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WO1999010459A1 - Procede de production de granules d'agents de surface anioniques exempts d'eau et de poussiere - Google Patents

Procede de production de granules d'agents de surface anioniques exempts d'eau et de poussiere Download PDF

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Publication number
WO1999010459A1
WO1999010459A1 PCT/EP1998/005212 EP9805212W WO9910459A1 WO 1999010459 A1 WO1999010459 A1 WO 1999010459A1 EP 9805212 W EP9805212 W EP 9805212W WO 9910459 A1 WO9910459 A1 WO 9910459A1
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WIPO (PCT)
Prior art keywords
carbon atoms
alkyl
fatty acid
acid
radical
Prior art date
Application number
PCT/EP1998/005212
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German (de)
English (en)
Inventor
Hans-Christian Raths
Werner Seipel
Bernd Fabry
Hermann Hensen
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Cognis Deutschland Gmbh
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Filing date
Publication date
Priority claimed from DE19736906A external-priority patent/DE19736906A1/de
Priority claimed from DE19741911A external-priority patent/DE19741911C1/de
Priority claimed from DE1998106495 external-priority patent/DE19806495C1/de
Application filed by Cognis Deutschland Gmbh filed Critical Cognis Deutschland Gmbh
Priority to EP98943891A priority Critical patent/EP1007613A1/fr
Publication of WO1999010459A1 publication Critical patent/WO1999010459A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
    • C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A61K8/0275—Containing agglomerated particulates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/42—Amides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/463—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfuric acid derivatives, e.g. sodium lauryl sulfate
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/60—Sugars; Derivatives thereof
    • A61K8/604—Alkylpolyglycosides; Derivatives thereof, e.g. esters
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2615—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen the other compounds containing carboxylic acid, ester or anhydride groups
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2669—Non-metals or compounds thereof
    • C08G65/2672—Nitrogen or compounds thereof
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    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • C—CHEMISTRY; METALLURGY
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    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
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    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • C11D1/652—Mixtures of anionic compounds with carboxylic amides or alkylol amides
    • C—CHEMISTRY; METALLURGY
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    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
    • 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/042—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
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    • A61Q5/02—Preparations for cleaning the hair
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    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
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    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
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    • C11D1/04—Carboxylic acids or salts thereof
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    • 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
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    • 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
    • C11D1/16—Sulfonic acids or sulfuric acid esters; Salts thereof derived from divalent or polyvalent alcohols
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    • 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
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    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
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    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
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Definitions

