EP1451283A1 - Procede de production de granules activateurs de blanchiment - Google Patents

Procede de production de granules activateurs de blanchiment

Info

Publication number
EP1451283A1
EP1451283A1 EP02787771A EP02787771A EP1451283A1 EP 1451283 A1 EP1451283 A1 EP 1451283A1 EP 02787771 A EP02787771 A EP 02787771A EP 02787771 A EP02787771 A EP 02787771A EP 1451283 A1 EP1451283 A1 EP 1451283A1
Authority
EP
European Patent Office
Prior art keywords
granules
optionally
fluidized bed
alkyl
formula
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.)
Granted
Application number
EP02787771A
Other languages
German (de)
English (en)
Other versions
EP1451283B1 (fr
Inventor
Georg Assmann
Olaf Joachim Blochwitz
Horst-Dieter Speckmann
Jörg Poethkow
Birgit Middelhauve
Gerhard Blasey
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.)
Henkel AG and Co KGaA
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 EP1451283A1 publication Critical patent/EP1451283A1/fr
Application granted granted Critical
Publication of EP1451283B1 publication Critical patent/EP1451283B1/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
    • 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 the production of bleach activator-containing granules from a water-containing bleach activator preparation form 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 solution, likewise in a fluidized bed.
  • detergents and cleaning agents In addition to the ingredients that are indispensable for the washing process, such as surfactants and builder materials, detergents and cleaning agents generally contain other ingredients that can be summarized under the term washing aids and that include such different active ingredient groups as foam regulators, graying inhibitors, bleaching agents and color transfer inhibitors. Such auxiliaries also include substances that support the surfactant performance through the oxidative degradation of soiling on the textile or such in the fleet. The same applies analogously to cleaning agents for hard surfaces. Inorganic peroxygen compounds, in particular hydrogen peroxide and solid peroxygen compounds which dissolve in water with the liberation of hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfection and bleaching purposes.
  • oxidation effect of these substances in dilute solutions depends strongly on the temperature; For example, with H 2 O 2 or sodium perborate in alkaline bleaching liquors, sufficiently quick bleaching of soiled textiles can only be achieved at temperatures above about 60 ° C. At lower temperatures, the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, for which numerous suggestions, especially from the substance classes of the N- or O-acyl compounds, for example multiply acylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N- acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, Sulfurylamides and cyanurates, also carboxylic anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodium nonanoyloxy-
  • European patent application EP 0 464 880 discloses bleach-boosting cationic nitriles of the general formula R'R “R '" N + -CR 1 R 2 -CN X " , in which R and R 2 are hydrogen or a substituent with at least one C. -Atom, R 'is a C ⁇ alkyl, alkenyl or alkyl ether group or a group -CRjR 2 -CN, and R "and R"' are each a C, .24 alkyl or hydroxyalkyl group and the counter anion X " is organic sulfonate, an organic sulfate or a carboxylate.
  • cationic nitriles fall within the scope It can be produced in liquid form, for example as a particularly aqueous solution, and can be convert them into the pure solid only with considerable losses, so that their use in solid, for example particulate compositions causes difficulties.
  • cationic nitriles are particularly in combination with other ingredients of washing and Detergents usually have little storage stability and are particularly sensitive to moisture.
  • the object of the invention was therefore to provide a production process by means of which aqueous preparations which contain a cationic nitrile can be converted into particulate preparations, so that the bleach-activating active substance of the cationic nitrile is incorporated into solid detergents and cleaning agents without loss as far as possible leaves. It has now been found that the preparation of such preparations is possible using a fluidized bed granulation process. In this way, drying and granulation can be carried out in a simple manner in one device, the production of granules with a particularly high content of cationic nitrile being easily possible.
  • the invention relates to a process for the preparation of a particulate preparation comprising a compound of the formula (I),
  • R 1 for -H, -CH 3 a C 2 . 24 alkyl or alkenyl radical, a substituted C 2 _ 24 alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br, -OH, -NH 2 , -CN, an alkyl or alkenylaryl radical with a C L ⁇ alkyl group, or for a substituted alkyl or alkenylaryl radical with a C 1 .
  • the bleach activator granulate obtained in this way, or the proportion of good grains thereon 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 from 300 g / 1 to 1000 g / 1, in particular in the range from 400 g / 1 to 800 g / 1.
  • the proportion of compound of the formula (I) is preferably in the range from 10% by weight to 90% by weight, in particular from 15% by weight to 50% by weight. It is preferably used for the production of particulate detergents or cleaning agents.
  • an aqueous solution of the compound of the formula (I), as is obtained in the preparation thereof is preferably used.
  • the concentration of compound according to formula (I) is preferably 10% by weight to 90% by weight, in particular from 15% by weight to 50% by weight.
