WO2000031225A1 - Granulats antimoussants contenant du dialkylether - Google Patents

Granulats antimoussants contenant du dialkylether Download PDF

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Publication number
WO2000031225A1
WO2000031225A1 PCT/EP1999/008832 EP9908832W WO0031225A1 WO 2000031225 A1 WO2000031225 A1 WO 2000031225A1 EP 9908832 W EP9908832 W EP 9908832W WO 0031225 A1 WO0031225 A1 WO 0031225A1
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WO
WIPO (PCT)
Prior art keywords
weight
defoamer
silicones
contain
carrier materials
Prior art date
Application number
PCT/EP1999/008832
Other languages
German (de)
English (en)
Inventor
Karl-Heinz Schmid
Detlev Stanislowski
Original Assignee
Cognis Deutschland Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cognis Deutschland Gmbh filed Critical Cognis Deutschland Gmbh
Publication of WO2000031225A1 publication Critical patent/WO2000031225A1/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
    • C11D3/16—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/02—Foam dispersion or prevention
    • B01D19/04—Foam dispersion or prevention by addition of chemical substances
    • B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
    • 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
    • C11D3/2068—Ethers

Definitions

  • the present invention relates to defoamer granules containing ether and processes for producing such defoamer granules by means of simultaneous granulation and drying, in particular according to the SKET method, or in a thin-film evaporator or in a fluidized bed process, and 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 components are mixed in liquid form with the starch 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.
  • the silicones Because of their viscosity and their sticky, oily consistency, the silicones show problems with pumpability on the one hand, and stringing and sticking in the spray nozzle on the other, which means that the desired, finely divided spraying is hardly possible. Furthermore, the silicones are relatively expensive defoamers, so that there continues to be a need to at least partially replace the silicones with other defoaming substances with a comparable defoaming effect.
  • the object of the present invention was to provide defoamer granules which are free-flowing and non-dusting. 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 dialkyl ethers of the formula (I),
  • R 1 and R 2 independently of one another represent a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms, as defoamers.
  • dialkyl ethers of the formula (I) in which R 1 and R 2 independently of one another represent a linear or branched alkyl and / or alkenyl radical having 8 to 18 and in particular 12 to 18 carbon atoms.
  • the ethers can be constructed asymmetrically, but preferably symmetrically. Typical examples are di-n-octyl ether, di-i-octyl ether and di-n-stearyl ether; dialkyl ethers which have a melting point above 25 ° C., in particular above 40 ° C., are particularly suitable.
  • the ethers 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 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.
  • Methyl hydroxypropyl cellulose, methyl hydroxybutyl cellulose and anionic carboxy cellulose types such as the carboxymethyl cellulose sodium salt (abbreviation CMC).
  • 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 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 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.
  • Single or more of the above-mentioned compounds can be used as carrier materials, in particular selected from the group of alkali metal carbonates.
  • Mixtures of alkali carbonates, in particular sodium carbonate, alkali silicates, in particular sodium silicate, alkali sulfates, in particular sodium sulfate are particularly suitable.
  • the carrier materials can be composed as follows:
  • alkali silicate 0 to 30% by weight alkali silicate
  • 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. are understood as "wax-like" (Room temperature), preferably above 50 ° C and in particular above 70 ° C.
  • 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% by weight in 100 g of water.
  • 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.
  • Suitable esters of polyvalent alcohols include xylitol monopalmitate, Pentarythritmonostearat, glycerol, ethylene glycol and sorbitan monostearate, sorbitan, sorbitan Sorbitandilaurat, sorbitan, sorbitan dioleate, and also 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 (CH 2 ) 24COO (CH2) 27CH3 and CH 3 (CH 2 ) 26COO (CH 2 ) 25CH3, and carnauba wax, which is a mixture of alkylamate of camauba, often in combination with small amounts 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.
  • 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 dialkyl ethers of the formula (I) with simultaneous drying and granulation.
  • the way of preparing the aqueous emulsions of the silicones has already been described.
  • the preliminary products can be manufactured in various ways, depending on whether the Intermediates 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 ethers 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.
  • these are the cellulose ethers mentioned, homo- 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 liquid or melted ethers and any further melted 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.
  • solid precursors can be produced by simultaneous granulation and drying of an aqueous solution or slurry of carrier materials, dialkyl ethers 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 intermediate.
  • 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 passage 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 is preferably used simultaneously with the aqueous silicone emulsions, but separately from them Pre-product from the carrier material ether and possibly further wax-like defoamer substances 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 the weight compositions already given 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.
  • the simultaneous drying and granulation takes place in the fluidized bed above a circular inflow floor provided with through-openings for the drying air, the product to be dried remaining stationary above the inflow floor during this drying phase, so that a build-up granulation takes place.
  • Fluidized bed apparatuses which are preferably used have circular base plates (inflow base) with a diameter between 0.4 and 5 m, for example 1J 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.
  • classifier air drying air
  • 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 fluidizing air cools down through heat losses and through 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 0J 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 preferably 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, in granules over 5 mm as oversize fraction and into granules under 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 while drying and granulating at the same time in a fluidized bed above a rectangular inflow surface provided with through-openings for the drying air, the product to be dried preferably being conveyed pneumatically 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 conveyed, 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 precursor are introduced analogously to the SKET process already described, i.e. 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” to create a pipe that spans multiple zones can be tempered at different temperatures.
  • the preliminary product is metered in via one or more shafts, which are provided with blades or shares of flies as rotating internals, sprayed with the aqueous silicone emulsion sprayed in via one or more nozzles and flung against the heated wall, on which the drying takes place in a thin layer of typically 1 to 10 mm thickness.
  • the preliminary products are metered in via a pump.
  • 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 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 are Can be used both in spray-dried, in granulated and in chunky detergents, ie 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 0J 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, 10J% by weight of corn starch, 3J% by weight of sodium silicate, 21.2% by weight of sodium sulfate, 38.1% by weight .-% zeolite, 3.3 wt .-% polyacryl / methacrylate and 11.5 wt .-% distearyl ether and 3J wt .-% bis-stearylethylenediamide 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.
  • 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 to this powdery precursor 350 kg per hour of that prepared according to Example 4
  • SKET system fluidized bed apparatus
  • 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 and 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 100 wt .-% sodium sulfate and water incorporated.
  • the detergents obtained had perfect foaming behavior both at 30 ° C. and at 40 ° C., 60 ° C. and 95 ° C.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Dispersion Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne des granulats antimoussants contenant de la silicone et du dialkyléther, ainsi qu'un procédé permettant de produire de tels granulats antimoussants par granulation et séchage simultanés en particulier selon le procédé SKET, ou bien dans un vaporisateur à couche mince ou bien selon le procédé à lit fluidisé. L'invention concerne également l'utilisation des granulats antimoussants pour la production de produits de lavage solides.
PCT/EP1999/008832 1998-11-26 1999-11-17 Granulats antimoussants contenant du dialkylether WO2000031225A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19854531.2 1998-11-26
DE1998154531 DE19854531A1 (de) 1998-11-26 1998-11-26 Entschäumergranulate mit Ether