  • the invention relates to a process for the simultaneous drying and granulation of aqueous fatty acid polyglycol ester sulfate pastes using a thin film evaporator.
  • Fatty acid polyglycol ester sulfates are characterized by excellent detergent properties and high ecotoxicological compatibility. For this reason, these anionic surfactants are becoming increasingly important.
  • solid, water-free forms of supply which can also be incorporated, for example, in powder detergents, toothpastes or syndet soaps.
  • liquid surfactant preparations are generally dried by conventional spray drying, in which the aqueous surfactant paste is sprayed at the top of a tower in the form of fine droplets, to which hot drying gases are directed.
  • spray drying in which the aqueous surfactant paste is sprayed at the top of a tower in the form of fine droplets, to which hot drying gases are directed.
  • the drastic conditions often lead to hydrolysis, undesirable discoloration of the products, caking on the walls of the spray towers and, as a result, contamination of the dry material by charred residues.
  • the repeated cleaning of the towers also leads to downtimes, which can make the process costly.
  • a further problem is that prior art methods do not lead to the particularly preferred heavy powders with a bulk density above 500 g / l with a simultaneously greatly reduced dust content.
  • these two parameters are of particular importance for economic, application-related and safety-related reasons.
  • the complex object of the present invention was to convert aqueous fatty acid polyglycol ester sulfate pastes into practically water- and dust-free granules with as little technical effort as possible without the use of inorganic or organic carriers, which at the same time had an acceptable color quality, a high bulk density, and good Flowability, satisfactory storage stability and, in comparison to the products of the prior art, are characterized by at least comparable application properties.
  • the invention relates to a process for the preparation of water- and dust-free anionic side granules with a high bulk density, in which aqueous pastes of fatty acid polyglycol ester sulfates with a solids content of at least 20 and preferably in the range from 25 to 75% by weight in a horizontal Arranged thin-film evaporator with rotating internals dries down to a residual water content of less than 2, preferably less than 1, 5 and in particular less than 1% by weight and brings it into pieces, whereby a negative temperature gradient is applied to the thin-film evaporator from the product inlet to the product discharge, im Counter-current gassed with air and drying takes place exclusively via the heated wall.
  • a horizontally arranged thin-film evaporator is ideally suitable for converting aqueous fatty acid polyglycol ester sulfate pastes into dry, light-colored, free-flowing and non-sticky granules without product discoloration and caking on the walls.
  • the products have a high bulk density in the range of 550 to 650 g / l and an average grain diameter of 2.0 to 2.8 mm, which leads to a reduction in unwanted water absorption and caking of the particles. This also ensures high storage stability. At the same time, they are dust-free, ie the proportion of particles with a diameter below 200 ⁇ m is below 5% by weight.
  • R 1 CO is a linear or branched, saturated or unsaturated acyl radical having 6 to 22 carbon atoms
  • x is an average of 1 to 3
  • AO is a CH2CH2O-, CH 2 CH (CH 3 ) 0- and / or CH ( CH 3 ) CH 2 0 radical
  • X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium, are known anionic surfactants and are prepared by sulfation of the corresponding fatty acid polyglycol ester. These in turn can be obtained using the relevant preparative processes in organic chemistry.
  • ethylene oxide, propylene oxide or a mixture thereof - in random or block distribution - is added to the corresponding fatty acids, this reaction being acid-catalyzed, but preferably in the presence of bases, such as, for example, sodium methylate or calcined hydrotalcite.
  • bases such as, for example, sodium methylate or calcined hydrotalcite.
  • the intermediates can also be prepared by esterifying the fatty acids with an appropriate alkylene glycol.
  • the sulfation of the fatty acid polyglycol esters can be carried out in a manner known per se with chlorosulfonic acid or preferably gaseous sulfur trioxide, the molar ratio between fatty acid polyglycol ester and sulfating agent being in the range from 1: 0.95 to 1: 1, 2, preferably 1: 1 to 1: 1 , 1 and the reaction temperature can be 30 to 80 and preferably 50 to 60 ° C. It is also possible to undersulfate the fatty acid polyglycol esters, ie to use significantly fewer sulfating agents than would be stoichiometrically required for complete conversion.
  • Typical examples of suitable starting materials are the addition products of 1 to 3 moles of ethylene oxide and / or propylene oxide, but preferably the adducts with 1 mole of ethylene oxide or 1 mole of propylene oxide with caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, Palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures, which are then sulfated and neutralized as described above.