  • alkali metal sulphonate which can be used as a solid or as an aqueous solution and preferably in proportions (compound of the formula (I) to alkali metal sulphonate) from 10: 1 to 1: 5, in particular from 2: 1 to 1: 2, to Is used, adjusts the pH to an acidic value by adding system-compatible acid, for example sulfuric acid and / or citric acid, if one is not already available, and sprays the solution in a fluidized bed apparatus above one with openings for the fluidizing gas, in particular fluidizing air , provided on the inflow floor, whereby their water is extracted and granules form.
  • system-compatible acid for example sulfuric acid and / or citric acid
  • Fluidized bed devices which can be used in a method 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 through openings can be covered by a grid, in particular with mesh sizes of less than 600 ⁇ m.
  • the grid can be arranged inside or above the passage openings. However, the grid is preferably located directly below the through 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 onto the underside of a known inflow floor or attached in some other way.
  • the metal gauze preferably consists of the same material as the inflow floor, in particular of stainless steel.
  • the fine-meshed grid prevents particles from falling through, especially when the granulation system has come to an unscheduled standstill, but also in particular in the case of particularly heavy particles with bulk densities of around 1000 g / l, even during operation.
  • the mesh size of the grid mentioned is preferably between 200 and 400 microns. It is also advantageous if the inflow floor used has a pressure loss of at most 10 mbar and in particular at most 6 mbar.
  • the primary granules obtained in this way they can be powdered with fine-particle material selected from silica, zeolite and / or sodium cumene sulfonate after the granulation step.
  • 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 metal phosphonate can be used as an alternative or in addition to polymeric polycarboxylate. In the alkali metal salts mentioned, sodium is the preferred alkali metal in each case. Preference is given to setting the solidifying liquid to a viscosity which is as low as possible for good droplet distribution during atomization in the solidifying apparatus with simultaneous drying.
  • the granules are discharged from the fluidized bed in a manner known in principle and optionally massaged according to the particle size, undesirably small particles (fine particles) and undesirably large particles (coarse particles) being returned to the process after a grinding step.
  • the stirring can be carried out in the granulation step or the powdering step or in both steps.
  • the classified good grain can be introduced again into a fluidized bed apparatus and sprayed onto the hardening solution in order to further improve the product properties of the granulate if necessary.
  • Compounds of the formula I can be prepared by known processes or based on these, as described, for example, in the patent literature mentioned or by Abraham in Progr. Phys. Org. Chem. 11 (1974), pp. Lff, or from Arnett in J. Am. Chem. Soc. 102 (1980), p. 5892ff. have been published.
  • 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, hydrogen carbonate, sulfate, hydrogen sulfate, C,. 20 alkyl sulfate, C j .
  • halides such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, phosphate, hydrogen phosphate, dihydrogen phosphate, pyrophosphate, metaphosphate, hexafluorophosphate, carbonate, hydrogen carbonate, sulfate, hydrogen sulfate, C,. 20 alkyl sulfate, C j .
  • j o-alkyl sulfonate optionally C Mg alkyl-substituted aryl sulfonate, chlorate, perchlorate and / or the anions of C, 24 -carboxylic acids such as formate, acetate, laurate, benzoate or citrate, alone or in any mixtures Formula I, in which X " chloride, sulfate, hydrogen sulfate, ethosulfate, C 12 lg -, C 12/16 - or C 13/15 alkyl sulfate, lauryl sulfate, dodecyl benzenesulfonate, toluenesulfonate, cumene sulfonate, xylene sulfonate or methosulfate or mixtures of these is.
  • Toluene sulfonate or cumene sulfonate means the anion of the ortho, meta or ⁇ r ⁇ isomer of methylbenzenesulfonic acid or isopropylbenzenesulfonic acid and any mixtures thereof.
  • P ⁇ r ⁇ -isopropylbenzenesulfonic acid is particularly preferred.
  • a granulate produced by the process according to the invention is stable on storage, free-flowing and of sufficient grain stability to be able to be mixed in a customary manner with other particulate constituents of detergents or cleaning agents.
  • the process does not significantly impair the bleach-activating action of the compound of the formula (I).
  • Granules produced by the process according to the invention are in particular particulate washing or cleaning agents are preferably used in amounts such that these agents have contents of 0.1% by weight to 10% by weight, in particular from 0.2% by weight to 7% by weight, 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 trimethylammonium acetonitrile methosulfate and Na-cumolsulfonate (mass ratio 1: 1, dry matter content 30%) with a throughput of the solution of 3 kg / h within 5 h, a granulate which 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 regard to the 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 from 0.4 mm to 2.0 mm, the bulk density was 700 g / 1.
  • the granules were then sieved and the portion with particle sizes of between 0.8 and 1.6 mm was mixed with the other detergent components of a detergent formulation. The finished detergent could be used without clumping.
  • the granules obtained according to Example 2 were reintroduced into the fluidized bed apparatus and sprinkled from the side with the 20% polymer solution already used at 130 ° C. supply air temperature and 65 ° C. exhaust air temperature, so that a 20 percent by weight coating was obtained.
  • the granules obtained according to Example 3 were reintroduced into the fluidized bed apparatus and sprinkled with the 20% polymer solution from the side at 130 ° C. supply air temperature and 65 ° C. exhaust air temperature, so that a 10 percent by weight coating was obtained.

