EP0859048B1 - Process for making surfactant granules - Google Patents

Process for making surfactant granules Download PDF

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Publication number
EP0859048B1
EP0859048B1 EP98100768A EP98100768A EP0859048B1 EP 0859048 B1 EP0859048 B1 EP 0859048B1 EP 98100768 A EP98100768 A EP 98100768A EP 98100768 A EP98100768 A EP 98100768A EP 0859048 B1 EP0859048 B1 EP 0859048B1
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EP
European Patent Office
Prior art keywords
weight
granules
surfactant
cleaning
process according
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.)
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EP98100768A
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German (de)
French (fr)
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EP0859048A3 (en
EP0859048A2 (en
Inventor
Georg Dr. Assmann
Hans-Friedrich Kruse
Volker Dr. Bauer
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP0859048A3 publication Critical patent/EP0859048A3/en
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/66—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
    • 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
    • C11D11/0088—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 the liquefied ingredients being sprayed or adsorbed onto solid particles
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • 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
    • 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
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof

Definitions

  • the invention relates to a process for the production of concentrated surfactant granules Active substance content of more than 45 wt .-%, based on the granules, which a low hygroscopicity, a significantly improved silage capacity and an increased Have bulk density.
  • Granulation is an alternative to spray drying surfactant pastes describes EP-B-0 603 207 (Henkel) a process for the production of washing and cleaning active Surfactant granules with a bulk density above 500 g / l by simultaneous Granulation and drying in all devices in which granulation can be done with simultaneous drying.
  • a surfactant preparation form which is a non-surfactant liquid component (usually water) has, if desired granulated with the addition of a solid component and dried at the same time.
  • the simultaneous spraying also provides of active substance and carrier component solution through one and the same nozzle here is a possible but not a mandatory process parameter.
  • the object of the invention was to provide a method for producing heavy, free-flowing, to provide highly concentrated surfactant granules with bulk densities above 600 g / l, the granules obtained have advantages in terms of ensiling ability and Show hygroscopicity.
  • the process according to the invention has the advantage that the resulting grain is conditional due to the inclusion of surfactant phases in phases of the carrier material, an increased mechanical Stability and an extremely reduced water absorption during storage.
  • the granules obtained by the process according to the invention are accordingly very easy to pour and ensilage and stick together due to their low tendency to absorb water. With separate injection of active substance and carrier paste in the granulation unit is the product even at low surfactant concentrations sticky and cakes on drying, adding the products are hygroscopic and stick in the course of heavy water absorption.
  • the solutions of the active substance and the carrier substance are carried out according to the invention one and the same nozzle atomized.
  • the solutions can only be mixed in the nozzle mixed, i.e. fed to the nozzle via separate storage containers and feed lines but also a mixture of both solutions from a single storage container can be injected through a nozzle.
  • the non-surfactant solvent which may contain one or more components, has a boiling point or boiling range preferably below normal pressure 250 ° C and especially below 200 ° C. With particular advantage, it contains components which boil between 60 and 180 ° C at normal pressure.
  • organic constituents of the non-surfactant solvent are preferably mono- and / or polyfunctional alcohols, for example methanol, ethanol, propanol, Isopropanol, butanol, secondary and tertiary butanol, pentanol, ethylene glycol, 1,2-propanediol, Glycerin or mixtures of these are used.
  • the inorganic component of the non-surfactant Solvent water optionally together with organic components such as ethanol, 1,2-propanediol or glycerin.
  • the share is of the water preferably 25 to 80 wt .-%, based on the total amount of non-surfactant solvent.
  • the solutions of surfactants and carrier materials in Non-surfactant solvents can be used in a wide range of concentrations are taken into account, with only a viscosity that is still suitable for atomization got to.
  • the proportion of the non-surfactant is Solvent 30 to 70 wt .-% and in particular 45 to 60 wt .-%.
  • alkylbenzenesulfonates ABS
  • alkylpolyglycosides APG
  • APG alkylpolyglycosides
  • APG alkylpolyglycosides
  • R is one primary, straight-chain or in the 2-position methyl branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms
  • G is a symbol which represents a glucose unit with 5 or 6 carbon atoms
  • the degree of oligomerization x between 1 and 10, preferably between 1 and 2 and in particular is significantly smaller than 1.4.
  • ABS and / or APG surfactants in addition to the ABS and / or APG surfactants also other anionic, nonionic, cationic or amphoteric surfactants can be used in combination with the former. While the process is mainly used to manufacture ABS and / or APG compounds suitable are additions of up to 20% by weight of other surfactants, based on the total amount of surfactant, possible without losing the advantages of the method according to the invention.
  • the carrier materials used in the process according to the invention can be inorganic and / or organic in nature.
  • they consist of amorphous alkali silicates of the formula (SiO 2 ) m (M 2 O) n1 (so-called water glasses) and / or crystalline layered silicates of the formula (SiO 2 ) m ((M 2 O) n2 (H 2 O ) x , where M is lithium, sodium or potassium, m and n1 are integers or fractional numbers greater than 0, n2 is 1 and x is 0 or integers from 1 to 20.
  • inorganic salts or organic polycarboxylates into consideration.
  • sodium carbonate is among the inorganic salts preferred, while as polycarboxylates preferably citric acid / citrates and / or Acrylic acid / maleic acid copolymers are used.
  • the detergent granules which are active in washing and cleaning, have, based on the finished granulate, Carrier material contents of 10 to 50 wt .-%. Because highly concentrated surfactant granules Preferred for economic reasons are carrier material contents from below 40, in particular below 30% by weight, is preferred. In addition to the so-called over-dried Water glasses can also be found in preferred embodiments of the invention Sodium carbonate, acrylic acid / maleic acid copolymers and trisodium citrate as carrier materials Use. Mixtures of the carrier substances are also preferred, in particular Carbonate / silicate mixtures as well as citrate / silicate mixtures.
  • the surfactant preparation form is granulated and dried, using the method according to the invention.
  • Process granulate particles are obtained in which the active substance is partially enclosed by the carrier. Under drying, this becomes partially or completely remove the non-surfactant solvent.
  • the non-surfactant solvent is preferably removed almost completely.
  • the preparation of the surfactant granules can be carried out by the process according to the invention in all devices take place in which a granulation under drying conditions can be carried out.
  • Examples include heated mixers and granulators, especially high-speed ring mix dryers such as Turbo dryer® granulators (Device from Vomm, Italy).
  • the Invention however, that the combination of the two process steps in a batch or continuously running fluidized bed is carried out. It is special preferred to carry out the process continuously in the fluidized bed.
  • there the surfactant preparation form is introduced into the fluidized bed from a common nozzle.
  • the mixture of the two liquid to pasty components of the surfactant preparation form can be done beforehand or only in the nozzle.
  • Fluid bed apparatuses used have base plates with dimensions of at least 0.4 m.
  • fluidized bed apparatuses are preferred which have a base plate have a diameter between 0.4 and 5 m, for example 1.2 m or 2.5 m.
  • fluidized bed apparatuses are also suitable which have a base plate with a have a diameter greater than 5 m.
  • a perforated base plate is preferably used as the base plate or a Conidur plate (commercial product from Hein & Lehmann, Federal Republic Germany).
  • the method according to the invention is preferred at vortex air speeds between 1 and 8 m / s and in particular between 1.5 and 5.5 m / s performed.
  • the granules are discharged from the fluidized bed advantageously via a size classification of the granules.
  • This classification can for example with a screening device or through an opposed air flow (Classifier air), which is regulated so that only particles above a certain particle size removed from the fluidized bed and smaller particles retained in the fluidized bed become.
  • Classifier air opposed air flow
  • the inflowing settles Air from the heated or unheated classifier air and the heated soil air together.
  • the soil air temperature is preferably between 80 and 400 ° C, in particular between 90 and 350 ° C.
  • the vortex air cools down due to heat loss and by the heat of vaporization of the components of the non-surfactant solvent from.
  • the temperature of the fluidizing air is about 5 cm above the base plate 60 to 120 ° C, preferably 65 to 90 ° C and especially 70 to 85 ° C.
  • the air outlet temperature is preferably between 60 and 120 ° C, especially below 100 ° C and with particular advantage between 70 and 85 ° C.
  • the evaporate Components of the non-surfactant solvent partially or completely, the dried-on to dry germs with additional amounts of surfactant preparation be encased in such a way that the carrier substance is the active substance envelops.
  • This special structure of the granulate which can only be achieved by simultaneous injection Obtain active substance and carrier material solution through one and the same nozzle is the result of the evaporating non-surfactant solvent in the evaporation process Backing material from the freshly condensed layer on the grain carries and deposits on the surface of the grain when evaporating.
  • a powdering agent preferably zeolite or sodium carbonate Fluidized bed
  • these powdering agents reduce the amount of granulation the stickiness of the moist granules and thus promote turbulence and drying to the desired product.
  • this variant can be advantageous is, however, not absolutely necessary to carry out the invention.
  • the process according to the invention results in surfactant granules which dissolve easily in cold water without being hygroscopic.
  • the granules have high mechanical stability and therefore excellent flow and silage properties.
  • Leave with organic solvents that do not destroy the grain structure only small amounts of active substance dissolve from the uncrushed granules, while most of the active substance can be extracted from the ground granules is.
  • the washing and cleaning active produced by the inventive method Surfactant granules have bulk densities above 600 g / l. They are ideal as components suitable for the production of detergents and cleaning agents, preferred Detergents and cleaning agents which are produced by the process according to the invention detergent-active and surfactant granules in amounts of more than 10% by weight, in particular in amounts above 20 wt .-%, based on the total washing and Detergent included.
  • a bulk density according to the invention Process produced washing and cleaning active surfactant granules above of 700 g / l, in particular above 800 g / l, is preferred.
  • the process according to the invention can advantageously be active in washing and cleaning Surfactant granules are produced, the total surfactant content, based on the total granulate is more than 40% by weight.
  • Surfactant contents above 50% by weight and in particular above 60% by weight are preferred.
  • ABS alkylbenzenesulfonate
  • APG alkylpolyglycoside
  • the process is suitable for the production of highly concentrated surfactant granules and has particular advantages if the surfactants to be processed are sticky per se Are natural, as is the case with alkylbenzenesulfonates and alkylpolyglycosides.
  • the proportion of other surfactants is 20% by weight, based on the total surfactant content, does not exceed in the granules according to the invention.
  • composition [% by weight] E1 E2 E3 E4 E5 E6 E7 E8 SECTION 45 - - - 60 50 - 61 APG - 67 80 50 - - 62 - silicate 21 22 17.5 10 13 15 - - Sokalan CP5® - - - - - - 33 - sodium citrate - - - - - - - 14 sodium 28 - - 35 - - - - zeolite - - - - 22 30 - 20 water 6 11 2.5 5 5 5 5 5 5 bulk weight [G / l] 632 641 612 651 702 734 611 633 Sokalan CP5 ® is an acrylic acid-maleic acid copolymer from BASF
  • solubilities of E1 and E2 were determined by adding 5 g each of the agent to a 1 l vessel containing 500 ml of demineralized water which was stirred by a propeller stirrer at 900 rpm. The conductivity was detected via a conductivity measuring cell and recorded on a recorder. The measurement was carried out until no increase was ascertainable. The time to reach the conductivity of the agent was set to 100%, the corresponding other dissolving times were calculated. solubility E1 E2 95% solved [min] 2.59 2.57 90% solved [min] 2.27 2.25 80% solved [min] 1.45 1.48 Residue after 1.5 min [% by weight] 2 5 Residue after 5 min [% by weight] 0 0 0
  • All compounds E1 to E8 produced according to the invention can be stored in the air without sticking or losing their free-flowing properties.
  • a comparison test between ES and a commercially available comparable ABS compound with a bulk density of 400 g / l and an active substance content of 85% by weight showed the following values after 8 hours of storage (55% relative luminous humidity): Hygroscopicity (8-hour storage trial) E5 comparison Water absorption [% by weight] 5 20 Remarks pourable bonding
  • ABS / APG compounds produced according to the invention are ideal additives suitable for detergents since they give the detergents improved solubility.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
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Abstract