  • Fatty acid polyglycol ester sulfates of the formula (I) are preferably used in which R 1 CO stands for an acyl radical having 12 to 18 carbon atoms, x for an average of 1 or 2, AO for a CHaCH ⁇ O group and X for sodium or ammonium, such as, for example, lauric acid + 1EO sulfate sodium salt, lauric acid + 1 EO sulfate ammonium salt, coconut fatty acid + 1 EO sulfate sodium salt, coconut fatty acid + 1 EO sulfate ammonium salt, tallow fatty acid + 1EO sulfate sodium salt, tallow fatty acid + 1EO sulfate ammonium salt and mixtures thereof.
  • R 1 CO stands for an acyl radical having 12 to 18 carbon atoms
  • x for an average of 1 or 2
  • AO for a CHaCH ⁇ O group
  • X for sodium or ammonium, such as, for example, lauric acid +
  • Alkyl and alkenyl oligoglycosides which can be dried as optional surfactants, are known nonionic surfactants which follow the formula (II),
  • R represents an alkyl and / or alkenyl radical having 4 to 22 carbon atoms
  • G represents a sugar radical having 5 or 6 carbon atoms
  • p represents numbers from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry.
  • the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucos.de.
  • alkyl and / or alkenyl oligoglycosides are preferred whose degree of oligomerization is less than 1.7 and is in particular between 1.2 and 1.4.
  • the alkyl or alkenyl radical R 2 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capro alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
  • the alkyl or alkenyl radical R 2 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms.
  • Typical examples are lauryl 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, brassidyl alcohol and their technical mixtures, as described above, which can be obtained as described above.
  • Alkyl oligoglucosides based on hardened Ci2 / are preferred.
  • Fatty acid N-alkylpolyhydroxyalkylamides which can also be mini-dried as optional surfactants, are nonionic surfactants which follow the formula (III)
  • R 3 CO for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R 4 for an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 12 carbon atoms and 3 to 10 hydroxyl groups stands.
  • the fatty acid N-alkylpolyhydroxyalkylamides are known substances which are usually obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride can. With regard to the processes for their production, reference is made to US Pat. Nos.
  • the fatty acid N-alkylpolyhydroxyalkylamides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
  • the preferred fatty acid N-alkyl polyhydroxyalkylamides are therefore fatty acid N-alkylglucamides, as represented by the formula (IV):
  • the fatty acid N-alkylpolyhydroxyalkylamides used are preferably glucamides of the formula (IV) in which R 4 is methyl and R 3 CO is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid , Elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic acid or erucic acid or their technical mixtures.
  • Fatty acid N-alkylglucamides of the formula (IV) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or Ci2 / i4 coconut fatty acid or a corresponding derivative are particularly preferred.
  • the polyhydroxyalkylamides can also be derived from maltose and palatinose.
  • Monoglyceride sulfates and monoglyceride ether sulfates which can also be dried as further anionic surfactants, are known substances which can be obtained by the relevant methods of preparative organic chemistry.
  • the usual starting point for their preparation is triglycerides, which, if appropriate, are transesterified to the monoglycerides after ethoxylation and subsequently sulfated and neutralized. It is also possible to react the partial glycerides with suitable sulfating agents, preferably gaseous sulfur trioxide or chlorosulfonic acid [cf. EP-B1 0561825, EP-B1 0561999 (Henkel)].
  • the neutralized substances can be subjected to ultrafiltration in order to reduce the electrolyte content to a desired level [DE-A1 4204700 (Henkel)].
  • Overviews of the chemistry of the monoglyceride sulfates are, for example, by A.K.Biswas et al. in J.Am.Oil.Chem.Soc. 37, 171 (1960) and F.U. Ahmed J.Am. Oil.Chem. Soc. 67, 8 (1990).
  • the monoglyceride (ether) sulfates to be used in accordance with the invention preferably follow the formula (V),
  • R 5 CO stands for a linear or branched acyl radical with 6 to 22 carbon atoms, x, y and z in total for 0 or for numbers from 1 to 30, preferably 2 to 10, and X stands for an alkali or alkaline earth metal.
  • Typical examples of monoglyceride (ether) sulfates which are suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monogiyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride and their ethylene oxide adducts or their form of sulfuric acid with sulfuric acid trioxide.
  • Monoglyceride sulfates of the formula (V) are preferably used in which R 5 CO represents a linear acyl radical having 8 to 18 carbon atoms.
  • the monoglyceride (ether) sulfates are preferably used as dried granules or powders, which can be obtained, for example, by drying aqueous pastes in a flash dryer.
  • Betaines which can also be dried as representatives of the amphoteric or zwitterionic surfactants, are known substances which are predominantly prepared by carboxyalkylation, preferably carboxymethylation, of aminic compounds.
  • the starting materials are preferably mixed with halocarboxylic acids or their salts, in particular with sodium chloroacetate condenses, forming one mole of salt per mole of betaine.
  • unsaturated carboxylic acids such as acrylic acid
  • R 6 for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms
  • R 7 for hydrogen or alkyl radicals with 1 to 4 carbon atoms