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

Abstract

L'objectif de l'invention est d'améliorer un procédé de production de granulés activateurs de blanchiment de façon à accroître la stabilité au stockage et la faculté d'écoulement des granulés. Cet objectif est atteint essentiellement grâce à un procédé comprenant les étapes suivantes : a) préparation d'une solution aqueuse contenant du nitrile cationique et éventuellement du cumènesulfonate alcalin, b) ajustage éventuel du pH de la solution sur une valeur acide, c) atomisation et séchage de la solution dans un appareil à lit fluidisé, d) poudrage éventuel des granulés primaires ainsi obtenus dans le lit fluidisé, e) durcissement des granulés primaires éventuellement poudrés par pulvérisation sur ces granulés d'une solution aqueuse de durcissement, contenant comme agent de durcissement du polycarboxylate polymère et/ou du phosphonate alcalin, et séchage simultané dans le même appareil à lit fluidisé ou éventuellement dans un deuxième appareil à lit fluidisé situé en aval, f) extraction des granulés de l'appareil à lit fluidisé et séparation éventuelle de ces granulés en granulés acceptables et granulés gros/fins, en particulier par tamisage, g) renvoi éventuel des granulés fins et/ou des gros granulés broyés dans le lit fluidisé à l'étape c), h) renvoi éventuel des granulés fins et/ou des gros granulés broyés à l'étape de poudrage d).
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 true EP1451283A1 (fr) 2004-09-01
EP1451283B1 EP1451283B1 (fr) 2007-01-03

Family

ID=7707894

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02787771A Expired - Lifetime EP1451283B1 (fr) 2001-12-04 2002-11-22 Procede de production de granules activateurs de blanchiment

Country Status (8)

Country Link
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03048289A1 *

Also Published As

Publication number Publication date
US7064100B2 (en) 2006-06-20
ATE350449T1 (de) 2007-01-15
AU2002352097A1 (en) 2003-06-17
EP1451283B1 (fr) 2007-01-03
JP2005511822A (ja) 2005-04-28
DE50209196D1 (de) 2007-02-15
ES2278990T3 (es) 2007-08-16
US20040248755A1 (en) 2004-12-09
DE10159386A1 (de) 2003-06-12
WO2003048289A1 (fr) 2003-06-12

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