A method for the preparation of wash- and cleaning-active surfactant granules with bulk weights greater than 600 g/l by granulating surfactant formulations, comprises: (1) solutions of (A) alkyl benzene sulphonate (ABS) and/or alkyl polyglycoside (APG) surfactants and (B) carrier materials chosen from polycarboxylates or inorganic salts (preferably amorphous silicates) in a non-surfactant solvent are simultaneously nebulised through the same nozzle ; and (2) the nebulised solutions are dried in standard dryers, preferably in fluidised bed dryers or a ring mixer dryer with a high rpm, during which the two liquids separate to leave the strongly hygroscopic and tacky active substance at least partially surrounded by the non-tacky carrier material. Also claimed are washing or cleaning agents with bulk weights greater than 600 g/l which contain either (i) more than 60 wt.% ABS, (ii) more than 60 (70) wt.% APG or (iii) at least 10 (20) wt.% end product of the above method.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung konzentrierter Tensidgranulate mit Aktivsubstanzgehalten von mehr als 45 Gew.-%, bezogen auf das Granulat, welche eine geringe Hygroskopizität, eine deutlich verbesserte Silierfähigkeit und ein erhöhtes Schüttgewicht aufweisen.The invention relates to a process for the production of concentrated surfactant granules Active substance content of more than 45 wt .-%, based on the granules, which a low hygroscopicity, a significantly improved silage capacity and an increased Have bulk density.

Die wirtschaftliche Herstellung von hellfarbigen Tensidpulvern. insbesondere von Aniontensiden auf der Basis von Fettalkoholsulfaten (FAS) und Alkylbenzolsulfonaten (ABS), ist heute gesicherter Stand des technischen Wissens. Die entsprechenden Tensidsalze fallen dabei in wäßrigen Zubereitungsformen an, wobei Wassergehalte im Bereich von etwa 20 bis 80 Gew.-% und insbesondere von etwa 35 bis 60 Gew.-% einstellbar sind. Produkte dieser Art haben bei Raumtemperatur eine pastenförmige bis schneidfähige Beschaffenheit, wobei bei Raumtemperatur die Fließ- und Pumpfähigkeit solcher Pasten schon im Bereich von etwa 50 Gew.-% Aktivsubstanz eingeschränkt ist oder verlorengeht, so daß bei der Lagerung und der Weiterverarbeitung solcher Pasten, insbesondere bei ihrer Einarbeitung in Mischungen, beispielsweise in Wasch- und Reinigungsmittel, beträchtliche Probleme entstehen. Es ist dementsprechend ein altes Bedürfnis, Waschmitteltenside in trockener, insbesondere rieselfähiger Form zur Verfügung zu stellen. Tatsächlich gelingt es auch, durch die konventionelle Trocknungstechnik, insbesondere im Sprühturm, rieselfähige Tensidpulver, beispielsweise rieselfähige FAS-Pulver zu gewinnen. Hier zeigen sich jedoch gravierende Einschränkungen, die insbesondere die Wirtschaftlichkeit des großtechnischen Einsatzes der so gewonnenen Pulver in Frage stellen. Über den Turm getrocknete Tensidpulver zeigen häufig sehr geringe Schüttgewichte, so daß bei der Verpackung und dem Vertrieb dieser Pulver unrentable Verhältnisse auftreten oder solche Pulver durch Granulation zu schwereren Granulaten kompaktiert werden müssen. Aber auch schon bei der Herstellung der Turmpulver können sicherheitstechnische Bedenken eine derart stark einschränkende Fahrweise der Turmtrocknung erforderlich machen, daß hier praktische Schwierigkeiten auftreten. So können z.B. im Turm Anbackungen auftreten, die zu braunen Verfärbungen des Pulvers führen.The economical production of light colored surfactant powders. especially of Anionic surfactants based on fatty alcohol sulfates (FAS) and alkylbenzenesulfonates (ABS), is today a reliable state of technical knowledge. The corresponding surfactant salts are obtained in aqueous preparation forms, with water contents in the range adjustable from about 20 to 80% by weight and in particular from about 35 to 60% by weight are. Products of this type have a paste-like to cutting ability at room temperature Condition, whereby at room temperature the flow and pumpability of such Pastes are restricted or lost in the range of approximately 50% by weight of active substance, so that when storing and processing such pastes, in particular when incorporated into mixtures, for example in detergents and cleaning agents, considerable problems arise. Accordingly, there is an old need for detergent surfactants to be made available in a dry, in particular free-flowing form. Indeed it also succeeds in using conventional drying technology, especially in Spray tower to obtain free-flowing surfactant powder, for example free-flowing FAS powder. Here, however, there are serious restrictions, in particular the economy question the industrial use of the powders obtained in this way. Surfactant powders dried over the tower often show very low bulk densities, see above that unprofitable conditions occur in the packaging and distribution of these powders or such powders are compacted into heavier granules by granulation have to. But safety technology can also be used in the manufacture of the tower powders Consider such a restrictive way of tower drying required make practical difficulties arise. For example, caking in the tower occur, which lead to brown discolouration of the powder.

