EP0772674B1 - Procede de fabrication de granules de tensioactif - Google Patents

Procede de fabrication de granules de tensioactif Download PDF

Info

Publication number
EP0772674B1
EP0772674B1 EP95926892A EP95926892A EP0772674B1 EP 0772674 B1 EP0772674 B1 EP 0772674B1 EP 95926892 A EP95926892 A EP 95926892A EP 95926892 A EP95926892 A EP 95926892A EP 0772674 B1 EP0772674 B1 EP 0772674B1
Authority
EP
European Patent Office
Prior art keywords
acid
spray
weight
surfactant
anionic surfactants
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Lifetime
Application number
EP95926892A
Other languages
German (de)
English (en)
Other versions
EP0772674A1 (fr
Inventor
Thomas LÜDER
Bernhard Gutsche
Gilbert Roegel
Christoph Wissenmeyer
Karl-Heinz Schmid
Ditmar Kischkel
Andreas Syldath
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cognis IP Management GmbH
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0772674A1 publication Critical patent/EP0772674A1/fr
Application granted granted Critical
Publication of EP0772674B1 publication Critical patent/EP0772674B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying

Definitions

  • the invention relates to a process for the production of washing and cleaning active Surfactant granules with high bulk density and good dissolving behavior in Water, the grain size of the granules being controllable at least in such a way that dust-free or at least low-dust granules are formed.
  • Surfactant granules can, for example, by conventional drying techniques of surfactant-containing solutions and pastes, especially manufactured in the spray tower will.
  • EP-A-0 319 819 describes a process for the production of surfactant granules by a Spray drying discloses one anionic surfactant in its acid form and one highly concentrated aqueous alkaline component separated with a gaseous Medium applied, then brought together in stoichiometric amounts, neutralized in a multi-fuel nozzle and at a high propellant pressure in Drying tower to be sprayed.
  • the products obtained are solid or paste-like, whereby solid products are mostly relatively dusty, a relative have a high water content and a low bulk density.
  • Granulation is an alternative to spray drying surfactant pastes
  • European patent application EP-A-0 430 148 Process for the production of fatty alcohol sulfate granules in cold water are dispersible.
  • a highly concentrated aqueous fatty alcohol sulfate paste which less than 14% by weight water and less than 20% by weight contains further additives, mechanically at temperatures between 10 and 45 ° C processed until granules are formed.
  • This way though Obtain fatty alcohol sulfate granules that are already at washing temperatures between 4 and 30 ° C are dispersed; the process temperature to be included and the relatively low maximum water content of the surfactant paste, however critical process parameters. It is also not disclosed which Bulk weights which have granules produced by this process.
  • EP-A-0 402 112 a method for Production of fatty alcohol sulfate and / or alkylbenzenesulfonate granules known, the neutralization of the anionic surfactants in acid form to a paste with a maximum of 12% by weight of water with the addition of auxiliaries such as polyethylene glycols, ethoxylated alcohols or alkylphenols, which one Have melting point above 48 ° C, and the granulation in a high-speed Mixer done. Again, the amount of water to be observed sets one critical process parameters. It is also not disclosed which Bulk weights which have surfactant granules obtained by this process.
  • EP-A-0 402 111 a method for Production of detergent-active granules with a bulk density that are active in washing and cleaning known between 500 and 1200 g / l, a surfactant preparation form, which contains water as a liquid component and additional organic polymers and may contain builder substances, mixed with a finely divided solid and granulated in a high speed mixer.
  • the water content of the surfactant paste represents a critical process parameter If the water content of the surfactant paste is too high, the solid becomes dispersed so that it can no longer act as a deagglomeration agent. On the other hand, if the solids content exceeds a certain value, it has the mass does not have the consistency required for granulation.
  • the object of the invention was to develop a method that Disadvantages of the above method does not have. In particular, you should low-dust granules with increased bulk density are produced, the nevertheless have good dissolving behavior in water.
  • the invention accordingly relates to a method for producing Surfactant granules by spray drying, one or more anionic surfactants Anionic surfactants in its / its acid form and a highly concentrated aqueous alkaline Component separately charged with a gaseous medium, brought together, neutralized in a multi-component nozzle and at a high Propellant gas pressure are sprayed in the drying tower, bringing together the acidic and alkaline components in almost stoichiometric amounts and the solid, finely divided products obtained in a mechanical working mixer are transferred in which the fine particles to granules be agglomerated with a bulk density of at least 400 g / l.
