EP0847243A1 - Pourable organic acid-based granulates, process for their preparation and their use - Google Patents

Pourable organic acid-based granulates, process for their preparation and their use

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Publication number
EP0847243A1
EP0847243A1 EP96930104A EP96930104A EP0847243A1 EP 0847243 A1 EP0847243 A1 EP 0847243A1 EP 96930104 A EP96930104 A EP 96930104A EP 96930104 A EP96930104 A EP 96930104A EP 0847243 A1 EP0847243 A1 EP 0847243A1
Authority
EP
European Patent Office
Prior art keywords
acid
granules
organic
granules according
salts
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.)
Withdrawn
Application number
EP96930104A
Other languages
German (de)
French (fr)
Inventor
Ulrich Bröckel
Hans Müschen
Joachim Meyer
Beate Salvador
Bruno Käsler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP0847243A1 publication Critical patent/EP0847243A1/en
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/003—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic followed by coating of the granules
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K30/00—Processes specially adapted for preservation of materials in order to produce animal feeding-stuffs
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K30/00—Processes specially adapted for preservation of materials in order to produce animal feeding-stuffs
    • A23K30/10—Processes specially adapted for preservation of materials in order to produce animal feeding-stuffs of green fodder
    • A23K30/15—Processes specially adapted for preservation of materials in order to produce animal feeding-stuffs of green fodder using chemicals or microorganisms for ensilaging
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K40/00—Shaping or working-up of animal feeding-stuffs
    • A23K40/30—Shaping or working-up of animal feeding-stuffs by encapsulating; by coating
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
    • A23P10/00—Shaping or working of foodstuffs characterised by the products
    • A23P10/30—Encapsulation of particles, e.g. foodstuff additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/30—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic using agents to prevent the granules sticking together; Rendering particulate materials free flowing in general, e.g. making them hydrophobic

