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WO2006066730A1 - Procede pour produire des granules enzymatiques presentant une meilleure resistance a l'abrasion - Google Patents

Procede pour produire des granules enzymatiques presentant une meilleure resistance a l'abrasion Download PDF

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Publication number
WO2006066730A1
WO2006066730A1 PCT/EP2005/013090 EP2005013090W WO2006066730A1 WO 2006066730 A1 WO2006066730 A1 WO 2006066730A1 EP 2005013090 W EP2005013090 W EP 2005013090W WO 2006066730 A1 WO2006066730 A1 WO 2006066730A1
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WO
WIPO (PCT)
Prior art keywords
granules
preparation
enzyme
aqueous
aqueous preparation
Prior art date
Application number
PCT/EP2005/013090
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German (de)
English (en)
Inventor
Wilfried Rähse
Lars Kucka
Werner Pichler
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO2006066730A1 publication Critical patent/WO2006066730A1/fr

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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
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38672—Granulated or coated enzymes

Definitions

  • the present invention relates to a process for the preparation of enzyme granules having improved abrasion resistance and to the enzyme granules thus obtainable and their use in detergents and / or cleaners.
  • Industrially produced solids which are offered either as finished products or for further processing, are generally present in the form of powders, flakes or granules.
  • the granules are characterized by a good debris and pourability and a high bulk density.
  • the solids are preferably used in the form of granules in many industrial processes.
  • An example of such processes is the production of detergents and cleaning agents in granulation systems, eg. As in fluidized beds, mixers, extruders, rollers or in a combination of these systems.
  • the manufactured products which are produced either as detergent precursors or admixed components or as finished detergents and cleaners, are characterized by relatively high bulk densities in comparison to sprayed products and by a good debris and trickle. In addition, they have the advantage that their particle size distribution is adjusted so that the dust content is low.
  • enzymes in solid or in liquid form for various technical purposes, especially in detergents and cleaners, is well established in the art.
  • the enzymes in question are required in solid form, for example as granules or as a rounded extrudate.
  • they are usually coated with protective layers.
  • the protective layer serves essentially to prevent chemical reactions of the enzyme or with the enzyme, which is of crucial importance for long-term stability.
  • the protective layer but also to the exclusion of direct skin contact, the avoidance of Lung abrasion, the increase in mechanical stability and the setting of a controlled release effect bill.
  • the aesthetics of the particles, in particular the color, but also the odor can be improved via the protective layer.
  • Protective layers for particulate detergent ingredients, in particular for enzyme particles are described in detail in the prior art. These include, for example, those in which the active ingredient is surrounded as a particle core of a simple protective layer.
  • Protective compounds which are applied, for example, as a solution or as a melt for example, oily or waxy substances, usually water-soluble polymers, surfactants or plastics formed in situ by condensation polymerization, but also inorganic materials such as silicates (water glass) or kaolins are described.
  • pigments can be incorporated, which improve the encapsulation effect or color serve; For example, minerals such as clays or white pigments such as CaCO 3, ZnO or TiO 2 are described for this purpose.
  • the waxy substances such as polyethylene glycols (PEG) or polyvinyl alcohols (PVA) then additionally fulfill a binder function compared to the pigments.
  • PEG polyethylene glycols
  • PVA polyvinyl alcohols
  • the enzyme component does not itself need to represent the substantial nucleus of the particle, but rather can be used in the form of a protein-salt mixture as a separate layer on an inert core, the so-called seed particle (seed Particle) are applied.
  • seed Particle seed Particle
  • starch, modified starch, carrageenan, gum arabic, guar gum, polyethylene oxide, polyvinylpyrrolidone or polyethylene glycol are used.
  • a second layer of compounds such as polyvinyl alcohols (PVA), polyvinylpyrrolidone, cellulose derivatives, polyethylene glycols (PEG), polyethylene oxide, chitosan, gum arabic, xanthan and carrageenan can be applied to the enzyme layer to coat the seed particle or the enzyme-coated particle protect outside.
  • PVA polyvinyl alcohols
  • PEG polyethylene glycols
  • chitosan chitosan