  • the first stage of the process, spray neutralization can be carried out, for example the teaching of the European patent application EP-A-0 319 819 can be carried out. At this point, it is expressly based on the revelation in the European Patent application EP-A-0 319 819 pointed out.
  • a preferred embodiment of the present invention provides that the separately charged with a gaseous medium acidic and alkaline Reactant flows via a single multi-component nozzle, for example via a 2-substance nozzle or a 3-substance nozzle, brought together and into the drying room be sprayed. It is also possible to merge the to carry out gas-charged reactant flows before the nozzle.
  • the distance of the place of the merge from the Spray device from the process conditions and the used Is dependent on material systems but is preferably kept as small as possible, to clog the nozzle due to premature neutralization reactions to avoid.
  • the first-mentioned variant of the merge of the reactant streams in the nozzle are preferred, since in this case neutralization essentially in the nozzle or directly when exiting the Nozzle takes place.
  • the merged acidic and alkaline reactant flows via several multi-component nozzles be sprayed into the drying room. This is particularly preferred when products are made from different types of anionic surfactants and thus different types of merged acidic and alkaline reactant streams sprayed should be.
  • the starting materials for example using piston pumps almost dosed stoichiometrically into one or two non-modified commercially available ones Nozzle (s) or one or two spray tube (s) introduced.
  • the gaseous medium (propellant) is mixed in before the nozzle. This means that the admixing of the gaseous medium in the reactant streams before they meet in front of or in the nozzle.
  • More technical Details on the implementation of the method for example with regard to the Control of reaction temperatures, the flow rate of the Reactant flows or the pressure at which the reaction mixture enters the drying room is sprayed, the European patent application EP-A-0 319 819.
  • “almost stoichiometric amounts "that the ratio of the number of acidic groups to alkaline Groups preferably in the range from 1.1: 1 to 0.8: 1 and in particular from 1: 1 to 0.9: 1.
  • carboxylic acids, sulfuric acid semiesters and sulfonic acids preferably fatty acids, alkylarylsulfonic acids, ⁇ -sulfofatty acid esters as well as the sulfuric acid semiesters of if necessary alkoxylated, especially ethoxylated alcohols and fatty alcohols and / or the sulfosuccinic acid can be used.
  • too Fatty acid esters, especially fatty acid methyl esters are used, wherein in in this case not a neutralization reaction, but a saponification of the ester group is carried out.
  • Suitable anionic surfactants in their acid form are therefore in particular either an anionic surfactant in its acid form or a mixture of the group of anionic surfactants in their acid form, optionally in combination with nonionic, amphoteric and / or cationic surfactants.
  • Preferred anionic surfactants in their acid form are C 8 -C 22 alkylsulfonic acids, C 9 -C 13 alkylbenzenesulfonic acid, usually called dodecylbenzenesulfonic acid, and methyl ⁇ -sulfofatty acid in their acid form.
  • Particularly preferred alkyl sulfonic acids are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, in particular from fatty alcohols, e.g. B.
  • coconut fatty alcohols coconut fatty alcohols, tallow fatty alcohols, oleyl alcohols, lauryl, myristyl, palmityl or stearyl alcohol, or the C 10 -C 20 oxo alcohols, and those secondary alcohols of this chain length.
  • esters of ⁇ -sulfofatty acids obtained by sulfonating the methyl esters of fatty acids of plant and / or animal origin with 10 to 20 C atoms in the fatty acid molecule, for example the ⁇ -sulfonated methyl esters of the hydrogenated coconut and palm kernels, are obtained by the process according to the invention - or tallow fatty acids, and the ⁇ -sulfofatty acids (diacids) obtainable by ester cleavage.
  • alkanesulfonic acids which can be obtained from C 12 -C 18 alkanes by sulfochlorination or sulfoxidation.
  • nonionic surfactants come, but also Builder substances such as phosphates and zeolites or polycarboxylic acids or their Salts and polymeric polycarboxylates and inorganic salts such as carbonates, Bicarbonates, silicates, sulfates and bisulfates into consideration.
  • Solid substances can be blown into the spray drying room, for example, while for liquid components there is also the possibility of combining them with one of the reactant streams in the spray drying room.
