EP1451283B1 - Procede de production de granules activateurs de blanchiment - Google Patents

Procede de production de granules activateurs de blanchiment Download PDF

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Publication number
EP1451283B1
EP1451283B1 EP02787771A EP02787771A EP1451283B1 EP 1451283 B1 EP1451283 B1 EP 1451283B1 EP 02787771 A EP02787771 A EP 02787771A EP 02787771 A EP02787771 A EP 02787771A EP 1451283 B1 EP1451283 B1 EP 1451283B1
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EP
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Prior art keywords
granules
alkyl
weight
formula
compound according
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EP02787771A
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German (de)
English (en)
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EP1451283A1 (fr
Inventor
Georg Assmann
Olaf Joachim Blochwitz
Horst-Dieter Speckmann
Jörg Poethkow
Birgit Middelhauve
Gerhard Blasey
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/3925—Nitriles; Isocyanates or quarternary ammonium nitriles
    • 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 preparing bleach activator-containing granules from a water-containing bleach activator preparation by granulation and simultaneous drying in a fluidized bed and subsequent solidification of the primary granules by treatment with an aqueous polymer and / or phosphonate also in a fluidized bed.
  • Detergents and cleaners in addition to the indispensable for the washing process ingredients such as surfactants and builders usually other ingredients that can be summarized under the term laundry aids and include as different drug groups such as foam regulators, graying inhibitors, bleaching agents and dye transfer inhibitors.
  • Such excipients also include substances which promote surfactant performance by the oxidative degradation of soils or those in the liquor susceptible to textiles. The same applies mutatis mutandis to cleaners for hard surfaces.
  • inorganic peroxygen compounds particularly hydrogen peroxide and solid peroxygen compounds which dissolve in water releasing hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes.
  • the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, for the numerous proposals, especially from the classes of N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N- acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, Sulfurylamides and cyanurates, in addition carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxy-benzenesulfonate and acylated sugar derivatives, such as pentaacetylglucose, have become known in the literature.
  • bleach activators for the
  • European Patent Application EP 0 464 880 discloses bleach-enhancing cationic nitriles of the general formula R'R''R '''N + -CR 1 R 2 -CN X - in which R 1 and R 2 are hydrogen or a substituent having at least a C atom, R 'is a C 1-24 alkyl, alkenyl or alkyl ether group or a group -CR 1 R 2 -CN, and R "and R"' are each a C 1-24 alkyl or hydroxyalkyl group and the counter anion is X - an organic sulfonate, an organic sulfate or a carboxylate.
  • the bleach activator granules thus obtained, or the proportion of good grain therefrom preferably has average particle diameters in the range from 0.2 mm to 2.5 mm, in particular in the range from 0.4 mm to 2.0 mm. Its bulk density is preferably in the range of 300 g / l to 1000 g / l, in particular in the range of 400 g / l to 800 g / l.
  • the proportion of compound of formula (I) is preferably in the range of 10 wt .-% to 90 wt .-%, in particular from 15 wt .-% to 50 wt .-%. It is preferably used to prepare particulate detergents or cleaners.
  • the concentration of compound of formula (I) is preferably 10 wt .-% to 90 wt .-%, in particular from 15 wt .-% to 50 wt .-%.
