WO2000031230A1 - Procede de production de granules tensioactifs - Google Patents

Procede de production de granules tensioactifs Download PDF

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Publication number
WO2000031230A1
WO2000031230A1 PCT/EP1999/008763 EP9908763W WO0031230A1 WO 2000031230 A1 WO2000031230 A1 WO 2000031230A1 EP 9908763 W EP9908763 W EP 9908763W WO 0031230 A1 WO0031230 A1 WO 0031230A1
Authority
WO
WIPO (PCT)
Prior art keywords
aqueous
surfactant
anionic surfactants
granulation
granules
Prior art date
Application number
PCT/EP1999/008763
Other languages
German (de)
English (en)
Inventor
Karl-Heinz Schmid
Christoph Breucker
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
Priority to EP99963299A priority Critical patent/EP1131400B1/fr
Priority to DE59915230T priority patent/DE59915230D1/de
Priority to AT99963299T priority patent/ATE492626T1/de
Publication of WO2000031230A1 publication Critical patent/WO2000031230A1/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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/044—Hydroxides or bases
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads

Definitions

  • the invention relates to a process for the preparation of anionic surfactant granules by means of granulation and simultaneous drying in the fluidized bed, which is carried out in the presence of volatile bases, and to the use thereof for the production of, in particular, pH-neutral detergents, dishwashing detergents and agents for oral hygiene.
  • Anionic surfactants such as alkyl sulfates and alkyl ether sulfates are common surfactants which, due to their high detergency, are widely used in cleaning processes of all kinds. Due to their manufacturing processes, these are usually obtained in salt form as aqueous solutions or pastes, which are converted into their powders or granules, for example, by conventional drying technology, in particular in the spray tower or in granulating devices. At the drying temperatures prevailing there, however, pH-neutral solutions or pastes of the alkyl (ether) sulfates would decompose autocatalytically into the corresponding olefinic base bodies and the corresponding salts of hydrogen sulfate, which themselves act as an acid in aqueous solution.
  • such pastes are equipped with a so-called alkali reserve according to the prior art, ie such pastes are treated with an excess of free hydroxides, in particular sodium hydroxide.
  • the sodium hydroxide is then able to trap the acid that may form through autocatalysis and thus stop the decomposition process.
  • the alkali reserve is added in excess, usually in such amounts that, for example, a fatty alcohol sulfate paste has a pH value above 10, small residual amounts of unused sodium hydroxide always remain in the aqueous solution or paste of the alkyl (ether) sulfates.
  • a process for the preparation of surfactant granules containing anionic surfactants is known from German published patent application DE-Al-43 04 062, which granules are produced from aqueous pastes by means of granulation and simultaneous drying.
  • aqueous pastes of the anionic surfactants in the acid form and an aqueous alkaline solution are separately charged with a gaseous medium (air, nitrogen) and sprayed into the fluidized bed system separately or combined at a high propellant pressure.
  • a gaseous medium air, nitrogen
  • the object of the present invention was accordingly to provide a new process for the preparation of surfactant granules containing anionic surfactants which overcomes the disadvantages of the prior art described.
  • the new process should continue to effectively prevent the autocatalytic decomposition of the anionic surfactants when they dry.
  • the object was achieved if volatile bases were added to the aqueous surfactant pastes containing anionic surfactants (in salt form) before and / or during the granulation and simultaneous drying in the fluidized bed.
  • the invention includes the knowledge that anionic surfactant granules are available with the method according to the invention which contain little or no residual amounts of alkaline substances, so that they do not cause any undesirable interactions with perfumes or dyes. Furthermore, the invention includes the knowledge that through the ubiquitous presence of the volatile bases in the fluidized bed even at the most distant parts of the apparatus, for example in the filter, decomposition of dried anionic surfactants already formed can be effectively reduced under thermal stress and wall caking of the decomposed product can be reduced.
  • One object of the present invention therefore relates to a process for the production of surfactant granules by granulation and simultaneous drying of an aqueous surfactant preparation containing anionic surfactants in the fluidized bed, characterized in that volatile bases are added before or during the granulation and simultaneous drying.
  • aqueous surfactant preparations containing anionic surfactants are used for the process.
  • these are aqueous surfactant preparations that only contain anionic surfactants.