  • anionic surfactants and / or nonionic, surfactant pastes are added in addition to the reactant streams into the spray drying room.
  • the invention therefore uses an anionic surfactant in its acid form or a mixture from anionic surfactants in their acid form in combination with anionic, nonionic, amphoteric and / or cationic surfactants used.
  • anionic surfactants which are introduced into the process in particular in paste form can be, all are concordant to the acid forms mentioned above Salts.
  • Nonionic surfactants preferably used in combination with these anionic surfactants in acid form are derived from liquid alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 9 to 18 carbon atoms and an average of 1 to 40 moles of ethylene oxide per mole of alcohol in which the alcohol residue is linear or can be methyl-branched in the 2-position, or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • linear residues of alcohols of native origin with 12 to 18 carbon atoms such as, for example, coconut oil, tallow oil or oleyl alcohol, are particularly preferred.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Alcohol ethoxylates with a narrow homolog distribution are also suitable.
  • alcohol ethoxylates are preferred which have an average of 2 to 8 ethylene oxide groups.
  • the preferred ethoxylated alcohols include, for example, C 9 -C 11 oxo alcohol with 7 E0, C 13 -C 15 oxo alcohol with 3 E0, 5 E0 or 7 E0 and in particular C 12 -C 14 alcohol with 3 E0 or 4 E0, C 12 -C 18 alcohols with 3 E0, 5 E0 or 7 E0 and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 E0 and C 12 -C 18 alcohol with 5 E0.
  • alcohols are preferred which have more than 10 E0 per molecule of alcohol, for example 11 E0, 14 E0, 20 E0, 25 E0, 30 E0 or even 40 E0 such as tallow fatty alcohol with 40 E0.
  • alkyl glycosides of the general formula R-0- (G) x in which R is a primary straight-chain or aliphatic radical which is methyl-branched in the 2-position and has 8 to 22, preferably 12 to 18, carbon atoms, G is a symbol , which stands for a glycose unit with 5 or 6 carbon atoms, and the degree of oligomerization x is between 1 and 10, preferably between 1 and 2 and in particular is significantly less than 1.4.
  • the neutralization or saponification reaction is preferably concentrated aqueous alkaline solutions, for example solutions of hydroxides, Carbonates or hypochlorites of sodium or potassium, in particular carried out with a concentrated aqueous sodium hydroxide solution and / or potassium hydroxide solution, concentrations around 45 to 55% by weight are particularly preferred. A further dilution of the reactant streams with water is not necessary.
  • the gaseous medium is particularly suitable compared to the initial and end products are inert gases such as air or nitrogen.
  • inert gases such as air or nitrogen.
  • steam is also suitable, especially if one of the reactant streams or the reactant streams are heated prior to merging should).
  • Such solid products can now be transferred to any of the known mechanically operating mixers or granulators, with the aid of which the powders can be granulated and, at the same time, compacted to bulk densities of at least 400 g / l, preferably of about 420 to 650 g / l.
  • Such mixers are, for example, ploughshare mixers or ring-layer mixers, such as those sold by Lödige, Imcatec or Drais, but also types of mixers from Schugi (Flexomix (R) ) or Niro (ZigZag mixer (R) or HEC granulator (R) ). Both batch and continuous mixer types can be used, with the continuously operating mixer types being preferred.
  • this granulation is carried out at a temperature at which the solid products softened and can thus be shaped.
  • too high temperatures there is too much softening of the granules to be granulated Mix and thus to clog the mixer due to pasty caking Walls and tools.
  • Moves at a given chemical composition the preferred temperature range also increases with increasing water content downward.
  • drying may be necessary or humidification, cooling or heating of the spray-neutralized product be advantageous before or during granulation.
  • the spray-neutralized Powder before granulation of a treatment in a fluidized bed subjected whereby the powders can be dried and / or cooled.
  • the powders can be dried and / or cooled.
  • Advantageously is cooling or first drying and then then cooling the products, preferably such Product temperatures can be set, which in the granulation as favorable have proven so that direct processing of the product is possible becomes.
  • the Spray room even produce powdered products directly, i.e. without intermediate storage and without treatment in the fluidized bed in the mechanically working Mixer processed.
  • the applicant assumes that the relatively high water content of the sprayed and dusty products the first stage of the process serves as a "liquid reserve", whereby a Granulation is made possible.