  • Alkalicumolsulfonat which can be used as a solid or as an aqueous solution and preferably in proportions (compound of formula (I) to Alkalicumolsulfonat) of 10: 1 1 to 1: 5, in particular from 2: 1 to 1: 2 is used, the pH value by adding system-compatible acid, such as sulfuric acid and / or citric acid, to an acidic value, if such is not already present, and sprays the solution in a fluidized bed apparatus above one with passages for the fluidizing gas, in particular Vortex air, provided inflow, whereby their water is extracted and form granules.
  • system-compatible acid such as sulfuric acid and / or citric acid
  • Fluidized bed apparatus which can be used in a process according to the invention are known, for example, from European Patent EP 0 603 207 B1 or German Patent Application DE 197 50 424.
  • the passage openings can be covered by a grid, in particular with mesh sizes smaller than 600 ⁇ m.
  • the grid can be arranged within or above the passage openings.
  • the grid is preferably located directly below the openings of the inflow floor, as is known in principle from German Patent Application DE 197 50 424.
  • a metal gauze with the appropriate mesh size can be sintered or otherwise secured to the underside of a known inflow base.
  • the metal gauze preferably consists of the same material as the distributor plate, in particular of stainless steel.
  • the fine-meshed grid is a falling through of particles especially at an unscheduled shutdown of the granulation, but also in particular in the case of very heavy particles with bulk densities of 1000 g / l, even during operation, prevented.
  • the mesh size of said grid is between 200 and 400 microns. It is also advantageous if the inlet plate used has a pressure drop of at most 10 mbar and in particular at most 6 mbar.
  • the primary granules In order to improve the flowability of the primary granules thus obtained, it can be powdered subsequent to the granulation step with finely divided material selected from silica, zeolite and / or sodium cumenesulfonate.
  • solidification apparatus which may be identical in construction to the previously used fluidized bed apparatus, sprayed with an aqueous solidifying solution.
  • Suitable solidifying agents are polymeric polycarboxylates, in particular polymerization products of acrylic acid, methacrylic acid or maleic acid, or copolymers of at least two of these, which are used in completely or at least partially neutralized form, in particular in the form of the alkali metal salts.
  • alkali phosphonate can be used.
  • sodium is the particular preferred alkali metal.
  • the setting of the solidification liquid to the lowest possible viscosity for good droplet distribution in the atomization in the solidification apparatus with simultaneous drying.
  • the granules are discharged in known manner from the fluidized bed and optionally classified according to the particle size, whereby undesirable small particles (fine grain) and undesirably large particles (coarse grain) can be returned to the process after a grinding step.
  • the recycling can be carried out in the granulation step or the powdering step or in both steps.
  • the classified good grain can be re-introduced into a fluidized bed apparatus and sprayed onto it solidifier solution in order to further improve the product properties of the granules if necessary.
  • the anions X - include in particular the halides such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, phosphate, hydrogen phosphate, dihydrogen phosphate, pyrophosphate, metaphosphate, hexafluorophosphate, carbonate, bicarbonate, sulfate, hydrogen sulfate, C 1-20 alkyl sulfate, C 1-20 alkyl sulfonate, optionally C 1-18 alkyl-substituted aryl sulfonate, chlorate, perchlorate and / or the anions of C 1-24 carboxylic acids such as formate, acetate, laurate, benzoate or citrate, alone or in any mixtures.
  • halides such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, phosphate, hydrogen phosphate, dihydrogen phosphate, pyrophosphate, metaphosphate