  • gum arabic xanthan and carrageenan
  • WO 03/055967 discloses an improved process for coating core particles with a salt layer.
  • EP 804532 Bl coated enzyme granules wherein the enzyme granules have been obtained by coating an inert core and thereon applied a coating material consisting of a non-aqueous liquid or an aqueous emulsion thereof or an ointment-like mixture of such liquid or Emulsion having a melting between 30 and 90 ° C component.
  • the protective layer should contain a coagulation-inhibiting agent such as silica fume, calcium phosphate, titanium dioxide, talc or starch, and cause low dust-induced dust particle number.
  • the production of such particles is possible in any type of mixer or by spraying on the coating materials.
  • one or more pre-coatings of the enzyme-containing particles can be carried out before the actual coating, preferably in a fluidized-bed reactor.
  • the application WO 00/01793 A1 discloses a coating with a high moisture content. It consists of at least 60 wt .-% of a water-soluble substance having a molecular weight of less than 500, a certain pH and having a constant moisture content of more than 81% at 2O 0 C. This coating is applied as a solution and the solvent then distilled off. These water-soluble substances include inorganic salts such as sodium sulfate and citrate. The resulting particles may optionally be coated with additional layers, both under the high moisture content coating and above.
  • Patent specification EP 610 321 B1 discloses multiple-coated enzyme granules having a low dust rate, good stability values and a delayed release behavior. These contain a core of a water-soluble or -dispersible agent, for example clays, inorganic salts or starches, which can be obtained and coated by various granulation techniques, for example fluidized bed reactors. Then, an enzyme layer, which also contains vinyl polymer or vinyl copolymer, is applied directly or optionally via an intermediate layer containing vinyl polymer or vinyl copolymer.
  • a water-soluble or -dispersible agent for example clays, inorganic salts or starches
  • this is outwardly - optionally via another intermediate layer, which in turn contains an enzyme-protecting compound (in particular a chlorine scavenger) - completed by a layer which also contains vinyl polymer or vinyl copolymer and optionally pigments and / or binders.
  • an enzyme-protecting compound in particular a chlorine scavenger
  • vinyl polymers in each case polyvinyl alcohols of different molecular weight, different degrees of hydrolysis or viscosities or mixtures of different polyvinyl alcohols are particularly preferred.
  • the present invention thus relates to a process for the preparation of coated enzyme-containing granules, which is characterized in that applied to the granules particles with a urea-containing aqueous preparation and the water at least partially removed by drying.
  • the preparation can be present as a solution of the urea in water or, if in addition to the water-soluble urea also sparingly water-soluble or water-insoluble additives, in particular pigments, are present as a corresponding suspension.
  • the aqueous preparation to be applied to the enzyme granules for wrapping purposes preferably contains at least 2% by weight, in particular 20% by weight to 60% by weight and more preferably 30% by weight to 45% by weight, of urea.
  • the aqueous preparation may contain all otherwise usual wrapping materials for detergent ingredient granules which do not interact undesirably with the enzyme and thus can be incorporated into the urea-containing aqueous preparation so as not to lose its flowability, pumpability and sprayability.
  • the water content of the aqueous preparation is preferably in the range of 20 wt .-% to 60 wt .-%, in particular 30 wt .-% to 45 wt .-%.
  • the aqueous preparation preferably contains polyethylene glycol as a further coating material, with polyethylene glycols having an average molecular weight of from 4,000 to 70,000, in particular from 8,000 to 20,000, for example about 12,000, being preferred. Their content is preferably 5 wt .-% to 40 wt .-%, in particular 10 wt .-% to 25 wt .-%, based on the total amount of non-aqueous constituents of the preparation. Among them, urea preferably accounts for from 30% to 70%, more preferably from 45% to 60%, by weight, based on the total amount of non-aqueous components of the composition.
  • the wrapping material and thus the aqueous preparation may also contain customary additives coloring the finished granulate, in particular inorganic pigments and among these preferably titanium dioxide.
  • Their content is preferably 3 wt .-% to 25 wt .-%, in particular 5 wt .-% to 15 wt .-%, based on the total amount of non-aqueous constituents of the preparation.