  • the parameter that is in the first stage of the process to the manifold disadvantages of powdered Products leads to particularly advantageous after the second stage of the process Products are created.
  • Add usual ingredients of washing or cleaning agents come primarily here and inorganic salts. Additives are particularly preferred but also peroxy bleaching agents such as perborate and percarbonate, but also conventional ones Graying inhibitors and substances that prevent the re-soiling of the tissue prevent. Enzymes can also be granulated at this stage; it However, it is preferred to add these to the end product in granular form.
  • Water and aqueous solutions are less preferred at this point: once As stated above, the water is not required as a granulating liquid and on the other hand, a subsequent drying would have to be connected in most cases which is not preferred.
  • a second process stage can be used, for example in a so-called Long-term dryer, for example in a fluidized bed or a vacuum dryer, be performed.
  • Long-term dryer for example in a fluidized bed or a vacuum dryer
  • Farther can be common processing steps such as screening and, if necessary Connect the return of fine and coarse particles in the mixer.
  • finely divided solids for example zeolites, in particular Zeolite A and / or Zeolite P, silicates, silicas, sulfates, calcium stearates and mixtures of these advantageously become the end of the granulation step added to improve the storage stability of the granules.
  • solid additional components also soaps, alkyl sulfates and / or fatty acid isethionates in the Granulation stage added. It has been shown that the dissolving behavior of the Granular end products according to the invention in water, which per se already have good values, by adding these solids, for example in Amounts of 0.5 to 15 wt .-%, preferably in amounts of 1 to 10 wt .-%, yet can be increased.
  • the products obtained in accordance with the invention which are rapidly soluble in water are one low-dust granules.
  • the grain sizes or certain grain size ranges are about the process parameters of the mechanically operating mixers used or granulators controllable.
  • surfactant granules are produced with the following composition, which more than 40 wt .-%, preferably 50 to 95 wt .-% and in particular 80 to 90 wt .-% anionic surfactants, preferably C 8 -C 22 Alkyl sulfates, in particular C 12 -C 18 alkyl sulfates, C 16 -C 18 alkyl sulfates or cuts with higher proportions of C 12 and C 14 .
  • Example 1 analogously to the disclosure of EP-A-0 319 819, half-sulfuric acid (FAS1 and FAS2) were spray-neutralized with 50% by weight sodium hydroxide solution via a multi-component nozzle.
  • the spray-neutralized products FAS1 and FAS2 obtained had the composition given below (Table 1).
  • the spray-neutralized, relatively dusty products were transferred directly, that is to say without intermediate storage, to the mixers specified below.
  • granules with a bulk density of at least 400 g / l were produced which had good dissolving behavior in water.
  • composition of the spray-neutralized products Examples 1, 2, 3 Examples 4, 5, 6 Balance fatty alkyl sulfates FAS 1 Balance fatty alkyl sulfates FAS 2 (C chain cut: (C chain cut: 2% by weight of C 12 , C 14 24% by weight of C 12 , C 14 29% by weight of C 16 23% by weight of C 16 69% by weight C 18 ) 54% by weight C 18 ) 2.0% by weight sodium sulfate 2.0% by weight sodium sulfate 1.5% by weight sodium hydroxide 1.5% by weight sodium hydroxide 5.0% by weight unsulfated fatty alcohol 4.0% by weight of unsulfated fatty alcohol Water like in Water like in Table 2 indicated Table 2 indicated Properties of products 2 to 6 compared to 1 Examples 1 2nd 3rd 4th 5 6 spray neutralized powder granular end product ex ploughshare mixer ex ring layer mixer FAS type FAS1 FAS1 FAS1 FAS2 FAS2 FAS2 Bulk density in g / l 310 480
  • Example 1 was repeated with the FAS 2 type. Composition, Bulk weight and grain size distribution were in the same size range as at FAS 1.
  • Examples 2 and 3 show the effects of the residence time on the grain size distribution and the bulk weight.
  • Examples 4 and 5 show the effects of the granulation temperature on the bulk weight.
  • the improved flow properties of the products produced according to the invention 2 to 6 are one at the value of the required outlet diameter Bunkers readable: For the perfect further processing of a relative dusty, only spray-neutralized product according to Example 1 after storage in a bunker this should have an outlet diameter of 3.1 m, while for products according to one of the examples 2 to 6 outlet diameter of less than 1 m are sufficient.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Materials For Medical Uses (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Compounds Of Unknown Constitution (AREA)