  • toluenesulfonate or cumene sulfonate is understood as meaning the anion of the ortho, meta or para isomers of methylbenzenesulfonic acid or isopropylbenzenesulfonic acid and any mixtures thereof.
  • Para- isopropylbenzenesulfonic acid is particularly preferred.
  • a granulate produced by the process according to the invention is storage-stable, free-flowing and of sufficient grain stability, in order to be able to be mixed in a conventional manner with other particulate constituents of washing or cleaning agents.
  • the bleach-activating effect of the compound according to formula (I) is not significantly impaired by the process.
  • Granules produced by the process according to the invention are in particular particulate detergents or cleaners preferably used in amounts such that these agents have contents of 0.1 wt .-% to 10 wt .-%, in particular from 0.2 wt .-% to 7 wt .-% of bleach activator according to formula (I).
  • a supply air temperature of 95 ° C and an exhaust air temperature of 55 ° C from a homogeneous aqueous solution of trimethylammoniumacetonitrile and Na-cumene sulfonate (mass ratio 1: 1, dry matter content 30%) produced at a throughput of the solution of 3 kg / h within 5 h granules that was still very sticky.
  • the stickiness could be eliminated by repeated granulation with a 20% aqueous solution of polymeric polycarboxylate (Sokalan® CP45, manufacturer BASF) under the same conditions with respect to supply air flow, supply air temperature and exhaust air temperature.
  • the polymer content in the granules thus obtained was 5% by weight.
  • the grain size of the granules was in the range of 0.4 mm to 2.0 mm, the bulk density was 700 g / l.
  • the granules were sieved and mixed the proportion with particle sizes of between 0.8 and 1.6 mm with the other detergent components of a detergent formulation. The finished detergent could be used without clumping.
  • a primary granulate was prepared from a 40% strength aqueous solution of the cationic nitrile used in Example 1 while being powdered with sodium cumenesulfonate powder.
  • the supply air volume was 21000 m 3 / h, the supply air temperature was 145 ° C.
  • the exhaust air temperature was adjusted to 65 ° C by the water evaporation of the solution.
  • the batch-operated fluidized bed was so full that the granulation was stopped.
  • the solidification was carried out with the 20% polymer solution used in Example 1 at 110 ° C supply air.
  • the polymer content in the finished granules was 10 wt .-%.
  • the resulting granules were screened between 0.8 and 1.6 mm.
  • the bulk density was 730 g / l.
  • the finished granules were treated with conventional particulate detergent components to a particulate detergent.
  • a primary granulate was prepared from a 40% strength aqueous solution of the cationic nitrile used in Example 1 by powdering with silica powder (Thixosil® 38A).
  • the supply air volume was 20,000 m 3 / h, the supply air temperature was 140 ° C.
  • the exhaust air temperature was adjusted to 65 ° C by the water evaporation of the solution.
  • the batch-operated fluidized bed was so full that the granulation was stopped.
  • the solidification was carried out with the 20% polymer solution used in Example 1 at 110 ° C supply air.
  • the polymer content in the finished granules was 7 wt .-%.
  • the resulting granules were screened between 0.8 and 1.6 mm.
  • the bulk density was 710 g / l.
  • the granules obtained according to Example 2 was reintroduced into the fluidized bed apparatus and sprayed there at 130 ° C supply air temperature and 65 ° C exhaust air temperature with the previously used 20% polymer solution from the side, so that a 20 wt% coating was formed.
  • the granules obtained according to Example 3 was reintroduced into the fluidized bed apparatus and sprayed there at 130 ° C supply air temperature and 65 ° C exhaust air temperature with the 20% polymer solution from the side, so that a 10 weight percent coating was formed.