  • These are preferably used in the form of aqueous pastes, in particular with an active substance content of 25 to 90% by weight, based on aqueous anionic surfactant paste.
  • anionic surfactants are fatty alcohol sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates and alkyl oligoglucoside sulfates. If the anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
  • fatty alcohol sulfates and / or fatty alcohol ether sulfates are preferably used as anionic surfactants. Particularly suitable are those which follow the formula (I)
  • R 1 is a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms
  • m is 0 or numbers from 1 to 10
  • X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • Particularly preferred is the use of sulfates based on technical C 12 / ⁇ 4 - or C 12/18 -Alkoholfr hopeen based seed oil on natural oils and fats such as coconut oil, palm oil, tallow or Palstearin or bwz also based on Ziegler alcohols.
  • oxo alcohols in the range from C8 to C15 (or their mixtures of the aforementioned linear alcohols made from natural oils and fats or Ziegleral alcohols with oxo alcohols) in the form of their sodium, potassium and / or magnesium salts.
  • Typical examples of ether sulfates of alcohols ethoxylated with an average of 1 to 10 and in particular 2 to 5 moles of ethylene oxide are selected from the group capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol Isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, in the form of their sodium and / or magnesium salts.
  • the ether sulfates can have both a conventional and a narrow homolog distribution.
  • aqueous surfactant preparations to be used in accordance with the invention can optionally contain further surfactants or also additives, which are preferably ingredients of detergents and cleaning agents.
  • the aqueous surfactant preparations preferably contain nonionic surfactants as further surfactants.
  • Suitable nonionic surfactants are liquid alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 9 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, the underlying alcohols being linear or methyl-branched in the 2-position, or contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • the nonionic surfactants of the type described are derived from linear alcohols of native origin with 12 to 18 carbon atoms, such as coconut, tallow or oleyl alcohol.
  • 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 -C -oxoalcohol with 7 EO, C ljC 15 -oxoalcohol with 3 EO, 5 EO or 7 EO and in particular C 1 -C 1 4 -
  • nonionic surfactants are present in the aqueous surfactant preparations with the anionic surfactants, the amount used can vary widely. As a rule, the nonionic surfactants are present in the aqueous surfactant preparations in amounts of up to 50% by weight, calculated as the active substance and based on the active substance of the surfactants.
  • the aqueous surfactant preparation can contain additives, which are preferably ingredients of detergents and cleaning agents, as further constituents, preferably in amounts of 0.001 to 80% by weight, based on the active substance of the aqueous surfactant preparation.
  • additives are inorganic builder substances such as zeolite, SKS6, sodium carbonate, sodium sulfate, Aerosil and / or organic builder substances such as starch, cellulose, cellulose ether, microcrystalline cellulose and the like.
  • aqueous pastes are preferred as aqueous surfactant preparations which contain exclusively anionic surfactants, in particular fatty alcohol sulfates and / or fatty alcohol ether sulfates in the form of their sodium, potassium and / or magnesium salts.
  • Such pastes are commercially available and currently have an addition of aqueous hydroxides as an alkali reserve.
  • the aqueous hydroxides according to the prior art are usually added in such amounts that, for example, fatty alcohol sulfate pastes (measured as a 1% by weight aqueous solution) have a pH above 10 have.
  • the aqueous hydroxides are added during the production of the fatty alcohol sulfates by means of continuous neutralization.
  • the anionic surfactant pastes have such an amount of alkali reserves that the pH is between 7 and 9.5.
  • Such pH values of the anionic surfactant pastes can be adjusted during the preparation of the sulfates in the neutralization step after sulfonation of the alcohols by adding the calculated amount of hydroxides, in particular sodium hydroxide. This is particularly recommended for highly viscous anionic surfactant pastes, especially those that have active substance contents of 60 to 90% by weight. The same procedure can be followed for low-viscosity anionic surfactant pastes with active substance contents below 30% by weight.
  • low-viscosity anionic surfactant pastes with high alkali reserves, preferably initially with customary inorganic and / or organic acids, for example citric acid, phosphoric acid, lactic acid, glycolic acid. Neutralize gluconic acid or sulfuric acid, especially citric acid, preferably up to a pH between 7 and 9.5. If desired, the acids can also be used to set a low pH below 7, for example in the case of low-viscosity fatty alcohol ether sulfate pastes. In the context of the invention it is of course also possible to use neutral aqueous pastes of anionic surfactants which have not been additionally stabilized by adding hydroxides with an alkali reserve. For the purposes of the present invention, all anionic surfactants (pastes) that have a pH between 7 and 9.5 are considered to be pH-neutral anionic surfactants (pastes).