Claims (12)

  1. Procédé de fabrication de granulés de tensioactifs par séchage par pulvérisation, dans lequel un tensioactif anionique ou plusieurs tensioactifs anioniques sous sa/leur forme acide et un composant alcalin aqueux hautement concentré sont soumis séparément à un milieu gazeux, sont réunis, neutralisés dans une buse à plusieurs constituants et sont pulvérisés à une pression élevée de gaz moteur dans la tour de séchage,
    caractérisé en ce que
    la jonction des composants acides et alcalins a lieu dans des quantités à peu près stoechiométriques et les produits obtenus solides, finement divisés sont transformés dans un mélangeur opérant mécaniquement, dans lequel les particules fines sont agglomérées en granulés ayant une densité apparente d'au moins 400 g/l.
  2. Procédé selon la revendication 1,
    caractérisé en ce que
    la poudre neutralisée par pulvérisation est soumise avant la granulation à un traitement dans une couche fluidisée, dans lequel la poudre peut être séchée et/ou refroidie, de préférence être refroidie ou être séchée d'abord et ensuite refroidie.
  3. Procédé selon la revendication 1,
    caractérisé en ce que
    les produits pulvérulents fabriqués dans la chambre de pulvérisation sont traités à nouveau sans stockage intermédiaire dans le mélangeur opérant mécaniquement.
  4. Procédé selon une des revendications 1 à 3,
    caractérisé en ce que
    la granulation est exécutée dans le mélangeur à des températures de produit comprises entre 30 et 80°C, de préférence entre 40 et 70°C.
  5. Procédé selon une des revendications 1 à 4,
    caractérisé en ce que
    la granulation des poudres séchées par pulvérisation a lieu sans addition de composants liquides.
  6. Procédé selon une des revendications 1 à 5,
    caractérisé en ce que
    la granulation des poudres séchées par pulvérisation a lieu avec des composants d'addition solides.
  7. Procédé selon la revendication 6,
    caractérisé en ce qu'
    on utilise comme composants d'addition solides des savons, des sulfates d'alkyle et/ou des iséthionates d'acide gras dans l'étape de granulation.
  8. Procédé selon une des revendications 1 à 7,
    caractérisé en ce qu'
    on utilise comme tensioactifs anioniques sous leur forme acide des acides gras, des acides d'aryle d'alkyle sulfoniques comme l'acide benzène sulfonique d'alkyle en C9-C13, des esters d'acide gras α-sulfonés ainsi que les semi-esters d'acide sulfurique d'alcools et d'alcools gras éventuellement alcoxylés, en particulier éthoxylés et/ou de l'acide sulfosuccinique.
  9. Procédé selon une des revendications 1 à 8,
    caractérisé en ce qu'
    on utilise un tensioactif anionique sous sa forme acide ou un mélange du groupe des tensioactifs anioniques sous leur forme acide en combinaison avec des tensioactifs anioniques, non ioniques, amphotères et/ou cationiques.
  10. Procédé selon une des revendications 1 à 9,
    caractérisé en ce que
    lors de la neutralisation par pulvérisation le rapport du nombre des groupes acides aux groupes alcalins se situe dans le domaine de 1,1:1 à 0,8:1, de préférence de 1:1 à 0,9:1.
  11. Procédé selon une des revendications 1 à 10,
    caractérisé en ce qu'
    on ajuste des densités apparentes de 400 à 600 g/l et des domaines granulométriques, dans lesquels moins de 5 % en poids comportent un diamètre de particules inférieur à 0,1 mm et au moins 85 % en poids ont un diamètre de particules maximum de 1,6 mm.
  12. Procédé selon une des revendications 1 à 11,
    caractérisé en ce qu'
    on fabrique des granulés tensioactifs, qui comprennent plus de 40 % en poids, de préférence de 50 à 95 % en poids et en particulier de 80 à 90 % en poids de tensioactifs anioniques, de préférence des sulfates d'alkyle en C8-C22, en particulier des sulfates d'alkyle en C12-C18, des sulfates d'alkyle en C16-C18 ou des coupes avec des proportions plus élevées de C12 et de C14.
EP95926892A 1994-07-25 1995-07-14 Procede de fabrication de granules de tensioactif Expired - Lifetime EP0772674B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4425968 1994-07-25
DE4425968A DE4425968A1 (de) 1994-07-25 1994-07-25 Verfahren zur Herstellung von Tensidgranulaten
PCT/EP1995/002777 WO1996003488A1 (fr) 1994-07-25 1995-07-14 Procede de fabrication de granules de tensioactif