Definitions

  • the present invention relates to a free-flowing granulate, consisting of a core and a shell, the core material containing an organic acid and a porous carrier and the shell having a water-soluble or water-swellable covering agent.
  • the invention further relates to a process for the production of free-flowing, odor-reduced granules based on organic acids, preferably formic, acetic and / or propionic acid, and the use of the granules for the treatment of food and feed, and for use in silages.
  • organic acids preferably formic, acetic and / or propionic acid
  • liquid organic acids can only be incorporated in concentrated form, for example in animal feed, by considerable technical effort.
  • DE 28 33 727 AI discloses a particulate, fungicidal material which contains propionic acid and a carrier material. With this material, the number of mold colonies in stored agricultural harvest products should not increase even if the incubation period is several days. However, it has been shown that such material itself is not stable in storage (loss of acid) and that the maximum amount of propionic acid which can be applied depends heavily on the carrier material used. In addition, this material gives off unpleasant odors due to the volatilization of the propionic acid.
  • the present invention was therefore based on the object of providing free-flowing, low-odor granules for the treatment of food and animal feed, with which the handling properties for the user are significantly improved.
  • the focus here was on the production of a "solid organic acid" in the form of an adsorbate, which should differ essentially from simple drinking products in that by (a) allowing an acid fraction> 30% by weight in the solid, independent of the carrier material, and thus carrying the highest possible "active ingredient fraction” and (b) limiting the leakage of the organic acid from the adsorbate to a minimum and thus reducing the " Active ingredient content "retained.
  • the powdery end product should have good storage, flow and processing properties.
  • a granulate consisting of a core and a shell, the core material containing an organic acid and a porous carrier and the shell having a cover agent which is water-soluble or water-swellable at 20 ° C.
  • the granulate according to the invention has the advantage that a reduction in the strong pungent acid smell is achieved and the acid component, despite the solid formulation, is readily and quickly released from the solid powder.
  • the invention further relates to a process for the production of granules containing organic acids and porous carrier materials, which is characterized in that the carrier material is soaked with the liquid organic acid, then with a covering agent which is obtained at room temperature stares, is agglomerated, the covering agent being added to such an extent that the resulting granules are coated and, if appropriate, further odorization is carried out by adding fragrances and, if appropriate, the pourability of the agglomerates is ensured by powdering with a finely dispersed powdering agent.
  • Liquid organic acid is understood to mean acids or acid mixtures which are liquid at the processing temperatures or which are converted into liquids by increasing the temperature or dissolving or dispersing them in liquids.
  • the granules according to the invention have a powdering agent on the surface of the casing.
  • the core preferably contains 30-90% by weight, in particular 50-80% by weight, of organic acid.
  • the organic acid preferably consists of one or more Ci-Cg-mono- or di-carboxylic acids, especially formic, acetic and / or propionic acid.
  • Porous, organic or inorganic carrier materials can be used as carriers, the particle sizes of which are between 1 ⁇ m and 1,000 ⁇ m, preferably between 5 ⁇ m and 100 ⁇ m.
  • the core can also contain other solids, for example solids suitable as feed additives, such as Ca propionate.
  • Water-soluble polymers, organic acids, their salts or low-melting inorganic salts can be used as covering agents.
  • Cereal bran, silicates, pearlite or silica are preferably used as carriers in proportions between 10% by weight and 70% by weight, preferably 20 to 40% by weight, based on the weight of the core.
  • Polyethylene glycols, polyvinylpyrrolidones or organic acids and their salts from C3 to C14, preferably C3 to C6, in particular citric acid, fumaric acid, succinic acid, adipic acid, benzoic acid and their salts or amino acids and their salts, are preferably used as covering agents.
  • the carrier material is placed in a mixer, soaked with the organic acid and then agglomerated and coated with the covering agent.
  • the size of the granules can be set by means of process parameters during mixing and also by subsequent sieving or grinding.
  • the granules preferably have an average diameter of less than 3 mm, in particular 0.3-1.3 mm.
  • residual water may be present in the binding liquid used for coating and agglomerating. After the agglomeration process, this water can be bound by a powdering process with a dry and finely dispersed powder. This powdering process also prevents the agglomerates from sticking later and, for example, additionally applies the salt of the organic acid used (for example sodium or calcium propionate) to the agglomerate.
  • a fragrance or flavoring agent is added, such as, for example, vanillin, citral or fructin, as a result of which an additional odor-masking effect and, for example, attracting animal feed intake can be achieved.
  • organic or inorganic porous carriers are suitable for the production of such free-flowing, odor-reduced agglomerates, provided that they are acid-resistant.
  • examples are cereal bran, perlite, clay materials, silicates and silicic acids, preference being given to the inorganic carriers, since their material properties can be better controlled.
  • Particularly suitable covering agents (binding liquids) for the agglomeration process and for coating are those which have a softening temperature of over 30 ° C., preferably over 60 ° C., in order to prevent deformation of the agglomerates at a higher storage temperature. It is preferred to use cover agents which, moreover, do not counteract the pH-lowering action of the adsorbed organic acid or, if appropriate, support or strengthen it.
  • binding liquids For example, highly concentrated, heated sugar solutions or alkali / alkaline earth metal / formate / acetate / propionate solutions are suitable as binding liquids.
  • the final watering step allows their residual water content to be absorbed.
  • Low melting polyethylene glycols such as PEG 4000, melts of citric acid, adipic acid, fumaric acid or benzoic acid or their salts, highly concentrated solutions of amino acids or mixtures of these acids are preferably suitable as binary liquids. 5-80% binding liquid is used, but preferably 10 to 25% by weight, based on the weight of the granulate.
  • suitable powdering agents are themselves finely dispersed, ground organic acids or their salts, for example Na formate, and also inorganic salts or Aerosil. ⁇ 10%, preferably between 0.5 and 5% by weight, of the powdering agents are added.
  • the porous carrier is placed in the mixer, for example, in an Eichrich mixer and soaked with the organic acid at low energy inputs.
  • the procedure can also be such that the liquid is placed in the mixer and the carrier 5 is metered in. In this case, higher energy inputs must be used.
  • the viscosity of the binding liquid should be adjusted by an appropriate temperature selection in such a way that it is below 1,000 mPas, preferably in the range ⁇ 100 mPas, in order to spray the binding fluids.
  • the proportion of these fragrances can be ⁇ 1% by weight, preferably from 0.05 to 0.5% by weight, based on the granules.
  • the agglomerates produced in this way are low in dust, reduce odor and their organic acid content is
  • the granules according to the invention are suitable for the treatment of food and feed, and for use in silages.
  • Food and animal feed are to be understood in particular as crop products such as hay, silage, moist cereals, legumes or cereal fruits, but also milk exchange, liquid, mixed and mineral feed, fish silages or fish meal.
  • the granules according to the invention can also contain other additives, such as minerals, vitamins, antibiotics or protein additives. Examples
  • Sipernat ® roch ⁇ disperse silica, Fa. Degussa
  • an acid mixture consisting of equal parts of formic acid and propionic acid, soaked.
  • the acid mixture is readily absorbed; a loose, free-flowing product is created.
  • the product has a pungent - smelly formic acid / propionic acid smell.
  • Example 2 Analogously to Example 1, 100 g of pearlite are introduced and soaked in formic acid. The acid is readily absorbed, but the product tends to stick and smells strongly of formic acid.
  • Example 2 Analogously to Example 2 were charged with 400 g of Sipernat ® in an Eirich mixer and impregnated with 1.100 g of formic acid; the ants' acidity is then 71%. 260 g of citric acid melt are injected into the mixing chamber at 170 ° C. as a binding liquid from a heated storage container through a two-component nozzle. The resulting agglomerates are powdered with 44 g Sipernat ® and 8 g vanillin. The total acidity is * 74%. The resulting agglomerates are significantly reduced in the smell of formic acid.
  • Powdered Sipernat ® and 24 g vanillin The total acidity is * 74 ..
  • the resulting agglomerates are significantly reduced in smell and easy to pour.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Food Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Zoology (AREA)
  • Organic Chemistry (AREA)
  • Animal Husbandry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microbiology (AREA)
  • Health & Medical Sciences (AREA)
  • Nutrition Science (AREA)
  • Fodder In General (AREA)
  • Fats And Perfumes (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Glanulating (AREA)
  • General Preparation And Processing Of Foods (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Cereal-Derived Products (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Paints Or Removers (AREA)
  • Medicinal Preparation (AREA)

Abstract

The invention concerns pourable granulates comprising a core and a casing, characterized in that the core material contains an organic acid and a porous carrier, and the casing comprises a covering agent which is water-soluble or can swell in water at 20 °C.