  • bases are preferably to be understood as meaning those compounds which, in the Broenstedt base definition, are capable of taking up protons. This includes compounds which are in themselves bases, such as ammonia or amines, and also compounds which only release bases, such as ammonium carbonate, by decomposition. Such bases are referred to as volatile in the sense of the invention if they are preferably used in the fluidized bed plants prevailing temperatures, especially at 60 ° C and below, are gaseous.
  • volatile bases are those which are volatile even at room temperature (about 20 ° C.), such as ammonia and / or mono-, di- and trialkylamines with 1 and / or 2 carbon atoms in the alkyl radical.
  • Ammonia is particularly suitable. Ammonia can be used as a gas or in the form of its aqueous solutions such as concentrated ammonia.
  • the volatile bases are preferably added in amounts of 0.05 to 5, in particular 0J to 1% by weight, calculated as the active substance content of base and based on the active substance content of anionic surfactants in the aqueous surfactant preparation.
  • the volatile bases can be added in accordance with the surfactant pastes containing anionic surfactant directly before they are granulated and simultaneously dried.
  • the volatile bases in particular ammonia
  • the volatile bases are expediently added in the form of their aqueous solutions, in particular as concentrated ammonia, to the aqueous, anionic surfactants, if appropriate containing pH-neutral preparations, before they are injected into the fluidized bed apparatus and subjected to the granulation and simultaneous drying .
  • the aqueous anionic surfactants may contain surfactant preparations which may have previously been adjusted to be pH-neutral and, independently of this, to inject an aqueous base solution into the fluidized bed apparatus.
  • the aqueous surfactant preparations with the anionic surfactants into the fluidized bed apparatus via a nozzle and to spray the aqueous base solutions, in particular concentrated ammonia, preferably above the sieve bottom of the fluidized bed apparatus. Since there is negative pressure above the sieve bottom, the aqueous base solution is sucked into the fluidized bed in a simple manner.
  • the volatile bases are added to the fluidizing air fed into the fluidized bed apparatus for the granulation and drying.
  • the aqueous, optionally pH-neutral, anionic surfactant-containing surfactant preparations are injected into the fluidized bed apparatus and are only granulated and dried there in the presence of the volatile bases, preferably ammonia as gas, supplied with the fluidizing air. It is of course also possible within the scope of the invention to combine two or more of the described embodiments with one another.
  • the aqueous surfactant preparations containing anionic surfactants, preferably the aqueous anionic surfactant pastes can be granulated alone or with the addition of solid carrier materials in the fluidized bed and dried at the same time.
  • the water evaporates from the preparation (paste), resulting in dried to dried germs, which are coated with the optionally mixed carrier materials, granulated and again dried at the same time.
  • carrier materials are to be mixed in, they are mixed in simultaneously with the aqueous surfactant preparations (pastes), but separately from these, preferably via an automatically regulated solids metering.
  • carrier materials are mixed in for the purposes of the invention, they are preferably inorganic carrier materials and in particular alkali metal carbonates, alkali metal sulfates, crystalline or amorphous alkali metal silicates, crystalline or amorphous sheet silicates and / or zeolites.
  • the proportion of carrier materials to surfactant is not critical and can be in the weight ratio between 0: 100 to 50:50, preferably up to 80:20.
  • Fluidized bed apparatuses which are preferably used have base plates (sieve bases) 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.
  • 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 opposed air flow (classifier air), which is regulated in such a way that only particles above a certain particle size are removed from the fluidized bed and smaller particles are retained in the fluidized bed.
  • classifier air opposed air flow
  • 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 approximately 5 cm above the base plate 60 to 120 ° C., preferably 65 to 90 ° C. and in particular 70 to 85 ° C.
  • the air outlet temperature is preferably between 60 and 120 ° C, in particular below 80 ° C.
  • a starting mass is present at the beginning of the process, which serves as an initial carrier for the sprayed-in surfactant paste.