Vergleichbare und/oder andere Schwierigkeiten treten bei der Umwandlung wäßriger, insbesondere pastenförmiger Zubereitungsformen zahlreicher anderer wasch- und reinigungsaktiver Tensidverbindungen zu lagerbeständigen Feststoffen auf. Beispielsweise ist zur Gewinnung hellfarbiger wasch- und reinigungsaktiver Alkylglycoside im Rahmen der Synthese eine abschließende Bleiche, beispielsweise mit wäßrigem Wasserstoffperoxid erforderlich, so daß auch hier die heutige Technologie zur wäßrigen Pastenform führt. Solche wäßrigen Alkylglycosid-Pasten (APG-Pasten) sind z.B. durch Hydrolyse oder mikrobielle Verunreinigungen stärker gefährdet als entsprechende Trockenprodukte. Auch hier bereitet die Trocknung nach bisher üblichen Technologien beträchtliche Schwierigkeiten. Schließlich kann aber auch schon die Trocknung einer wäßrigen Paste der Alkalisalze waschaktiver Seifen und/oder von ABS-Pasten beträchtliche Probleme mit sich bringen.Comparable and / or other difficulties arise when converting aqueous, especially pasty preparation forms of numerous other washing and cleaning active Surfactant compounds to storage-stable solids. For example for the production of light colored wash and cleaning active alkyl glycosides within the scope of Synthesis of a final bleach, for example with aqueous hydrogen peroxide required, so that here, too, today's technology leads to the aqueous paste form. Such aqueous alkyl glycoside pastes (APG pastes) are e.g. by hydrolysis or microbial Contamination is more at risk than corresponding dry products. Also Drying according to technologies that have been common up to now presents considerable difficulties. Finally, the drying of an aqueous paste of the alkali salts can also be carried out detergent soaps and / or ABS pastes have significant problems bring.

Eine Alternative zur Sprühtrocknung tensidischer Pasten stellt die Granulierung dar. So beschreibt die EP-B-0 603 207 (Henkel) ein Verfahren zur Herstellung wasch- und reinigungsaktiver Tensidgranulate mit einem Schüttgewicht oberhalb 500 g/l durch gleichzeitige Granulierung und Trocknung in allen Vorrichtungen, in denen eine Granulierung unter gleichzeitiger Trocknung erfolgen kann. Hierbei wird eine Tensid-Zubereitungsform, die eine nicht-tensidische Flüssigkomponente (in der Regel Wasser) aufweist, gewünschtenfalls unter Zumischung einer Feststoffkomponente granuliert und gleichzeitig getrocknet. Zur Silierfähigkeit und der Verteilung der Aktivsubstanz im resultierenden Korn, insbesondere zur Extrahierbarkeit des Tensids aus dem unzerkleinerten oder zerkleinerten Produkt mit Hilfe von nichtwäßrigen, das Korn nicht zerstörenden Lösungsmitteln, wird in der Anmeldung nichts ausgeführt. Auch stellt die gleichzeitige Verdüsung von Aktivsubstanz- und Trägerkomponentenlösung durch ein und dieselbe Düse hier einen möglichen, aber keinen zwingenden Verfahrensparameter dar.Granulation is an alternative to spray drying surfactant pastes describes EP-B-0 603 207 (Henkel) a process for the production of washing and cleaning active Surfactant granules with a bulk density above 500 g / l by simultaneous Granulation and drying in all devices in which granulation can be done with simultaneous drying. Here, a surfactant preparation form which is a non-surfactant liquid component (usually water) has, if desired granulated with the addition of a solid component and dried at the same time. The ability to ensilage and the distribution of the active substance in the resulting Grain, especially for extractability of the surfactant from the uncrushed or crushed product with the help of non-aqueous solvents that do not destroy the grain, nothing is carried out in the registration. The simultaneous spraying also provides of active substance and carrier component solution through one and the same nozzle here is a possible but not a mandatory process parameter.

Die Aufgabe der Erfindung bestand darin, ein Verfahren zur Herstellung schwerer, rieselfähiger, hochkonzentrierter Tensidgranulate mit Schüttgewichten oberhalb 600 g/l bereitzustellen, wobei die erhaltenen Granulate Vorteile hinsichtlich der Silierfähigkeit und der Hygroskopizität aufweisen.The object of the invention was to provide a method for producing heavy, free-flowing, to provide highly concentrated surfactant granules with bulk densities above 600 g / l, the granules obtained have advantages in terms of ensiling ability and Show hygroscopicity.

Gegenstand der Erfindung ist dementsprechend ein Verfahren zur Herstellung wasch- und reinigungsaktiver Tensidgranulate mit Schüttgewichten oberhalb 600 g/l durch Granulierung einer Tensid-Zubereitungsform, dadurch gekennzeichnet, daß man Lösungen von

  • a) Alkylbenzolsulfonat- und/oder Alkylpolyglycosid-Tensiden und
  • b) Trägermaterialien, ausgewählt aus der Gruppe der Polycarboxylate und der anorganischen Salze, insbesondere der amorphen Silikate,
    • The invention accordingly relates to a process for the production of detergent granules with active detergent and cleaning activity with bulk densities above 600 g / l by granulating a surfactant preparation form, characterized in that solutions of
  • a) Alkylbenzenesulfonate and / or alkylpolyglycoside surfactants and
  • b) carrier materials selected from the group of the polycarboxylates and the inorganic salts, in particular the amorphous silicates,

    • in einem nicht-tensidischen Lösungsmittel gleichzeitig durch ein- und dieselbe Düse verdüst und in herkömmlichen Trocknern, vorzugsweise in der Wirbelschicht oder einem Ringmischtrockner mit hohen Drehzahlen, trocknet, wobei während der Trocknung eine Trennung zwischen den beiden Flüssigkeiten stattfindet, so daß die stark hygroskopische, klebrige Aktivsubstanz von der nicht klebrigen Trägersubstanz mindestens teilweise eingeschlossen wird.atomized in one non-surfactant solvent simultaneously through one and the same nozzle and in conventional dryers, preferably in the fluidized bed or in one Ring mixer dryer with high speeds, dries, during which a Separation between the two liquids takes place, so that the highly hygroscopic, sticky active substance at least partially enclosed by the non-sticky carrier substance becomes.