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  • 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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (9)

  1. Procédé pour la préparation d'une composition en forme de particules, contenant un composé selon la formule (I),
    Figure imgb0004
     dans laquelle R1 représente -H, -CH3, un radical alkyle ou alcényle en C2 à C24, un radical alkyle ou alcényle en C2 à C24 substitué par au moins un substituant du groupe -Cl, -Br, -OH, -NH2, -CN, un radical alkylaryle ou alcénylaryle présentant un groupe alkyle en C1 à C24 ou un radical alkylaryle ou alcénylaryle substitué présentant un groupe alkyle en C1 à C24 et au moins un autre substituant sur le cycle aromatique, R2 et R3 sont choisis, indépendamment l'un de l'autre, parmi -CH2-CN, -CH3, -CH2-CH3, -CH2-CH2-CH3, -CH(CH3)-CH3, -CH2-OH, -CH2-CH2-OH, -CH(OH)-CH3, -CH2-CH2-CH2-OH, -CH2-CH(OH)-CH3, -CH(OH)-CH2-CH3, -(CH2CH2-O)nH avec n = 1, 2, 3, 4, 5 ou 6, R4 et R5 présentent, indépendamment l'un de l'autre, une signification indiquée ci-dessus pour R1, R2 ou R3 et X est un anion compensant la charge, caractérisé par les étapes
    a) formation d'une solution aqueuse, contenant le nitrile cationique et le cas échéant du cumènesulfonate alcalin, en particulier le cumènesulfonate de sodium,
    b) le cas échéant réglage de la solution à un pH acide, en particulier par addition d'acide sulfurique et/ou d'acide citrique,
    c) évaporation et séchage de la solution dans un appareil à lit fluidisé,
    d) le cas échéant saupoudrage du granulat primaire ainsi obtenu avec utilisation de silice, de zéolithe, et/ou de cumènesulfonate de sodium dans le lit fluidisé,
    e) solidification du granulat primaire, le cas échéant saupoudré, par une aspersion consécutive avec une solution d'agent de solidification aqueux, qui contient comme substance active de solidification du polycarboxylate polymère et/ou du phosphonate alcalin avec séchage simultané dans le même appareillage à lit fluidisé ou le cas échéant dans un deuxième appareillage à lit fluidisé disposé en aval,
    f) évacuation des granulats de l'appareillage à lit fluidisé et le cas échéant séparation des granulats en bons grains et grains gros/fins, en particulier par tamisage,
    g) le cas échéant recyclage des grains fins et/ou des gros grains broyés dans le lit fluidisé dans l'étape c),
    h) le cas échéant recyclage des grains fins et/ou des gros grains broyés dans l'étape de saupoudrage d).
  2. Procédé selon la revendication 1, caractérisé en ce qu'on part d'une solution aqueuse du composé selon la formule (I), dans laquelle la concentration est de 10% en poids à 90% en poids, en particulier de 15% en poids à 50% en poids.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce qu'on utilise comme substance active de solidification un produit de polymérisation d'acide acrylique, d'acide méthacrylique ou d'acide maléique ou des copolymères d'au moins deux de ceux-ci, sous forme complètement ou du moins partiellement neutralisée, en particulier sous forme des sels alcalins et/ou un phosphonate de métal alcalin.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'on utilise un composé selon la formule I, dans laquelle R1, R2 et R3 sont identiques et signifient en particulier des groupes méthyle.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'on utilise un composé selon la formule I, dans laquelle l'anion X- représente un anion halogénure, tel que chlorure, fluorure, iodure et bromure, nitrate, hydroxyde, phosphate, hydrogénophosphate, dihydrogénophosphate, pyrophosphate, métaphosphate, hexafluorophosphate, carbonate, hydrogénocarbonate, sulfate, hydrogénosulfate, (alkyle en C1 à C20)sulfate, (alkyle en C1 à C20)sulfonate, arylsulfonate le cas échéant substitué par alkyle en C1 à C18, chlorate, perchlorate et/ou un anion d'un acide carboxylique en C1 à C24, tel qu'un anion formiate, acétate, laurate, benzoate ou citrate, seul ou dans des mélanges quelconques.
  6. Procédé selon la revendication 5, caractérisé en ce qu'on utilise un composé selon la formule I, dans laquelle l'anion X- représente un anion chlorure, sulfate, hydrogénosulfate, méthosulfate, éthosulfate, (alkyle en C12/18, en C12/16 ou en C13/15)sulfate, laurylsulfate, dodécylbenzènesulfonate, toluènesulfonate, cumènesulfonate, xylènesulfonate ou des mélanges de ceux-ci.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que la composition sous forme de particules présente un diamètre moyen des particules dans la plage de 0,2 mm à 2,5 mm, en particulier dans la plage de 0,4 mm à 2,0 mm.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que la densité apparente de la composition en forme de particules se situe dans la plage de 300 g/l à 1 000 g/l, en particulier dans la plage de 400 g/l à 800 g/l.
  9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que la proportion du composé selon la formule (I) dans la composition sous forme de particules se situe dans la plage de 10% en poids à 90%. en poids, en particulier de 15% en poids à 50% en poids.
EP02787771A 2001-12-04 2002-11-22 Procede de production de granules activateurs de blanchiment Expired - Lifetime EP1451283B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10159386A DE10159386A1 (de) 2001-12-04 2001-12-04 Verfahren zur Herstellung von Bleichaktivatorgranulaten
DE10159386 2001-12-04
PCT/EP2002/013126 WO2003048289A1 (fr) 2001-12-04 2002-11-22 Procede de production de granules activateurs de blanchiment