  • R 8 for alkyl radicals with 1 to 4 carbon atoms
  • n for numbers from 1 to 6
  • X for a Alkali and / or alkaline earth metal or ammonium.
  • Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, Removal cyldimethylamin, dodecylmethylamine, Dodecyldimethyiamin, Dodecylethylmethylamin, Ci ⁇ m-Kokosal- kyidimethyiamin, Myristyidimethylamin, cetyldimethylamine, stearyldimethylamine, Stearylethylmethyl- amine, oleyl dimethyl amine, tallow alkyl dimethyl amine Ci ⁇ and technical mixtures thereof.
  • Carboxyalkylation products of amidoamines which follow the formula (VII) are also suitable,
  • R 9 CO represents an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds
  • m represents numbers from 1 to 3
  • R 7 , R 8 , n and X have the meanings given above.
  • Typical examples are reaction products of fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, gynacholeic acid, arachene acid and erucic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N
  • the simultaneous drying and granulation takes place in a horizontally arranged thin-film evaporator with rotating internals, such as that sold by the VRV company under the name "Flashdryer".
  • this is a tube that has different temperatures across several zones
  • the paste-like feed material which is metered in via a pump, is thrown against the heated wall by means of one or more shafts, which are provided with blades or shares of flies as rotating internals, on which the drying takes place in a thin layer of typically 1 to
  • the thin film evaporator is operated at atmospheric pressure and gassed in countercurrent with air (throughput 50 to 150 m 3 / h).
  • the gas inlet temperature is usually 20 to 30 ° C, the outlet temperature 90 to 110 ° C.
  • the aqueous fatty acid polyglycol ester sulfate pastes which are suitable as starting materials can have a solids content in the range above 20, preferably from 25 to 75% by weight; typically it is 30 to 50% by weight.
  • 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 pastes at 40 to 60 ° C during the feed. After drying, it has also proven to be very advantageous to place the granules, which are still approximately 50 to 70 ° C., on a conveyor belt, preferably a vibratory zone, and there, ie within a dwell time of 20 to 60 s, with ambient air at temperatures of cool about 30 to 40 ° C. To further improve the resistance to undesired water absorption, the granules can also be subsequently depleted by adding 0.5 to 2% by weight of silica.
  • the granules obtainable by the process according to the invention can then be mixed with other ingredients of powdered surface-active agents, such as tower powders for detergents. It is also possible without problems to incorporate the powders into aqueous preparations. In fact, no differences in the application properties are observed when using the powders compared to the aqueous starting pastes. Even in bar soaps of the combibar or syndet type, the granules can be easily incorporated, for example together with fatty acids, fatty acid salts, fatty alcohols, starch, polyglycols and the like. Examples
  • Example 1 The granules were produced in a flash dryer from VRV SpA, Milan / IT. It was a horizontally arranged thin film evaporator (length 1100 mm, inside diameter: 155 mm) with 4 shafts and 22 blades, the distance to the wall of which was 2 mm. The dryer had three separate heating or cooling zones and a total heat exchanger area of 0.44 m 2 . The operation was carried out at normal pressure. An aqueous paste of a lauric acid + 1 EO sulfate sodium salt (solids content approx.
  • Example 2 Example 2 was repeated with a mixture of 60% by weight lauric acid + 1E0-suifat sodium salt and 40% by weight coconut alkyl oligoglucoside (Plantacare® APG 1200). The temperature in the two heating zones of the flash dryer was raised to 170 ° C. A pure white, free-flowing and non-clumping granulate was also obtained, which had a bulk density of 600 g / l and a residual water content of 0.8% by weight.
  • Example 3 Example 1 was repeated with a mixture of 60% by weight coconut fatty acid + 1PO sulfate sodium salt and 40% by weight coconut fatty alcohol (Lanette® O, Henkel KGaA). The temperature in the two heating zones of the flash dryer was raised to 170 ° C. A pure white, free-flowing and non-clumping granulate was also obtained, which had a bulk density of 600 g / l and a residual water content of 0.8% by weight.
  • Example 4 Example 1 was repeated with a mixture of 30% by weight lauric acid + 1EO sulfate sodium salt, 30% by weight coconut fatty acid monoglyceride sulfate and 40% by weight palm kernel fatty acid (Edenor PK®, Henkel KGaA). The temperature in the two heating zones of the flash dryer was raised to 170 ° C. A pure white, free-flowing and non-clumping granulate was also obtained, which had a bulk density of 590 g / l and a residual water content of 0.8% by weight.
  • Edenor PK® palm kernel fatty acid
  • Example 5 Example 5 was carried out with a mixture of 30% by weight lauric acid + 1 EO sulfate sodium salt, 30% by weight coconut fatty acid amidopropyibetaine (Dehyton® PK, Henkel KGaA) and 40% by weight palm kernel fatty acid (Edenor PK®, Henkel) KGaA) repeated. The temperature in the two heating zones of the flash dryer was raised to 170 ° C. A pure white, free-flowing and non-clumping granulate was also obtained, which had a bulk density of 600 g / l and a residual water content of 0.8% by weight.