    Das erfindungsgemäße Verfahren besitzt den Vorteil, daß das entstehende Korn bedingt durch den Einschluß von Tensidphasen in Phasen des Trägermaterials eine erhöhte mechanische Stabilität und eine äußerst verringerte Wasseraufnahme bei Lagerung aufweist. Die nach dem erfindungsgemäßen Verfahren erhaltenen Granulate sind dementsprechend sehr gut riesel- und silierfähig und verkleben auch bei offener Lagerung bedingt durch ihre geringe Neigung zur Wasseraufnahme nicht. Bei getrennter Eindüsung von Aktivsubstanz- und Trägerpaste in die Granuliereinheit ist das Produkt schon bei geringen Tensidkonzentrationen klebrig und backt bei der Trocknung zusammen, wobei die Produkte zusätzlich hygroskopisch sind und im Verlauf der starken Wasseraufnahme verkleben.The process according to the invention has the advantage that the resulting grain is conditional due to the inclusion of surfactant phases in phases of the carrier material, an increased mechanical Stability and an extremely reduced water absorption during storage. The granules obtained by the process according to the invention are accordingly very easy to pour and ensilage and stick together due to their low tendency to absorb water. With separate injection of active substance and carrier paste in the granulation unit is the product even at low surfactant concentrations sticky and cakes on drying, adding the products are hygroscopic and stick in the course of heavy water absorption.

    Die Lösungen der Aktivsubstanz und der Trägersubstanz werden erfindungsgemäß durch ein- und dieselbe Düse verdüst. Hierbei können die Lösungen erst in der Düse miteinander vermischt, also über getrennte Vorratsbehälter und Zuleitungen der Düse zugeführt werden, aber auch eine Mischung beider Lösungen aus einem einzigen Vorratsbehälter kann über eine Düse eingedüst werden.The solutions of the active substance and the carrier substance are carried out according to the invention one and the same nozzle atomized. The solutions can only be mixed in the nozzle mixed, i.e. fed to the nozzle via separate storage containers and feed lines but also a mixture of both solutions from a single storage container can be injected through a nozzle.

    Das nicht-tensidische Lösungsmittel, das einen oder mehrere Bestandteile enthalten kann, besitzt unter Normaldruck eine Siedepunkt bzw. Siedebereich vorzugsweise unterhalb 250°C und insbesondere unterhalb 200°C. Mit besonderem Vorteil enthält es Bestandteile, die bei Normaldruck zwischen 60 und 180°C sieden. Als gegebenenfalls vorhandener organischer Bestandteil des nicht-tensidischen Lösungsmittels werden vorzugsweise mono- und/oder polyfunktionelle Alkohole, beispielsweise Methanol, Ethanol, Propanol, Isopropanol, Butanol, sekundär- und tertiär- Butanol, Pentanol, Ethylenglykol, 1,2-Propandiol, Glycerin oder Mischungen aus diesen eingesetzt. Vorzugsweise beträgt der Anteil der als nicht-tensidisches Lösungsmittel eingesetzten mono- und/oder polyfunktionellen Alkohole 0,5 bis 10 Gew.-% uns insbesondere 45 bis 60 Gew.-%, jeweils bezogen auf die Tensid-Zubereitungsform.The non-surfactant solvent, which may contain one or more components, has a boiling point or boiling range preferably below normal pressure 250 ° C and especially below 200 ° C. With particular advantage, it contains components which boil between 60 and 180 ° C at normal pressure. As possibly existing organic constituents of the non-surfactant solvent are preferably mono- and / or polyfunctional alcohols, for example methanol, ethanol, propanol, Isopropanol, butanol, secondary and tertiary butanol, pentanol, ethylene glycol, 1,2-propanediol, Glycerin or mixtures of these are used. The is preferably Proportion of monofunctional and / or polyfunctional solvents used as non-surfactant solvents Alcohols 0.5 to 10 wt .-% and in particular 45 to 60 wt .-%, each based on the surfactant preparation form.

    Insbesondere ist es jedoch bevorzugt, als anorganischen Bestandteil des nicht-tensidischen Lösungsmittels Wasser, gegebenenfalls zusammen mit organischen Bestandteilen wie Ethanol, 1,2-Propandiol oder Glycerin einzusetzen. Dabei beträgt der Anteil des Wassers vorzugsweise 25 bis 80 Gew.-%, bezogen auf die Gesamtmenge des nicht-tensidischen Lösungsmittels. Die Lösungen der Tenside und Trägermaterialien im nicht-tensidischen Lösungsmittel können in breiten Konzentrationsbereichen eingesetzt werden, wobei lediglich auf eine zur Verdüsung noch geeignete Viskosität geachtet werden muß. Bezogen auf die gesamte zu verdüsende Lösung beträgt der Anteil des nicht-tensidischen Lösungsmittels 30 bis 70 Gew.-% und insbesondere 45 bis 60 Gew.-%.In particular, however, it is preferred as the inorganic component of the non-surfactant Solvent water, optionally together with organic components such as ethanol, 1,2-propanediol or glycerin. The share is of the water preferably 25 to 80 wt .-%, based on the total amount of non-surfactant solvent. The solutions of surfactants and carrier materials in Non-surfactant solvents can be used in a wide range of concentrations are taken into account, with only a viscosity that is still suitable for atomization got to. Based on the total solution to be sprayed, the proportion of the non-surfactant is Solvent 30 to 70 wt .-% and in particular 45 to 60 wt .-%.

    Als Tenside werden entweder Alkylbenzolsulfonate (ABS) oder Alkylpolyglycoside (APG) oder Mischungen aus diesen eingesetzt. Vorteilhaft eingesetzte Alkylbenzolsulfonate haben eine Kettenlänge von 9 bis 13 C-Atomen, aber auch nahezu reines C12-Alkylbenzolsulfonat kann bevorzugt eingesetzt werden.Die Alkyl- oder Alkenylglykoside (APG) besitzen die allgemeine Formel R-O-(G)x, in der R einen primären, geradkettigen oder in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet, G ein Symbol ist, das für eine Glucose-Einheit mit 5 oder 6 C-Atomen steht, und der Oligomerisierungsgrad x zwischen 1 und 10, vorzugsweise zwischen 1 und 2 liegt und insbesondere deutlich kleiner als 1,4 ist.Either alkylbenzenesulfonates (ABS) or alkylpolyglycosides (APG) or mixtures of these are used as surfactants. Advantageously used alkylbenzenesulfonates have a chain length of 9 to 13 carbon atoms, but almost pure C 12 -alkylbenzenesulfonate can also be used with preference.The alkyl or alkenylglycosides (APG) have the general formula RO- (G) x , in which R is one primary, straight-chain or in the 2-position methyl branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms, G is a symbol which represents a glucose unit with 5 or 6 carbon atoms, and the degree of oligomerization x between 1 and 10, preferably between 1 and 2 and in particular is significantly smaller than 1.4.

    Ohne die erfindungsgemäßen Verfahrensvorteile zu beeinträchtigen, können neben den ABS- und/oder APG-Tensiden auch andere anionische, nichtionische, kationische oder amphotere Tenside in Kombination mit den erstgenannten eingesetzt werden. Während sich das Verfahren hauptsächlich zur Herstellung von ABS- und/oder APG-Compounds eignet, sind Zusätze von bis zu 20 Gew.-% anderer Tenside, bezogen auf die Gesamt-Tensidmenge, möglich, ohne dabei die Vorteile des erfindungsgemäßen Verfahrens einzubüßen.Without adversely affecting the process advantages according to the invention, in addition to the ABS and / or APG surfactants also other anionic, nonionic, cationic or amphoteric surfactants can be used in combination with the former. While the process is mainly used to manufacture ABS and / or APG compounds suitable are additions of up to 20% by weight of other surfactants, based on the total amount of surfactant, possible without losing the advantages of the method according to the invention.