Publications (2)

Publication Number Publication Date
EP0772674A1 EP0772674A1 (fr) 1997-05-14
EP0772674B1 true EP0772674B1 (fr) 1998-06-24

Family

ID=6523862

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95926892A Expired - Lifetime EP0772674B1 (fr) 1994-07-25 1995-07-14 Procede de fabrication de granules de tensioactif

Country Status (6)

Country Link
EP (1) EP0772674B1 (fr)
AT (1) ATE167700T1 (fr)
DE (2) DE4425968A1 (fr)
DK (1) DK0772674T3 (fr)
ES (1) ES2117433T3 (fr)
WO (1) WO1996003488A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004005761A1 (de) * 2004-02-05 2005-06-02 Henkel Kgaa Neutralisationsverfahren
US7186677B2 (en) 2001-12-21 2007-03-06 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Method for the production of surfactant granulates containing builders

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19617085A1 (de) * 1996-04-29 1997-10-30 Bayer Ag Verfahren zur Herstellung von feinstteiligen Kristallisationsprodukten
DE19820943A1 (de) 1998-05-11 1999-11-18 Henkel Kgaa Alkylsulfat-Granulate
DE19844523A1 (de) * 1998-09-29 2000-03-30 Henkel Kgaa Granulationsverfahren
DE19844522A1 (de) 1998-09-29 2000-03-30 Henkel Kgaa Granulationsverfahren
DE19855380A1 (de) * 1998-12-01 2000-06-08 Henkel Kgaa Granulationsverfahren
DE19910789A1 (de) * 1999-03-11 2000-09-14 Henkel Kgaa Granulationsverfahren
DE10003124A1 (de) 2000-01-26 2001-08-09 Cognis Deutschland Gmbh Verfahren zur Herstellung von Tensidgranulaten
EP2138565A1 (fr) * 2008-06-25 2009-12-30 The Procter and Gamble Company Procédé de séchage par atomisation
EP2138566A1 (fr) * 2008-06-25 2009-12-30 The Procter and Gamble Company Procédé de séchage par atomisation
US7811980B1 (en) 2009-06-09 2010-10-12 The Procter & Gamble Company Spray-drying process
EP2341123A1 (fr) * 2009-12-18 2011-07-06 The Procter & Gamble Company Procédé de séchage par atomisation
ES2390219T3 (es) * 2009-12-18 2012-11-07 The Procter & Gamble Company Procedimiento de secado por pulverización
EP2338969B1 (fr) 2009-12-18 2017-07-26 The Procter & Gamble Company Procédé de séchage par atomisation
EP2338968A1 (fr) * 2009-12-18 2011-06-29 The Procter & Gamble Company Procédé de séchage par atomisation
EP2341124B1 (fr) * 2009-12-18 2017-07-26 The Procter & Gamble Company Procédé de séchage par atomisation

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH555888A (it) * 1966-03-18 1974-11-15 Micol Anstalt Procedimento e dispositivo per la produzione di detergenti sintetici in forma granulare.
ZA72295B (en) * 1971-02-01 1973-09-26 Colgate Palmolive Co Method for neutralization of detergent acid
DE3741401A1 (de) * 1987-12-07 1989-06-15 Henkel Kgaa Verfahren zur herstellung von festen oder pastenfoermigen produkten
JPH08501118A (ja) * 1992-09-08 1996-02-06 ユニリーバー・ナームローゼ・ベンノートシヤープ 洗剤組成物及びその製造方法
JPH06166898A (ja) * 1992-12-01 1994-06-14 Lion Corp 高嵩密度洗剤組成物の製造方法
DE4304062A1 (de) * 1993-02-11 1994-08-18 Henkel Kgaa Verfahren zur Herstellung von Tensidgranulaten