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Abstract

L'invention concerne un procédé de production de granulés d'agents de surface anioniques exempts d'eau et de poussière et ayant une densité en vrac élevée. Selon ce procédé, on sèche des pâtes aqueuses de sulfates d'ester polyglycol d'acides gras, ayant une teneur en matières solides d'au moins 20 % en poids, dans un vaporisateur à couche mince placé horizontalement et doté d'objets intégrés rotatifs, jusqu'à obtention d'une teneur en eau résiduelle inférieure à 2 % en poids. Ensuite, on fragmente ces pâtes en appliquant au vaporisateur à couche mince un gradient de température décroissant entre l'entrée et la sortie du produit, et on les charge d'air en contre-courant. Le séchage est effectué exclusivement par la paroi chauffée. Les granulés conviennent notamment à la production de pains de savon.
PCT/EP1998/005212 1997-08-25 1998-08-17 Procede de production de granules d'agents de surface anioniques exempts d'eau et de poussiere WO1999010459A1 (fr)

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EP98943891A EP1007613A1 (fr) 1997-08-25 1998-08-17 Procede de production de granules d'agents de surface anioniques exempts d'eau et de poussiere

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
DE19736906A DE19736906A1 (de) 1997-08-25 1997-08-25 Verfahren zur Herstellung von sulfatierten Fettsäurealkylenglykolestern
DE19736906.5 1997-08-25
DE19741911.9 1997-09-25
DE19741911A DE19741911C1 (de) 1997-09-25 1997-09-25 Stark schäumende Detergensgemische
DE1998106495 DE19806495C1 (de) 1998-02-17 1998-02-17 Verfahren zur Herstellung wasser- und staubfreier Aniontensidgranulate
DE19806495.0 1998-02-17

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US09/407,981 Continuation US6444832B1 (en) 1995-11-30 1999-09-29 Amino alcohol derivatives, method of producing said derivatives and medicaments containing them

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993019155A1 (fr) * 1992-03-23 1993-09-30 Henkel Kommanditgesellschaft Auf Aktien Procede de fabrication de produits de lavage et de detergents coulants se presentant sous forme de granules et/ou de granules partiels
DE4242185A1 (de) * 1992-12-15 1994-06-16 Henkel Kgaa Granulare Wasch- und Reinigungsmittel mit hohem Tensidgehalt
DE19641275C1 (de) * 1996-10-07 1998-03-12 Henkel Kgaa Verfahren zur Herstellung wasser- und staubfreier Aniontensidgranulate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993019155A1 (fr) * 1992-03-23 1993-09-30 Henkel Kommanditgesellschaft Auf Aktien Procede de fabrication de produits de lavage et de detergents coulants se presentant sous forme de granules et/ou de granules partiels
DE4242185A1 (de) * 1992-12-15 1994-06-16 Henkel Kgaa Granulare Wasch- und Reinigungsmittel mit hohem Tensidgehalt
DE19641275C1 (de) * 1996-10-07 1998-03-12 Henkel Kgaa Verfahren zur Herstellung wasser- und staubfreier Aniontensidgranulate

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