  • Suitable starting materials are the surfactant granules themselves, which may contain carrier materials, which have already been obtained in a previous process, or the carrier materials can be used as starting materials.
  • surfactant granules with a grain size in the range between 0J and 1.6 mm obtained from one of the preceding process sequences are used as starting mass.
  • the granules obtained from the fluidized bed are then preferably cooled in a separate fluidized bed and classified by means of a sieve into granules with grain sizes between 0J and 1.6 mm as good grain fraction and in granules over 1.6 mm as Uberkom fraction, while particles below 0.1 mm already get into an exhaust air filter during drying in the fluidized bed, separated from the exhaust air there and then fed back into the fluidized bed as germ material.
  • the Uberkom fraction is ground and also returned to the fluidized bed.
  • the surfactant granules are regarded as dried if the free water content is preferably below 10% by weight, in particular from 0J to 2% by weight, based in each case on the finished granules.
  • Surfactant granules with a high bulk density are obtained by the process according to the invention, preferably above 500 g / 1 and in particular between 550 and 1000 g / 1.
  • the active substance content fluctuates depending on the addition of carrier materials used and is in particular above 50% by weight, preferably between 85 and 98% by weight.
  • the surfactant granules obtained by the process according to the invention are pH neutral, i.e. after dissolving the surfactant granules in water, the aqueous solution has a pH between 7 and 9.5. Furthermore, the surfactant granules are dust-free and free-flowing and not or hardly sticky, so that they are easy to handle and silage-compatible in big bags.
  • Another object of the present invention relates to the use of the granules produced according to the invention as pH-neutral surfactants for the production of washing, rinsing and cleaning agents.
  • the detergents, rinsing agents and cleaning agents can contain the granules according to the invention in customary amounts, preferably in the range from 0J to 50% by weight, based on the agent.
  • the surfactant granules produced according to the invention are preferably suitable for the production of pH-neutral washing, rinsing and cleaning agents such as pH-neutral powder cleaners and pH-neutral soaps, as well as for detergents mixed with colorants such as toilet blocks.
  • the pH-neutral washing, rinsing and cleaning agents can be in powder, granular or lumpy form.
  • Another object of the present invention relates to the use of the granules according to the invention as surfactants for the production of cleaning cosmetics for teeth, hair and skin, in particular for the production of hair shampoos, shower baths, washing lotions, toothpaste and the like.
  • These agents can contain the granules according to the invention in amounts of 0J to 30% by weight, based on the agent.
  • the use for the production of agents for oral hygiene, in particular for toothpaste, is particularly preferred. Examples
  • a 1% aqueous solution of the granules showed a pH of 8.8 at 25 ° C.
  • 500 g of this sodium lauryl sulfate granulate were stored in a porcelain bowl in a drying cabinet at 80 ° C. for 72 hours. After this time, no gray spots were found in the product.
  • Example 1 10,000 kg of an aqueous paste containing 65% by weight sodium lauryl sulfate (52% C12 / 21% C 14/10% C 16/17% C 18) with a free alkali content of 0.1% .-% sodium hydroxide continuously injected at 2,000 kg per hour at a temperature of 70 ° C into the fluidized bed system (SKET system), the drying air having a temperature of 180 ° C when entering the fluidized bed, and 90 ° C at the outlet.
  • the temperature in the fluidized bed was 70 ° C. 24 kg of a 25% aq.
  • Ammonia solution were operated in parallel using a positively controlled
  • the multi-piston metering pump together with the aqueous surfactant paste is continuously fed into the fluidized bed of the SKET system.
  • a 1% aqueous solution of the granules showed a pH of 9.5 at 25 ° C.
  • 500 g of this sodium lauryl sulfate granulate were stored in a porcelain bowl in a drying cabinet at 80 ° C. for 72 hours. After this time, no gray spots were found in the product.
  • Example 1 10,000 kg of an aqueous paste containing 65% by weight sodium lauryl sulfate (52% C12 / 21% C 14/10% C 16/17% C 18) with a free alkali content of 0J% by weight. % Sodium hydroxide continuously injected at 2,000 kg per hour at a temperature of 70 ° C into the fluidized bed system (SKET system), the drying air having a temperature of 160 ° C when entering the fluidized bed and 90 ° C at the outlet. The temperature in the fluidized bed was 60 ° C.
  • a 1% aqueous solution of the granules showed a pH of 9.2 at 25 ° C.
  • 500 g of this sodium lauryl sulfate granulate were stored in a porcelain bowl in a drying cabinet at 80 ° C. for 72 hours. After this time, gray specks appeared in the product, which were isolated and had an acidic pH.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Medicinal Preparation (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