  • the preparation may also contain stabilizers for the urea, among these in particular hydroxycarboxylic acids such as lactic acid. If present, they are preferably not more than 1% by weight, especially in an amount ranging from 0.01% by weight to 0.5% by weight, and preferably from 0.05% by weight to 0.1% by weight. %, based on the total amount of non-aqueous constituents of the preparation.
  • stabilizers for the urea among these in particular hydroxycarboxylic acids such as lactic acid. If present, they are preferably not more than 1% by weight, especially in an amount ranging from 0.01% by weight to 0.5% by weight, and preferably from 0.05% by weight to 0.1% by weight. %, based on the total amount of non-aqueous constituents of the preparation.
  • the aqueous preparation may also contain antioxidants and / or odor absorbers. If present, these are preferably present in an amount in the range of 0.5% to 50%, more preferably 3% to 30%, and more preferably 10% to 25% by weight, based on the total amount of non-aqueous components of the preparation.
  • the surfactants and cosurfactants optionally present in the composition are preferably present in an amount ranging from about 0.1% to about 10%, more preferably from 0.2% to 5%, and more preferably from 0.3% to 1%, based on the total amount non-aqueous constituents of the preparation.
  • the non-aqueous constituents of the preparation make up the coating layer of the coated enzyme granules obtainable by the process according to the invention, which, depending on the drying conditions, however, may also contain small amounts of water, but preferably not more than 5% by weight and in particular 0.01% by weight. Make up to 1% by weight of the coating layer.
  • the aqueous preparation is brought to a fluidized bed of enzyme granules to be enveloped in a fluidized bed system via nozzles.
  • the temperature of the fluidizing agent which is preferably 35 ° C to 50 0 C and and in particular at a granule temperature of not more than 42 ° C, the removal of the water can be achieved by drying in a simple manner.
  • Further objects of the present invention are enzyme granules which can be obtained by the process according to the invention, as well as detergents and / or cleaning agents which contain such granules, and the use of such granules for the production of detergents and / or cleaning agents.
  • the granules coated according to the invention have an improved abrasion resistance, which is particularly advantageous for the mentioned purpose.
  • the detergents and cleaners are preferably particulate, although the enzyme granules according to the invention or coated according to the invention can, if desired, also be incorporated into liquid or pasty detergents or cleaners.
  • Suitable enzymes are primarily those derived from microorganisms, such as bacteria or fungi, proteases, lipases, amylases, mannanases and / or cellulases, with proteases produced by Bacillus species, alone or in combination with the other enzymes, being preferred. They are obtained in a known manner by fermentation processes from suitable microorganisms, which are described, for example, in German Offenlegungsschriften DE 19 40 488, DE 2044 161, DE 21 01 803 and DE 21 21 397, US Pat. Nos. 3,632,957 and 4,264,738 and European Patent Application EP 006 638.
  • the process according to the invention can be used particularly advantageously for the formulation of very active proteases, which are known, for example, from international patent application WO 91/2792, because their storage-stable incorporation into detergents and cleaners often presents problems and according to the invention the formation of undesired enzyme dusts is avoided.
  • Enzymes are preferably present in the granules according to the invention or in accordance with the invention in amounts of from 0.5% by weight to 20% by weight.
  • the protease activity is preferably Example, 150 000 protease units (PE, determined by the method described in Tenside 7 (1970), 125) to 350 000 PE, in particular 160 000 PE to 300 000 PE, per gram of enzyme granules.
  • the enzyme granules to be coated can be prepared by any methods known for this purpose. In order to ensure the most uniform possible wrapping by the method according to the invention they should be as round as possible; Preferably, the form factor of the enzyme granules to be coated is more than 0.85.
  • enzymes are brought into granule form with the aid of inert carrier materials.
  • Suitable support materials for the enzyme are, in principle, all organic or inorganic powdery substances which do not destroy or deactivate the enzymes to be granulated, or tolerable, and are stable under granulation conditions.
  • Such substances include, for example, starch, cornmeal, cellulose powder, alkali metal aluminosilicate, in particular zeolite, layered silicate, for example bentonite or smectite, and water-soluble inorganic or organic salts, for example alkali metal chloride, alkali metal sulfate, alkali metal carbonate, citrate or acetate, where sodium or potassium preferred alkali metals.