    Die in dem erfindungsgemäßen Verfahren eingesetzten Trägermaterialien können anorganischer und/oder organischer Natur sein. In einer bevorzugten Ausführungsform bestehen sie aus amorphen Alkalisilikaten der Formel (SiO2)m(M2O)n1 (sog. Wassergläser) und/oder kristallinen Schichtsilikaten der Formel (SiO2)m((M2O)n2(H2O)x, wobei M für Lithium, Natrium oder Kalium, m und n1 für ganze oder gebrochene Zahlen größer als 0, n2 für 1 und x für 0 oder ganze Zahlen von 1 bis 20 steht. Als Trägerlösung für die Granulierung nach dem erfindungsgemäßen Verfahren haben sich insbesondere Lösungen von Wassergläsern bewährt, bei denen M für Natrium und x für 0 steht und deren Modul, d.h. deren m:n-Verhältnis 1,9 bis 4, vorzugsweise 1,9 bis 2,5 beträgt. Die vorzugsweise wäßrigen Wasserglaslösungen haben hierbei Feststoffgehalte von 1 bis 80 Gew.-%, vorzugsweise 30 bis 60 Gew.-%.The carrier materials used in the process according to the invention can be inorganic and / or organic in nature. In a preferred embodiment, they consist of amorphous alkali silicates of the formula (SiO 2 ) m (M 2 O) n1 (so-called water glasses) and / or crystalline layered silicates of the formula (SiO 2 ) m ((M 2 O) n2 (H 2 O ) x , where M is lithium, sodium or potassium, m and n1 are integers or fractional numbers greater than 0, n2 is 1 and x is 0 or integers from 1 to 20. As a carrier solution for the granulation according to the inventive method Solutions of water glasses in which M stands for sodium and x for 0 and whose modulus, ie whose m: n ratio is 1.9 to 4, preferably 1.9 to 2.5, have proven particularly useful Solids contents of 1 to 80% by weight, preferably 30 to 60% by weight.

    Als weitere Trägermaterialien, die allein oder in Kombination mit den Silikaten in Form von Lösungen eingesetzt werden, kommen anorganische Salze oder organische Polycarboxylate in Betracht. Unter den anorganischen Salzen ist insbesondere Natriumcarbonat bevorzugt, während als Polycarboxylate vorzugsweise Citronen-säure/Citrate und/oder Acrylsäure/Maleinsäure-Copolymere eingesetzt werden.As further carrier materials, alone or in combination with the silicates in the form solutions are used, inorganic salts or organic polycarboxylates into consideration. In particular, sodium carbonate is among the inorganic salts preferred, while as polycarboxylates preferably citric acid / citrates and / or Acrylic acid / maleic acid copolymers are used.

    Die wasch- und reinigungsaktiven Tensidgranulate weisen, bezogen auf das fertige Granulat, Trägermaterialgehalte von 10 bis 50 Gew.-% auf. Da hochkonzentrierte Tensidgranulate aus ökonomischen Gründen bevorzugt sind, sind Trägermaterialgehalte von unterhalb 40, insbesondere unterhalb 30 Gew.-%, bevorzugt. Neben den sogenannten übertrockneten Wassergläsern finden in bevorzugten Ausführungsformen der Erfindung auch Natriumcarbonat, Acrylsäure/Maleinsäure-Copolymere sowie Trinatriumcitrat als Trägermaterialien Verwendung. Bevorzugt sind auch Gemische der Trägersubstanzen, insbesondere Carbonat/Silikat-Gemische sowie Citrat/Silikat-Gemische.The detergent granules, which are active in washing and cleaning, have, based on the finished granulate, Carrier material contents of 10 to 50 wt .-%. Because highly concentrated surfactant granules Preferred for economic reasons are carrier material contents from below 40, in particular below 30% by weight, is preferred. In addition to the so-called over-dried Water glasses can also be found in preferred embodiments of the invention Sodium carbonate, acrylic acid / maleic acid copolymers and trisodium citrate as carrier materials Use. Mixtures of the carrier substances are also preferred, in particular Carbonate / silicate mixtures as well as citrate / silicate mixtures.

    Die Tensid-Zubereitungsform wird granuliert und getrocknet, wobei nach dem erfindungsgemäßen Verfahren Granulat-Teilchen erhalten werden, in denen die Aktivsubstanz teilweise von den Trägersubstanz eingeschlossen wird. Unter Trocknung wird hierbei das teilweise oder vollständige Entfernen des nicht-tensidischen Lösungsmittels verstanden. Vorzugsweise wird das nicht-tensidische Lösungsmittel nahezu vollständig entfernt.The surfactant preparation form is granulated and dried, using the method according to the invention Process granulate particles are obtained in which the active substance is partially enclosed by the carrier. Under drying, this becomes partially or completely remove the non-surfactant solvent. The non-surfactant solvent is preferably removed almost completely.

