, based in each case on the finished granules.
  • the defoamer granules produced by the processes according to the invention are easy-flowing products which do not dust. They show a good defoaming effect and can be used in spray-dried, in granulated as well as in lumpy detergents, i.e. also in detergent tablets.
  • Another object of the present invention relates to the use of the defoamer granules according to the invention for the production of solid detergents.
  • the defoamer granules can be present in amounts of 0.2 to 7.0% by weight, preferably in amounts of 0.5 to 4.0% by weight, based on the detergent.
  • the detergents can contain customary anionic, nonionic or cationic surfactants, as well as other customary constituents in customary amounts.
  • the detergents can contain softening agents such as tripolyphosphate or zeolite, as well as bleaching agents such as perborate or percarbonate in customary amounts as usual components.
  • the defoamer granules can easily be mixed in.
  • Granules having the following composition were obtained: 7% by weight of silicone, 2.1% by weight of cellulose ether, 10.3% by weight of corn starch, 3.2% by weight of sodium silicate, 21.2% by weight of sodium sulfate, 38.1% by weight of zeolite, 3.3% by weight of polyacrylic / methacrylate and 11.5% by weight of stearone and 3.3% by weight of bis-stearylethylenediamide with a bulk density of 780 g / 1 and a particle size distribution of 0.2 to 1.2 mm.
  • the product showed very good flow properties and had no dust content.
  • Example 5 650 kg per hour of the powdery precursor produced according to Example 1 were continuously fed into the fluidized bed apparatus (SKET system) at a drying air flow rate of approx. 20,000 m 3 air / h at a temperature of 100 ° C. via a solids metering and continuously sprayed 350 kg per hour of the aqueous silicone emulsion prepared according to Example 4 onto this powdery precursor.
  • the temperature in the fluidized bed above the fluidized bed was 65 ° C, the exhaust air 60 ° C.
  • Granules having the following composition were obtained: 7% by weight of silicone, 2.2% by weight of cellulose ether, 9.2% by weight of sodium silicate, 38.0% by weight of sodium sulfate, 29.1% by weight of sodium carbonate , 3.7 wt .-% polyacrylic / methacrylate, 1 1.0 wt .-% stearone with a bulk density of 780 g / 1 and a grain size distribution of 0.2 to 1.2 mm. The product showed very good flow properties and had no dust content. IV. Application tests
  • the defoamer granules produced were mixed in an amount of 1.5% by weight by simply mixing them into a powdered universal detergent formulation with 8% by weight sodium alkylbenzenesulfonate, 10% by weight alkyl ethoxylate, 1.5% by weight soap, 10% by weight sodium carbonate, 20% by weight zeolite, 3% by weight sodium silicate, 20% by weight sodium perborate, 2% by weight tetraacetylethylenediamine (TAED), 0.5% by weight protease, balance incorporated on 100 wt .-% sodium sulfate and water.
  • the detergents obtained had perfect foaming behavior both at 30 ° C. and at 40 ° C., 60 ° C. and 95 ° C.

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Abstract

La présente invention concerne des granulats antimoussants contenant des cétones, ainsi qu'un procédé de production de tels granulats par granulation et séchage simultanés, en particulier selon le procédé SKET, ou bien dans un vaporisateur à couche mince, ou bien encore selon un procédé à lit fluidifié. La présente invention concerne également l'utilisation de ces granulats antimoussants pour la production de produits de lavage solides.
PCT/EP1999/008290 1998-11-10 1999-10-30 Granulats antimoussants contenant des cetones WO2000027962A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP99955926A EP1129162A1 (fr) 1998-11-10 1999-10-30 Granulats antimoussants contenant des cetones

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1998151742 DE19851742A1 (de) 1998-11-10 1998-11-10 Entschäumergranulate mit Ketonen
DE19851742.4 1998-11-10

Publications (1)

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WO2000027962A1 true WO2000027962A1 (fr) 2000-05-18

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DE (1) DE19851742A1 (fr)
WO (1) WO2000027962A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021047954A1 (fr) 2019-09-11 2021-03-18 Unilever Ip Holdings B.V. Composition détergente

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1467613A1 (de) * 1965-08-20 1969-01-16 Henkel & Cie Gmbh Waschmittel mit geringem Schaumvermoegen
DE2242541A1 (de) * 1972-08-30 1974-03-07 Henkel & Cie Gmbh Schwachschaeumende wasch-, reinigungs- und enthaertungsmittel
EP0324339A2 (fr) * 1988-01-11 1989-07-19 Henkel Kommanditgesellschaft auf Aktien Agent antimousse pour détergents contenant du chlore actif
WO1994012604A1 (fr) * 1992-11-30 1994-06-09 Henkel Kommanditgesellschaft Auf Aktien Agent sans silicone pour la regulation de la mousse
WO1994025137A1 (fr) * 1993-04-28 1994-11-10 Henkel Kommanditgesellschaft Auf Aktien Dispersions aqueuses anti-mousse
WO1997013832A1 (fr) * 1995-10-06 1997-04-17 Unilever N.V. Systeme anti-mousse base sur des polymeres d'hydrocarbure et sur des solides particulaires hydrophobes
WO1997013833A1 (fr) * 1995-10-06 1997-04-17 Unilever N.V. Systeme anti-mousse destine a des compositions de lavage automatique de la vaisselle

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1467613A1 (de) * 1965-08-20 1969-01-16 Henkel & Cie Gmbh Waschmittel mit geringem Schaumvermoegen
DE2242541A1 (de) * 1972-08-30 1974-03-07 Henkel & Cie Gmbh Schwachschaeumende wasch-, reinigungs- und enthaertungsmittel
EP0324339A2 (fr) * 1988-01-11 1989-07-19 Henkel Kommanditgesellschaft auf Aktien Agent antimousse pour détergents contenant du chlore actif
WO1994012604A1 (fr) * 1992-11-30 1994-06-09 Henkel Kommanditgesellschaft Auf Aktien Agent sans silicone pour la regulation de la mousse
WO1994025137A1 (fr) * 1993-04-28 1994-11-10 Henkel Kommanditgesellschaft Auf Aktien Dispersions aqueuses anti-mousse
WO1997013832A1 (fr) * 1995-10-06 1997-04-17 Unilever N.V. Systeme anti-mousse base sur des polymeres d'hydrocarbure et sur des solides particulaires hydrophobes
WO1997013833A1 (fr) * 1995-10-06 1997-04-17 Unilever N.V. Systeme anti-mousse destine a des compositions de lavage automatique de la vaisselle

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021047954A1 (fr) 2019-09-11 2021-03-18 Unilever Ip Holdings B.V. Composition détergente
CN114364774A (zh) * 2019-09-11 2022-04-15 联合利华知识产权控股有限公司 洗涤剂组合物

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DE19851742A1 (de) 2000-05-11

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