  • a carrier material mixture is used which comprises water-swellable starch and optionally cereal flour, cellulose powder and / or alkali metal carbonate.
  • the water-swellable starch is preferably maize, wheat and rice and potato starch or mixtures thereof, the use of maize and wheat starch being preferred.
  • Swelling-capable starch is preferably present in the enzyme granules in amounts of from 20% by weight to 50% by weight, in particular from 25% by weight to 45% by weight.
  • the cereal flour optionally contained is, in particular, a product which can be produced from wheat, rye, barley or oats or a mixture of these flours, whole-wheat flours being preferred. Under a wholemeal flour is understood that not fully ground flour that has been made from whole, unpeeled grains or at least predominantly consists of such a product, the remainder of fully ground flour or starch.
  • wheat flour qualities such as Type 450 or Type 550, are preferably used.
  • the use of flour products of the above-mentioned swellable starches leading crops is possible, if care is taken that the flours have been made from whole grains.
  • the flour component of the aggregate mixture is known to achieve a substantial odor reduction of the enzyme preparation, which far exceeds the odor reduction by the incorporation of equal amounts of appropriate types of starch.
  • Such cereal flour is preferably present in enzyme granules in amounts of up to 35% by weight, in particular from 15% by weight to 25% by weight.
  • Enzyme granules may contain as further component of the support material preferably 1 wt .-% to 50 wt .-%, in particular 5 wt .-% to 25 wt .-%, based on total granules, of a Granulierangesniittelsystems containing alkali carboxymethylcellulose with degrees of substitution of 0 , 5 to 1 and polyethylene glycol and / or alkyl polyethoxylate.
  • this granulation auxiliary system are preferably, in each case based on finished enzyme granules, 0.5 wt .-% to 5 wt .-% alkali carboxymethylcellulose with degrees of substitution of 0.5 to 1 and up to 3 wt .-% polyethylene glycol and / or alkyl polyethoxylate , wherein is particularly preferred if at least 0.5 wt .-%, in particular 0.8 wt .-% to 2 wt .-% polyethylene glycol having an average molecular weight below 1000 and / or alkyl polyethoxylate with at least 7 ethoxy groups is present, if more contained as 2 wt .-% alkali carboxymethyl cellulose. Higher substituted carboxymethylcellulose, with degrees of substitution up to 3, is preferably not included in the granulation aid system.
  • Phosphated starch is understood to mean a starch derivative in which hydroxyl groups of the starch anhydroglucose units are replaced by the group -O-P (O) (OH) 2 or its water-soluble salts, in particular alkali metal salts, such as sodium and / or potassium salts.
  • degree of phosphating of the starch is meant the number of esterified oxygen atom carrying one phosphate group per saccharide monomer averaged over all saccharide units.
  • the average degree of phosphating in preferably used phosphated starches is in the range of 1.5 to 2.5, since much smaller amounts are required, especially when using them, in order to achieve a certain granule strength than when using carboxymethylcellulose.
  • partially hydrolysed starches are understood to mean oligomers or polymers of carbohydrates which are prepared by customary, for example acid or enzyme-catalyzed processes are accessible by partial hydrolysis of starch.
  • Preference is given to polysaccharides having a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, DE being a customary measure of the reducing effect of a polysaccharide compared to dextrose which has a DE of 100.
  • DE dextrose equivalent
  • maltodextrins DE 3 - 20
  • dry glucose syrups DE 20 - 37
  • so-called yellow dextrins and white dextrins with higher mean mobilities in the range of approximately 2,000 to 30,000 are useful.
  • Contents of enzyme granules to be coated are 0.1 wt .-% to 20 wt .-%, in particular 0.5 wt .-% to 15 wt .-% phosphated starch is preferred.
  • additional cellulose or starch ethers such as carboxyethyl starch, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and corresponding cellulose mixed ethers, gelatin, casein, tragacanth, Maltodextrose, sucrose, invert sugar, glucose syrup or other water-soluble or readily dispersible oligomers as additional constituents of Granulierysffensystems or polymers of natural or synthetic origin.
  • Useful synthetic water-soluble polymers are polyacrylates, polymethacrylates, copolymers of acrylic acid with maleic acid or vinyl group-containing compounds, furthermore polyvinyl alcohol, partially saponified polyvinyl acetate and polyvinylpyrrolidone.
  • the abovementioned compounds are those having free carboxyl groups, they are normally present in the form of their alkali metal salts, in particular their sodium salts.
  • Such additional granulation aids may optionally be present in the enzyme granules in amounts of up to 10% by weight, in particular from 0.5% by weight to 8% by weight.