Publications (2)

Publication Number Publication Date
EP1451283A1 EP1451283A1 (fr) 2004-09-01
EP1451283B1 true EP1451283B1 (fr) 2007-01-03

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EP02787771A Expired - Lifetime EP1451283B1 (fr) 2001-12-04 2002-11-22 Procede de production de granules activateurs de blanchiment

Country Status (8)

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US (1) US7064100B2 (fr)
EP (1) EP1451283B1 (fr)
JP (1) JP2005511822A (fr)
AT (1) ATE350449T1 (fr)
AU (1) AU2002352097A1 (fr)
DE (2) DE10159386A1 (fr)
ES (1) ES2278990T3 (fr)
WO (1) WO2003048289A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10159388A1 (de) * 2001-12-04 2003-06-12 Henkel Kgaa Verfahren zur Herstellung von umhüllten Bleichaktivatorgranulaten
DE10314441A1 (de) * 2003-03-31 2004-10-21 Henkel Kgaa Bleichaktivator-Compounds
JP2007509188A (ja) * 2003-05-02 2007-04-12 クラリアント・プロドゥクテ・（ドイチュラント）・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング 顆粒状アンモニウムニトリルの製造方法
US7796069B2 (en) * 2008-02-06 2010-09-14 02Micro International Limited Analog to digital converters

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9012001D0 (en) 1990-05-30 1990-07-18 Unilever Plc Bleaching composition
DE4127323A1 (de) 1991-08-20 1993-02-25 Henkel Kgaa Verfahren zur herstellung von tensidgranulaten
DE4129074A1 (de) * 1991-09-02 1993-03-04 Leuna Werke Ag Verfahren zur herstellung von granulaten aus pulverfoermigen, n-acetylierten bleichmittelaktivatoren
US5888419A (en) * 1995-06-07 1999-03-30 The Clorox Company Granular N-alkyl ammonium acetontrile compositions
US5814242A (en) * 1995-06-07 1998-09-29 The Clorox Company Mixed peroxygen activator compositions
DE19649375A1 (de) * 1996-11-29 1998-06-04 Henkel Kgaa Acetonitril-Derivate als Bleichaktivatoren in Reinigungsmitteln
DE19740671A1 (de) * 1997-09-16 1999-03-18 Clariant Gmbh Bleichaktivator-Granulate
DE19750424A1 (de) 1997-11-14 1999-05-20 Henkel Kgaa Verbessertes Verfahren zum Herstellen von Tensidgranulaten mit einem hohen Schüttgewicht
DE19841184A1 (de) * 1998-09-09 2000-03-16 Clariant Gmbh Bleichaktivatorgranulate
DE19908051A1 (de) * 1999-02-25 2000-08-31 Henkel Kgaa Verfahren zur Herstellung compoundierter Acetonitril-Derivate
DE19908069A1 (de) 1999-02-25 2000-08-31 Henkel Kgaa Compoundierte Acetonitril-Derivate als Bleichaktivatoren in Reinigungsmitteln
DE10038086A1 (de) * 2000-08-04 2002-02-14 Clariant Gmbh Verfahren zur Herstellung von hydrolysestabilen Ammoniumnitrilen

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Publication number Publication date
DE50209196D1 (de) 2007-02-15
DE10159386A1 (de) 2003-06-12
AU2002352097A1 (en) 2003-06-17
US7064100B2 (en) 2006-06-20
US20040248755A1 (en) 2004-12-09
WO2003048289A1 (fr) 2003-06-12
EP1451283A1 (fr) 2004-09-01
ATE350449T1 (de) 2007-01-15
JP2005511822A (ja) 2005-04-28
ES2278990T3 (es) 2007-08-16

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