L'invention concerne un procédé de production de granulés tensioactifs contenant des tensioactifs anioniques et obtenus par granulation et séchage simultané dans le lit fluidisé. On travaille en présence de bases volatiles. L'invention concerne également leur utilisation pour produire des produits de lavage, de rinçage et de nettoyage et des produits d'hygiène buccale notamment de ph neutre.
PCT/EP1999/008763 1998-11-23 1999-11-13 Procede de production de granules tensioactifs WO2000031230A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP99963299A EP1131400B1 (fr) 1998-11-23 1999-11-13 Procede de production de granules tensioactifs
DE59915230T DE59915230D1 (de) 1998-11-23 1999-11-13 Verfahren zur herstellung von tensidgranulaten
AT99963299T ATE492626T1 (de) 1998-11-23 1999-11-13 Verfahren zur herstellung von tensidgranulaten

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853893.6 1998-11-23
DE19853893A DE19853893A1 (de) 1998-11-23 1998-11-23 Verfahren zur Herstellung von Tensidgranulaten

Publications (1)

Publication Number Publication Date
WO2000031230A1 true WO2000031230A1 (fr) 2000-06-02

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Application Number Title Priority Date Filing Date
PCT/EP1999/008763 WO2000031230A1 (fr) 1998-11-23 1999-11-13 Procede de production de granules tensioactifs

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EP (1) EP1131400B1 (fr)
AT (1) ATE492626T1 (fr)
DE (2) DE19853893A1 (fr)
ES (1) ES2357380T3 (fr)
WO (1) WO2000031230A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2801606A1 (fr) * 2013-05-07 2014-11-12 The Procter and Gamble Company Particule séchée par pulvérisation comprenant du sulfate
CN117280017A (zh) 2021-05-10 2023-12-22 巴斯夫欧洲公司 基于异构十三烷醇混合物的醚硫酸盐

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993023520A1 (fr) * 1992-05-20 1993-11-25 Henkel Kommanditgesellschaft Auf Aktien Procede de fabrication de produits detergents et nettoyants renfermant des agents tensioactifs anioniques
DE4304062A1 (de) * 1993-02-11 1994-08-18 Henkel Kgaa Verfahren zur Herstellung von Tensidgranulaten
WO1998040461A1 (fr) * 1997-03-12 1998-09-17 Cognis Deutschland Gmbh Procede de preparation de granules tensioactifs anioniques
DE19707649C1 (de) * 1997-02-26 1998-10-22 Henkel Kgaa Verfahren zur Herstellung von Waschmittelrohstoffen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993023520A1 (fr) * 1992-05-20 1993-11-25 Henkel Kommanditgesellschaft Auf Aktien Procede de fabrication de produits detergents et nettoyants renfermant des agents tensioactifs anioniques
DE4304062A1 (de) * 1993-02-11 1994-08-18 Henkel Kgaa Verfahren zur Herstellung von Tensidgranulaten
DE19707649C1 (de) * 1997-02-26 1998-10-22 Henkel Kgaa Verfahren zur Herstellung von Waschmittelrohstoffen
WO1998040461A1 (fr) * 1997-03-12 1998-09-17 Cognis Deutschland Gmbh Procede de preparation de granules tensioactifs anioniques

Also Published As

Publication number Publication date
EP1131400B1 (fr) 2010-12-22
ES2357380T3 (es) 2011-04-25
EP1131400A1 (fr) 2001-09-12
ATE492626T1 (de) 2011-01-15
DE19853893A1 (de) 2000-05-25
DE59915230D1 (de) 2011-02-03

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