  • higher molecular weight polyethylene glycols ie those having an average molecular weight above 1000, are useful as synthetic water-soluble polymers with dust-binding effect, but the higher molecular weight polyethylene glycols cause an undesirable increase in the required granule dissolution time, so that these substances in the enzyme granules according to the invention or inventively produced preferably completely absence.
  • microfiltration is preferably as a cross-flow microfiltration under Use porous tubes with micropores greater than 0.1 microns, flow rates of the concentrate solution of more than 2 m / s and a pressure difference to the permeate side of less than 5 bar, as described for example in European Patent Application EP 200,032.
  • the microfiltration permeate is preferably concentrated by ultrafiltration, optionally followed by vacuum evaporation.
  • the concentration may, as described in international patent application WO 92/11347, be conducted in such a way that only relatively low contents of dry substance of preferably 5% by weight to 50% by weight, in particular 10% by weight, are obtained. reaches 40 wt .-%.
  • the concentrate may then be added to a suitably previously prepared dry, powdery to granular mixture of the above-described additives.
  • the water content of the mixture should be chosen so that it can be converted into granular, non-sticking at room temperature particles when working with stirring and striking tools and plastically deform and apply at higher pressures.
  • the free-flowing premix can then be processed in a manner known in principle in a kneader and a connected extruder to a plastic, homogeneous as possible mass, as a result of mechanical processing, the mass to temperatures between 40 0 C and 60 ° C, in particular 45 ° C can heat up to 55 ° C.
  • the material leaving the extruder is passed through a perforated disc with subsequent doctor blade and thereby comminuted to form cylindrical particles of defined size.
  • the diameter of the holes in the perforated disc is 0.7 mm to 1.2 mm, preferably 0.8 mm to 1.0 mm.
  • the particles present in this form are coated with the coating system according to the invention.
  • a device which consists of a cylindrical container with stationary, solid side walls and a base plate rotatably mounted friction plate.
  • any dust-like fractions with a grain size of less than 0.1 mm, in particular less than 0.4 mm and any coarse fractions with a grain size of more than 2 mm in particular be removed over 1.6 mm by screening or air classification and optionally returned to the manufacturing process.
  • the beads are continuously or batchwise, preferably using a fluidized bed dryer, at supply air temperatures of preferably 35 ° C to 50 ° C and in particular at a product temperature of not more than 42 ° C to the desired residual moisture content of, for example, 4 wt .-% to 10 wt .-%, in particular 5 wt .-% to 8 wt .-%, based on total granules, dried, if they previously had higher water contents.
  • a fluidized bed dryer at supply air temperatures of preferably 35 ° C to 50 ° C and in particular at a product temperature of not more than 42 ° C to the desired residual moisture content of, for example, 4 wt .-% to 10 wt .-%, in particular 5 wt .-% to 8 wt .-%, based on total granules, dried, if they previously had higher water contents.
  • the process according to the invention is carried out by applying the urea-containing aqueous preparation to the granulate particles.
  • the granules obtained by the process according to the invention consist of largely rounded, uniformly coated and dust-free particles, which generally have a bulk density of about 500 to 800 grams per liter, in particular 600 to 700 grams per liter.
  • the granules of the invention are characterized by a very high storage stability, especially at temperatures above room temperature and high humidity, and a rapid and complete solution behavior in the wash liquor.
  • the granules according to the invention preferably release 100% of their enzyme activity in water at 25 ° C. within 3 minutes, in particular within 90 seconds to 2 minutes.
  • the enzyme granulate according to the invention or produced by the process according to the invention is preferably used for the production of solid, in particular particulate detergents or cleaners, which can be obtained by simply mixing the enzyme granules with further powder components customary in such agents.
  • the enzyme granules preferably have average particle sizes in the range from 0.7 mm to 1.2 mm.
  • the granules coated according to the invention preferably contain less than 2% by weight, in particular at most 1.4% by weight of particles with grain sizes outside the range of 0.4 mm to 1.6 mm. The method is not limited to these particle sizes, but covers a grain size spectrum d 50 from 0.1 mm to over 2 mm.