Publications (1)

Publication Number Publication Date
WO2000031225A1 true WO2000031225A1 (fr) 2000-06-02

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PCT/EP1999/008832 WO2000031225A1 (fr) 1998-11-26 1999-11-17 Granulats antimoussants contenant du dialkylether

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WO (1) WO2000031225A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3067463A1 (fr) 2015-03-10 2016-09-14 Sasol Wax GmbH Dispersion de cire à base d'eau comprenant une cire hydrocarbure et une dialkyléther pour le revêtement de produits de papier

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993000144A1 (fr) * 1991-06-26 1993-01-07 Henkel Kommanditgesellschaft Auf Aktien Agents anti-moussants
DE4127323A1 (de) * 1991-08-20 1993-02-25 Henkel Kgaa Verfahren zur herstellung von tensidgranulaten
DE4325881A1 (de) * 1993-08-02 1995-02-09 Henkel Kgaa Schaumregulatorgranulat und Verfahren zu seiner Herstellung
DE19534371C1 (de) * 1995-09-15 1997-02-20 Henkel Kgaa Verfahren zur Herstellung wasser- und staubfreier Zuckertensidgranulate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993000144A1 (fr) * 1991-06-26 1993-01-07 Henkel Kommanditgesellschaft Auf Aktien Agents anti-moussants
DE4127323A1 (de) * 1991-08-20 1993-02-25 Henkel Kgaa Verfahren zur herstellung von tensidgranulaten
EP0603207A1 (fr) * 1991-08-20 1994-06-29 Henkel Kgaa Procede de fabrication de granulats tensioactifs.
DE4325881A1 (de) * 1993-08-02 1995-02-09 Henkel Kgaa Schaumregulatorgranulat und Verfahren zu seiner Herstellung
DE19534371C1 (de) * 1995-09-15 1997-02-20 Henkel Kgaa Verfahren zur Herstellung wasser- und staubfreier Zuckertensidgranulate

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