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7186677B2 (en) 2001-12-21 2007-03-06 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Method for the production of surfactant granulates containing builders
DE102004005761A1 (de) * 2004-02-05 2005-06-02 Henkel Kgaa Neutralisationsverfahren

Also Published As

Publication number Publication date
ATE167700T1 (de) 1998-07-15
DK0772674T3 (da) 1999-04-06
DE59502656D1 (de) 1998-07-30
EP0772674A1 (fr) 1997-05-14
WO1996003488A1 (fr) 1996-02-08
ES2117433T3 (es) 1998-08-01
DE4425968A1 (de) 1996-02-01

Similar Documents

Publication Publication Date Title
EP0642576B1 (fr) Procede de fabrication continue d'un detergent et/ou d'un nettoyant granulaire
EP0603207B1 (fr) Procede de fabrication de granulats tensioactifs
EP0772674B1 (fr) Procede de fabrication de granules de tensioactif
EP0541608B1 (fr) Procede de production de granules actifs de lavage et de nettoyage
EP0683814B1 (fr) Procede de production d'agents tensio-actifs granules
WO1993015180A1 (fr) Procede pour fabriquer des produits solides de lavage et de nettoyage de densite apparente elevee et presentant une vitesse de dissolution amelioree
EP0663005B1 (fr) Procede de fabrication de granules tensioactifs
EP0538294B1 (fr) Procede de production d'agents tensio-actifs granules de lavage et de nettoyage
EP0804529B1 (fr) Compose silicate alcalin amorphe
WO1993004154A1 (fr) Procede de fabrication de granulats carbonates
EP0839178B1 (fr) Compose amorphe de silicate alcalin
EP0724620B1 (fr) Procede de production d'extrudes de lavage ou de nettoyage a pouvoir ameliore de redispersion
EP1036158B1 (fr) Procede de production de melanges de matieres premieres de masse volumique apparente elevee
EP0874684B1 (fr) Procede de production d'un additif granule
EP0674703B1 (fr) Procede de fabrication d'un detergent et nettoyant granule
EP0888444A1 (fr) Procede de production de detergents ou de nettoyants granulaires coulants
DE4209434A1 (de) Verbessertes Verfahren zur Gewinnung von oberflächenaktiven Aniontensid-Salzen durch Sprühneutralisation in einer Heißgasphase
DE4201877A1 (de) Verfahren zur herstellung carbonathaltiger granulate
WO1997018290A1 (fr) Procede de preparation de detergents et de nettoyants granulaires ou constituants utilises pour les preparer
EP0871697A1 (fr) Procede de production d'agents de lavage et de nettoyage en granules ou composants utilises a cet effet

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19970116

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB IT LI NL SE

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 19970821

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB IT LI NL SE

REF Corresponds to:

Ref document number: 167700

Country of ref document: AT

Date of ref document: 19980715

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 19980713

Year of fee payment: 4

Ref country code: AT

Payment date: 19980713

Year of fee payment: 4

REF Corresponds to:

Ref document number: 59502656

Country of ref document: DE

Date of ref document: 19980730

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2117433

Country of ref document: ES

Kind code of ref document: T3

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19980817

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19980914

Year of fee payment: 4

ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN P. & C. S.N.C.

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990714

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990731

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990731

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990802

BERE Be: lapsed

Owner name: HENKEL K.G.A.A.

Effective date: 19990731

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20020705

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030715

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

NLS Nl: assignments of ep-patents

Owner name: COGNIS DEUTSCHLAND GMBH & CO. KG

EUG Se: european patent has lapsed
REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20090514 AND 20090520

NLS Nl: assignments of ep-patents

Owner name: COGNIS IP MANAGEMENT GMBH

Effective date: 20090507

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20140728

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20140825

Year of fee payment: 20

Ref country code: GB

Payment date: 20140729

Year of fee payment: 20

Ref country code: FR

Payment date: 20140731

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20140728

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20140930

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 59502656

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: V4

Effective date: 20150714

REG Reference to a national code

Ref country code: NL

Ref legal event code: V4

Effective date: 20150714

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20150713

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20151026

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20150713

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20150715