    Die Herstellung der Tensidgranulate kann nach dem erfindungsgemäßen Verfahren in allen Vorrichtungen erfolgen, in denen eine Granulierung unter trocknenden Bedingungen durchgeführt werden kann. Beispiele hierfür sind beheizbare Mischer und Granulatoren, insbesondere schnellaufende Ringmischtrockner wie Granulatoren vom Typ Turbo dryer® (Vorrichtung der Firma Vomm, Italien). In einer bevorzugten Ausführungsform sieht die Erfindung jedoch vor, daß die Kombination der beiden Verfahrensschritte in einer batchweise oder kontinuierlich laufenden Wirbelschicht durchgeführt wird. Es ist insbesondere bevorzugt, das Verfahren kontinuierlich in der Wirbelschicht durchzuführen. Dabei wird die Tensid-Zubereitungsform aus einer gemeinsamen Düse in die Wirbelschicht eingebracht. Die Mischung der beiden flüssigen bis pastenförmigen Bestandteile der Tensid-Zubereitungsform kann dabei bereits vorher oder erst in der Düse erfolgen. Bevorzugt eingesetzte Wirbelschicht-Apparate besitzen Bodenplatten mit Abmessungen von mindestens 0,4 m. Insbesondere sind Wirbelschicht-Apparate bevorzugt, die eine Bodenplatte mit einem Durchmesser zwischen 0,4 und 5 m, beispielsweise 1,2 m oder 2,5 m besitzen. Es sind jedoch auch Wirbelschicht-Apparate geeignet, die eine Bodenplatte mit einem größeren Durchmesser als 5 m aufweisen. Als Bodenplatte wird vorzugsweise eine Lochbodenplatte oder eine Conidurplatte (Handelsprodukt der Firma Hein & Lehmann, Bundesrepublik Deutschland) eingesetzt. Vorzugsweise wird das erfindungsgemäße Verfahren bei Wirbelluftgeschwindigkeiten zwischen 1 und 8 m/s und insbesondere zwischen 1,5 und 5,5 m/s durchgeführt. Der Austrag der Granulate aus der Wirbelschicht erfolgt vorteilhafterweise über eine Größenklassierung der Granulate. Diese Klassierung kann beispielsweise mit einer Siebvorrichtung oder durch einen entgegengeführten Luftstrom (Sichterluft) erfolgen, der so reguliert wird, daß erst Teilchen ab einer bestimmten Teilchengröße aus der Wirbelschicht entfernt und kleinere Teilchen in der Wirbelschicht zurückgehalten werden. In einer bevorzugten Ausführungsform setzt sich die einströmende Luft aus der beheizten oder unbeheizten Sichterluft und der beheizten Bodenluft zusammen. Die Bodenlufttemperatur liegt dabei vorzugsweise zwischen 80 und 400°C, insbesondere zwischen 90 und 350°C. Die Wirbelluft kühlt sich durch Wärmeverluste und durch die Verdampfungswärme der Bestandteile des nicht-tensidischen Lösungsmittels ab. In einer besonders bevorzugten Ausführungsform beträgt die Temperatur der Wirbelluft etwa 5 cm oberhalb der Bodenplatte 60 bis 120°C, vorzugsweise 65 bis 90°C und insbesondere 70 bis 85°C. Die Luftaustrittstemperatur liegt vorzugsweise zwischen 60 und 120°C, insbesondere unterhalb 100°C und mit besonderem Vorteil zwischen 70 und 85°C. Bei dem erfindungsgemäß durchgeführten Verfahren wird die Mischung der beiden Lösungen, die zusammen die Tensid-Zubereitungsform bilden, durch eine Düse in die Wirbelschicht eingeblasen, in der sich keine zusätzlichen Feststoffe als Startmasse befinden. In der kontinuierlich arbeitenden Wirbelschicht fungiert die getrocknete Tensid-Zubereitungsform als Träger- beziehungsweise Keimmaterial. Hierbei verdampfen die Bestandteile des nicht-tensidischen Lösungsmittels teilweise oder vollständig, wobei die angetrockneten bis trockenen Keime mit weiteren Mengen eingebrachter Tensid-Zubereitungsform in der Art umhüllt werden, daß die Trägersubstanz die Aktivsubstanz einhüllt. Dieser spezielle Aufbau des Granulats, der nur durch das gleichzeitige Eindüsen von Aktivsubstanz- und Trägermaterial-Lösung durch ein- und dieselbe Düse erhalten wird, resultiert daraus, daß das verdampfende nicht-tensidische Lösungsmittel beim Verdampfungsprozeß Trägermaterial aus der frisch auf das Korn aufkondensierten Schicht mitträgt und bei Verdampfen vom Korn an der Oberfläche ablagert.The preparation of the surfactant granules can be carried out by the process according to the invention in all devices take place in which a granulation under drying conditions can be carried out. Examples include heated mixers and granulators, especially high-speed ring mix dryers such as Turbo dryer® granulators (Device from Vomm, Italy). In a preferred embodiment, the Invention, however, that the combination of the two process steps in a batch or continuously running fluidized bed is carried out. It is special preferred to carry out the process continuously in the fluidized bed. there the surfactant preparation form is introduced into the fluidized bed from a common nozzle. The mixture of the two liquid to pasty components of the surfactant preparation form can be done beforehand or only in the nozzle. Prefers Fluid bed apparatuses used have base plates with dimensions of at least 0.4 m. In particular, fluidized bed apparatuses are preferred which have a base plate have a diameter between 0.4 and 5 m, for example 1.2 m or 2.5 m. However, fluidized bed apparatuses are also suitable which have a base plate with a have a diameter greater than 5 m. A perforated base plate is preferably used as the base plate or a Conidur plate (commercial product from Hein & Lehmann, Federal Republic Germany). The method according to the invention is preferred at vortex air speeds between 1 and 8 m / s and in particular between 1.5 and 5.5 m / s performed. The granules are discharged from the fluidized bed advantageously via a size classification of the granules. This classification can for example with a screening device or through an opposed air flow (Classifier air), which is regulated so that only particles above a certain particle size removed from the fluidized bed and smaller particles retained in the fluidized bed become. In a preferred embodiment, the inflowing settles Air from the heated or unheated classifier air and the heated soil air together. The soil air temperature is preferably between 80 and 400 ° C, in particular between 90 and 350 ° C. The vortex air cools down due to heat loss and by the heat of vaporization of the components of the non-surfactant solvent from. In a particularly preferred embodiment, the temperature of the fluidizing air is about 5 cm above the base plate 60 to 120 ° C, preferably 65 to 90 ° C and especially 70 to 85 ° C. The air outlet temperature is preferably between 60 and 120 ° C, especially below 100 ° C and with particular advantage between 70 and 85 ° C. In the process carried out according to the invention, the mixture of the two Solutions that together form the surfactant preparation form through a nozzle into the Fluidized bed blown in, in which there are no additional solids as starting mass. The dried surfactant preparation form acts in the continuously working fluidized bed as carrier or seed material. Here the evaporate Components of the non-surfactant solvent partially or completely, the dried-on to dry germs with additional amounts of surfactant preparation be encased in such a way that the carrier substance is the active substance envelops. This special structure of the granulate, which can only be achieved by simultaneous injection Obtain active substance and carrier material solution through one and the same nozzle is the result of the evaporating non-surfactant solvent in the evaporation process Backing material from the freshly condensed layer on the grain carries and deposits on the surface of the grain when evaporating.

    Bei der erfindungsgemäßen Granulation kann -insbesondere wenn Alkylbenzolsulfonate als Tenside eingesetzt werden- zur Aufrechterhaltung des Wirbelgranulationsprozesses kontinuierlich ein Bepuderungsmittel, vorzugsweise Zeolith oder Natriumcarbonat, in die Wirbelschicht eingebracht werden. Diese Bepuderungsmittel vermindern bei der Granulation die Klebrigkeit der feuchten Granulatkörner zusätzlich und fördern somit die Verwirbelung und die Trocknung zum gewünschten Produkt. Für die Herstellung von Granulaten nach dem erfindungsgemäßen Verfahren kann diese Variante vorteilhaft sein, sie ist zur Ausführung der Erfindung jedoch nicht zwingend erforderlich.In the granulation according to the invention, especially when alkylbenzenesulfonates used as surfactants to maintain the vortex granulation process continuously add a powdering agent, preferably zeolite or sodium carbonate Fluidized bed are introduced. These powdering agents reduce the amount of granulation the stickiness of the moist granules and thus promote turbulence and drying to the desired product. For the production of granules According to the method according to the invention, this variant can be advantageous is, however, not absolutely necessary to carry out the invention.

    Auf diese Weise resultieren aus dem erfindungsgemäßen Verfahren Tensid-Granulate, die sich leicht in kaltem Wasser lösen, ohne jedoch hygroskopisch zu sein. Die Granulate haben eine hohe mechanische Stabilität und somit ausgezeichnete Riesel- und Siliereigenschaften. Mit organischen Lösungsmitteln, die den Kornaufbau nicht zerstören, lassen sich aus den unzerkleinerten Granulaten nur geringe Aktivsubstanzgehalte herauslösen, während aus dem gemörserten Granulat die Aktivsubstanz zum größten Teil extrahierbar ist. In this way, the process according to the invention results in surfactant granules which dissolve easily in cold water without being hygroscopic. The granules have high mechanical stability and therefore excellent flow and silage properties. Leave with organic solvents that do not destroy the grain structure only small amounts of active substance dissolve from the uncrushed granules, while most of the active substance can be extracted from the ground granules is.

    Die nach dem erfindungsgemäßen Verfahren hergestellten wasch- und reinigungsaktiven Tensidgranulate weisen Schüttgewichte oberhalb von 600 g/l auf. Sie sind ideal als Komponenten zur Herstellung von Wasch- und Reinigungsmitteln geeignet, wobei bevorzugte Wasch- und Reinigungsmittel die nach dem erfindungsgemäßen Verfahren hergestellten wasch- und reinigungsaktiven Tensidgranulate in Mengen von mehr als 10 Gew.-%, insbesondere in Mengen oberhalb von 20 Gew.-%, bezogen auf das gesamte Wasch- und Reinigungsmittel, enthalten. Zur Verarbeitung in Waschmitteln mit hohem Schüttgewicht oder für andere spezielle Anwendungen ist ein Schüttgewicht der nach dem erfindungsgemäßen Verfahren hergestellten wasch- und reinigungsaktiven Tensidgranulate oberhalb von 700 g/l, insbesondere oberhalb von 800 g/l, bevorzugt.The washing and cleaning active produced by the inventive method Surfactant granules have bulk densities above 600 g / l. They are ideal as components suitable for the production of detergents and cleaning agents, preferred Detergents and cleaning agents which are produced by the process according to the invention detergent-active and surfactant granules in amounts of more than 10% by weight, in particular in amounts above 20 wt .-%, based on the total washing and Detergent included. For processing in detergents with a high bulk density or for other special applications is a bulk density according to the invention Process produced washing and cleaning active surfactant granules above of 700 g / l, in particular above 800 g / l, is preferred.