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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)
  • Detergent Compositions (AREA)
  • Enzymes And Modification Thereof (AREA)

Abstract

L'objectif de la présente invention est d'améliorer la résistance à l'abrasion de granulés enzymatiques enrobés. A cette fin, les particules de granulés sont mises en contact avec une préparation aqueuse contenant de l'urée et l'eau est au moins partiellement éliminée par séchage.
PCT/EP2005/013090 2004-12-20 2005-12-07 Procede pour produire des granules enzymatiques presentant une meilleure resistance a l'abrasion WO2006066730A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200410062326 DE102004062326A1 (de) 2004-12-20 2004-12-20 Verfahren zur Herstellung von Enzymgranulaten mit verbesserter Abriebfestigkeit
DE102004062326.0 2004-12-20

Publications (1)

Publication Number Publication Date
WO2006066730A1 true WO2006066730A1 (fr) 2006-06-29

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PCT/EP2005/013090 WO2006066730A1 (fr) 2004-12-20 2005-12-07 Procede pour produire des granules enzymatiques presentant une meilleure resistance a l'abrasion

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3324038A (en) * 1964-04-17 1967-06-06 Procter & Gamble Detergent composition
US4009076A (en) * 1972-11-03 1977-02-22 Lever Brothers Company Enzyme granules
WO1991017235A1 (fr) * 1990-05-04 1991-11-14 Genencor International, Inc. Granules contenant a la fois une enzyme et un agent protecteur d'enzyme, et compositions de detergent contenant lesdits granules
WO2004082564A2 (fr) * 2003-03-18 2004-09-30 Novozymes A/S Granules enzymatiques revetus

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69732775T2 (de) * 1996-04-12 2006-01-26 Novozymes A/S Enzymhaltige granulatkörner sowie verfahren zu deren herstellung

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3324038A (en) * 1964-04-17 1967-06-06 Procter & Gamble Detergent composition
US4009076A (en) * 1972-11-03 1977-02-22 Lever Brothers Company Enzyme granules
WO1991017235A1 (fr) * 1990-05-04 1991-11-14 Genencor International, Inc. Granules contenant a la fois une enzyme et un agent protecteur d'enzyme, et compositions de detergent contenant lesdits granules
WO2004082564A2 (fr) * 2003-03-18 2004-09-30 Novozymes A/S Granules enzymatiques revetus

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