    Vorteilhafterweise können nach dem erfindungsgemäßen Verfahren wasch- und reinigungsaktiven Tensidgranulate hergestellt werden, deren Gesamttensidgehalt, bezogen auf das gesamte Granulat, mehr als 40 Gew.-% beträgt. Tensidgehalte oberhalb von 50 Gew.-% und insbesondere oberhalb von 60 Gew.-% sind dabei bevorzugt. Bei der Herstellung von Alkylbenzolsulfonat(ABS)- und Alkylpolyglycosid(APG)-Granulaten sind ABS-Gehalte oberhalb von 40 Gew.-%, vorzugsweise oberhalb von 50 Gew.-% und insbesondere oberhalb von 60 Gew.-%, bezogen auf das Granulat, bevorzugt, während APG-Gehalte bevorzugt oberhalb von 50 Gew.-%, vorzugsweise oberhalb von 60 Gew.-% und insbesondere oberhalb von 70 Gew.-%, bezogen auf das Granulat, liegen.The process according to the invention can advantageously be active in washing and cleaning Surfactant granules are produced, the total surfactant content, based on the total granulate is more than 40% by weight. Surfactant contents above 50% by weight and in particular above 60% by weight are preferred. In the preparation of of alkylbenzenesulfonate (ABS) and alkylpolyglycoside (APG) granules are ABS contents above 40% by weight, preferably above 50% by weight and in particular above 60 wt .-%, based on the granules, preferred, while APG contents preferably above 50% by weight, preferably above 60% by weight and in particular above 70% by weight, based on the granules.

    Das Verfahren eignet sich zur Herstellung von hochkonzentrierten Tensidgranulaten und weist insbesondere dann Vorteile auf, wenn die zu verarbeitenden Tenside an sich klebriger Natur sind, wie dies bei Alkylbenzolsulfonaten und Alkylpolyglycosiden der Fall ist. Selbstverständlich können auch andere Tenside, die keine klebenden Eigenschaften aufweisen oder weitaus weniger kleben, zusätzlich eingesetzt werden. Dabei ist es aber bevorzugt, daß der Anteil anderer Tenside 20 Gew.-%, bezogen auf den Gesamttensidgehalt, in den erfindungsgemäßen Granulaten nicht überschreitet. The process is suitable for the production of highly concentrated surfactant granules and has particular advantages if the surfactants to be processed are sticky per se Are natural, as is the case with alkylbenzenesulfonates and alkylpolyglycosides. Of course, other surfactants that have no adhesive properties can also be used or glue much less, can also be used. However, it is preferred that the proportion of other surfactants is 20% by weight, based on the total surfactant content, does not exceed in the granules according to the invention.

    BeispieleExamples

    Durch gleichzeitiges Verdüsen von wäßrigen Tensid- und Trägermaterial-Lösungen durch eine Mehrkanaldüse in einen Wirbelschichttrockner wurden Compounds folgender Zusammensetzung erhalten: Zusammensetzung [Gew.-%]: E1 E2 E3 E4 E5 E6 E7 E8 ABS 45 - - - 60 50 - 61 APG - 67 80 50 - - 62 - Silikat 21 22 17,5 10 13 15 - - Sokalan CP5® - - - - - - 33 - Natriumcitrat - - - - - - - 14 Natriumcarbonat 28 - - 35 - - - - Zeolith - - - - 22 30 - 20 Wasser 6 11 2,5 5 5 5 5 5 Schüttgewicht
    [g/l]     632 641 612 651 702 734 611 633     Sokalan CP5® ist ein Acrylsäure-Maleinsäure-Copolymer der Firma BASF     Compounds of the following composition were obtained by simultaneously spraying aqueous surfactant and carrier material solutions through a multi-channel nozzle into a fluidized bed dryer: Composition [% by weight]: E1 E2 E3 E4 E5 E6 E7 E8 SECTION 45 - - - 60 50 - 61 APG - 67 80 50 - - 62 - silicate 21 22 17.5 10 13 15 - - Sokalan CP5® - - - - - - 33 - sodium citrate - - - - - - - 14 sodium 28 - - 35 - - - - zeolite - - - - 22 30 - 20 water 6 11 2.5 5 5 5 5 5 bulk weight
    [G / l]     632 641 612 651 702 734 611 633     Sokalan CP5 ® is an acrylic acid-maleic acid copolymer from BASF

    Zum Beweis dafür, daß große Teile des Tensids vom Trägermaterial eingeschlossen sind, wurde eine Probe von E2 flüssigchromatographisch untersucht. Direkt aus der Produktion entnommenes E2 wies bei Extraktion mit Methanol einen Aktivsubstanzgehalt von 23 Gew.-% auf, während eine Probe der gleichen Charge nach Mörsern bei sonst gleicher Verfahrensweise einen Aktivsubstanzgehalt von 65 Gew.-% ergab. To prove that large parts of the surfactant are enclosed by the carrier material, a sample of E2 was examined by liquid chromatography. Straight from production extracted E2 had an active substance content of 23 when extracted with methanol % By weight, while a sample of the same batch after mortars with otherwise the same The procedure gave an active substance content of 65% by weight.

    Die Löslichkeiten von E1 und E2 wurden bestimmt, indem jeweils 5 g des Mittels in ein 1-1-Gefäß gegegeben wurden, in dem sich 500 ml demineralisiertes Wasser befanden, das durch einen Propellerrührer mit einer Drehzahl von 900 U/min gerührt wurde. Die Leitfähigkeit wurde über eine Leitfähigkeitsmeßzelle detektiert und auf einem Schreiber festgehalten. Die Messung erfolgte, bis kein Anstieg mehr feststellbar war. Die Zeit zum Erreichen der Leitfähigkeitskonstanz des Mittels wurde 100% gesetzt, die entsprechenden anderen Lösezeiten rechnerisch ermittelt. Löslichkeitstest E1 E2 95% gelöst [min] 2,59 2,57 90% gelöst [min] 2,27 2,25 80% gelöst [min] 1,45 1,48 Rückstand nach 1,5 min [Gew.-%] 2 5 Rückstand nach 5 min [Gew.-%] 0 0 The solubilities of E1 and E2 were determined by adding 5 g each of the agent to a 1 l vessel containing 500 ml of demineralized water which was stirred by a propeller stirrer at 900 rpm. The conductivity was detected via a conductivity measuring cell and recorded on a recorder. The measurement was carried out until no increase was ascertainable. The time to reach the conductivity of the agent was set to 100%, the corresponding other dissolving times were calculated. solubility E1 E2 95% solved [min] 2.59 2.57 90% solved [min] 2.27 2.25 80% solved [min] 1.45 1.48 Residue after 1.5 min [% by weight] 2 5 Residue after 5 min [% by weight] 0 0

    Sämtliche erfindungsgemäß hergestellten Compounds E1 bis E8 lassen sich an der Luft lagern, ohne dabei zu verkleben, oder ihre Rieselfähigkeit einzubüßen. Ein Vergleichsversuch zwischen ES und einem käuflichen vergleichbaren ABS-Compound mit einem Schüttgewicht von 400 g/l und einem Aktivsubstanzgehalt von 85 Gew.-% ergab bei 8 Stunden Lagerung (55 % relative Luchtfeuchtigkeit) folgende Werte: Hygroskopizität (8-Stunden Lagerversuch) E5 Vergleich Wasseraufnahme [Gew.-% Eigengewicht] 5 20 Bemerkungen rieselfähig Verklebung All compounds E1 to E8 produced according to the invention can be stored in the air without sticking or losing their free-flowing properties. A comparison test between ES and a commercially available comparable ABS compound with a bulk density of 400 g / l and an active substance content of 85% by weight showed the following values after 8 hours of storage (55% relative luminous humidity): Hygroscopicity (8-hour storage trial) E5 comparison Water absorption [% by weight] 5 20 Remarks pourable bonding

    Die erfindungsgemäß hergestellten ABS-/APG-Compounds sind als ideale Zusatzstoffe zu Waschmitteln geeignet, da sie den Mitteln eine verbesserte Löslichkeit verleihen.The ABS / APG compounds produced according to the invention are ideal additives suitable for detergents since they give the detergents improved solubility.

    Wurden die Lösungen der Aktiv- und der Trägersubstanz nicht durch ein- und dieselbe Düse, sondern über zwei getrennte Düsen verdüst, so wurden keine rieselfähigen Granulate mit hohem Schüttgewicht erhalten. Vielmehr verklebten solche Mischungen bereits im Mischer zu zähflüssigen bis pastösen Massen, die sich nicht weiter trocknen ließen.The solutions of the active substance and the carrier were not the same Nozzle, but sprayed through two separate nozzles, so no free-flowing granules obtained with high bulk density. Rather, such mixtures are already glued in the mixer to viscous to pasty masses that could not be dried further.

    Claims (12)

    1. Process for the preparation of washing- and cleaning-active surfactant granules with bulk densities above 600 g/l by granulation of a surfactant preparation form, characterized in that solutions of
      a) alkylbenzenesulphonate surfactants and/or alkyl polyglycoside surfactants and
      b) carrier materials chosen from the group of polycarboxylates and of inorganic salts, in particular of amorphous silicates,
      in a non-surface-active solvent are atomized simultaneously through one and the same nozzle and dried in conventional dryers, preferably in the fluidized bed or a ring mixer dryer with a high number of revolutions, where, during the drying, the two liquids separate, meaning that the highly hygroscopic, tacky active substance is at least partially enclosed by the nontacky carrier substance.
    2. Process according to Claim 1, characterized in that the non-surface-active solvent used is mono and/or polyfunctional alcohols, preferably in amounts of from 0.5 to 10% by weight, based on the total solution to be atomized.
    3. Process according to one of Claims 1 or 2, characterized in that the non-surface-active solvent used is water, preferably in amounts of from 25 to 80% by weight, based on the total amount of the non-surface-active solvent.
    4. Process according to one of Claims 1 to 3, characterized in that, to maintain the fluidized granulation process, a powdering agent, preferably zeolite or sodium carbonate, is continuously introduced into the fluidized bed.
    5. Process according to one of Claims 1 to 4, characterized in that the carrier material used is a silicate/citrate mixture.
    6. Process according to one of Claims 1 to 5, characterized in that the alkylbenzenesulphonate (ABS) content of the washing- and cleaning-active surfactant granules is above 40% by weight, preferably above 50% by weight and in particular above 60% by weight, based on the granules.
    7. Process according to one of Claims 1 to 6, characterized in that the alkyl polyglycoside (APG) content of the washing- and cleaning-active surfactant granules is above 50% by weight, preferably above 60% by weight and in particular above 70% by weight, based on the granules.
    8. Process according to one of Claims 1 to 7, characterized in that the total surfactant content of the washing- and cleaning-active surfactant granules is above 40% by weight, preferably above 50% by weight and in particular above 60% by weight, based on the granules.
    9. Process according to one of Claims 1 to 8, characterized in that the washing- and cleaning-active surfactant granules comprise up to 20% by weight of other surfactants, based on the amount of ABS and APG.
    10. Washing- and cleaning-active surfactant granules with a bulk density above 600 g/l, prepared by a process according to one of Claims 1 to 9, comprising more than 60% by weight of alkylbenzenesulphonate.
    11. Washing- and cleaning-active surfactant granules with a bulk density above 600 g/l, prepared by a process according to one of Claims 1 to 9, comprising more than 60% by weight, preferably more than 70% by weight, of alkyl polyglycoside.
    12. Washing and cleaning composition comprising at least 10% by weight, preferably at least 20% by weight, of a process end product according to Claims 1 to 9.
    EP98100768A 1997-01-27 1998-01-17 Process for making surfactant granules Expired - Lifetime EP0859048B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    DE19702845A DE19702845A1 (en) 1997-01-27 1997-01-27 Process for the preparation of surfactant granules
    DE19702845 1997-01-27

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    EP0859048A2 EP0859048A2 (en) 1998-08-19
    EP0859048A3 EP0859048A3 (en) 1999-09-08
    EP0859048B1 true EP0859048B1 (en) 2003-10-29

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    AT (1) ATE253107T1 (en)
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    ES (1) ES2210601T3 (en)

    Cited By (3)

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    Publication number Priority date Publication date Assignee Title
    US11214763B2 (en) 2018-01-26 2022-01-04 Ecolab Usa Inc. Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a carrier
    US11377628B2 (en) 2018-01-26 2022-07-05 Ecolab Usa Inc. Solidifying liquid anionic surfactants
    US11655436B2 (en) 2018-01-26 2023-05-23 Ecolab Usa Inc. Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a binder and optional carrier

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    Publication number Priority date Publication date Assignee Title
    DE19824742A1 (en) * 1998-06-03 1999-12-09 Henkel Kgaa Production of alkyl polyglycoside-containing granules
    DE19923626A1 (en) * 1999-05-22 2000-11-23 Henkel Kgaa Production of surfactant granulates, useful for making laundry tablets, involves converting sugar surfactant to compound with water-soluble carrier material and granulating with non-aqueous solvent
    DE19951598A1 (en) * 1999-10-27 2001-05-03 Cognis Deutschland Gmbh Process for the production of solid sugar surfactants
    DE19961333B4 (en) * 1999-12-17 2006-12-14 Henkel Kgaa Process for the preparation of sugar surfactant granules
    DE10018812A1 (en) 2000-04-15 2001-10-25 Cognis Deutschland Gmbh Nonionic surfactant granulate, used in surfactant, cosmetic or pharmaceutical formulation or laundry or other detergent, is obtained by granulating and simultaneously drying aqueous surfactant paste in presence of organic polymeric carrier
    US20110005002A1 (en) * 2009-07-09 2011-01-13 Hiroshi Oh Method of Laundering Fabric

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    US3055835A (en) * 1958-11-18 1962-09-25 Colgate Palmolive Co Drying process for detergents
    US3733278A (en) * 1971-03-22 1973-05-15 Philadelphia Quartz Co Detergent slurry process
    CA995092A (en) * 1972-07-03 1976-08-17 Rodney M. Wise Sulfated alkyl ethoxylate-containing detergent composition
    ZA776946B (en) * 1976-12-02 1979-06-27 Colgate Palmolive Co Free flowing high bulk density particulate detergent softener
    JPH0384100A (en) * 1989-08-28 1991-04-09 Lion Corp Production of detergent composition having high bulk density
    DE4211699A1 (en) * 1992-04-08 1993-10-14 Henkel Kgaa Method for increasing the bulk density of spray-dried detergents
    DE4408502A1 (en) * 1994-02-18 1995-08-24 Henkel Ecolab Gmbh & Co Ohg Spray-dried granules with high bulk density
    DE19524287A1 (en) * 1995-07-06 1997-01-09 Henkel Kgaa Highly compacted detergent with good cold water solubility or dispersibility - comprises compacted core of active and auxiliary substances coated with relatively coarse particles of same substances with the aid of a solid, cold water soluble binder.

    Cited By (6)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US11214763B2 (en) 2018-01-26 2022-01-04 Ecolab Usa Inc. Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a carrier
    US11377628B2 (en) 2018-01-26 2022-07-05 Ecolab Usa Inc. Solidifying liquid anionic surfactants
    US11655436B2 (en) 2018-01-26 2023-05-23 Ecolab Usa Inc. Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a binder and optional carrier
    US11834628B2 (en) 2018-01-26 2023-12-05 Ecolab Usa Inc. Solidifying liquid anionic surfactants
    US11976255B2 (en) 2018-01-26 2024-05-07 Ecolab Usa Inc. Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a binder and optional carrier
    US12006488B2 (en) 2018-01-26 2024-06-11 Ecolab Usa Inc. Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a carrier

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    EP0859048A3 (en) 1999-09-08
    DE59809988D1 (en) 2003-12-04
    DE19702845A1 (en) 1998-07-30
    ATE253107T1 (en) 2003-11-15
    EP0859048A2 (en) 1998-08-19

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