Description

Rieselfahiges Granulat auf Basis organischer Sauren, Verfahren zu seiner Herstellung und seine VerwendungFree-flowing granules based on organic acids, process for their production and their use
Beschreibungdescription
Die vorliegende Erfindung betrifft ein rieselfahiges Granulat, bestehend aus einem Kern und einer Hülle, wobei das Kernmaterial eine organische Saure und eine porösen Trager enthalt und die Hülle ein wasserlösliches oder wasserquellbares Abdeckmittel auf¬ weist.The present invention relates to a free-flowing granulate, consisting of a core and a shell, the core material containing an organic acid and a porous carrier and the shell having a water-soluble or water-swellable covering agent.
Die Erfindung betrifft weiterhin ein Verfahren zur Herstellung rieselfahiger, geruchsreduzierter Granulate auf Basis organischer Sauren vorzugsweise Ameisen-, Essig-, und/oder Propionsäure, so¬ wie die Verwendung des Granulats zur Behandlung von Lebens- und Futtermitteln, sowie zur Anwendung in Silagen.The invention further relates to a process for the production of free-flowing, odor-reduced granules based on organic acids, preferably formic, acetic and / or propionic acid, and the use of the granules for the treatment of food and feed, and for use in silages.
Kurzket'tige organische Sauren, wie Ameisensaure, Essigsaure oder Propionsäure finden in der Ansauerung und Konservierung von Le¬ bens- und Futtermitteln Anwendung. Nachteile dieser Sauren sind (a) ihr flussiger Aggregatzustand bei Raumtemperatur, (b) der aus dem niedrigen Dampfdruck resultierende scharfe, stechende Geruch und (c) ihre Korrosivität.Kurzket 'term organic acids such as formic acid, acetic acid or propionic acid found in the Ansauerung and preservation of bens- Le¬ and feed application. Disadvantages of these acids are (a) their liquid state at room temperature, (b) the sharp, pungent odor resulting from the low vapor pressure and (c) their corrosiveness.
Ferner sind die flussigen organischen Sauren in konzentrierter Form nur durch erheblichen technischen Aufwand beispielsweise in Futtermittel einzuarbeiten.Furthermore, the liquid organic acids can only be incorporated in concentrated form, for example in animal feed, by considerable technical effort.
Aus der DE 28 33 727 AI ist ein teilchenförmiges, fungizid wir¬ kendes Material bekannt, das Propionsäure und ein Tragermaterial enthalt. Mit diesem Material soll auch bei mehrtägiger Inkubati¬ onsdauer die Zahl der Schimmelkolonien bei gelagerten landwirt¬ schaftlichen Ernteprodukten nicht ansteigen. Es hat sich aber ge- zeigt, daß derartiges Material selbst nicht lagerstabil ist (Sau- reverlust) und die Hochstmenge an Propionsäure, die aufgebracht werden kann, stark vom verwendeten Tragermaterial abhangt. Zudem treten mit diesem Material durch Verflüchtigung der Propionsäure unangenehme Gerüche auf.DE 28 33 727 AI discloses a particulate, fungicidal material which contains propionic acid and a carrier material. With this material, the number of mold colonies in stored agricultural harvest products should not increase even if the incubation period is several days. However, it has been shown that such material itself is not stable in storage (loss of acid) and that the maximum amount of propionic acid which can be applied depends heavily on the carrier material used. In addition, this material gives off unpleasant odors due to the volatilization of the propionic acid.
Der vorliegenden Erfindung lag daher die Aufgabe zugrunde, rieselfahige, geruchsarme Granulate zur Behandlung von Lebens¬ und Futtermitteln zur Verfugung zu stellen, mit denen die Hand¬ lingeigenschaften fur den Anwender wesentlich verbessert sind. Dabei stand im Vordergrund die Herstellung einer "festen organi¬ schen Saure" in Form eines Adsorbats, das sich im wesentlichen von einfachen Trankungsprodukten dadurch unterscheiden sollte, indem es (a) einen Saureanteil > 30 Gew.-% im Feststoff unabhän¬ gig vom Tragermaterial ermöglicht und damit einen möglichst hohen "Wirkstoffanteil" tragt und (b) das Austreten der organischen Saure aus dem Adsorbat auf ein Minimum beschrankt und somit den "Wirkstoffgehalt" beibehalt. Das pulverformige Endprodukt sollte gute Lager-, Fließ- und Verarbeitungseigenschaften aufweisen.The present invention was therefore based on the object of providing free-flowing, low-odor granules for the treatment of food and animal feed, with which the handling properties for the user are significantly improved. The focus here was on the production of a "solid organic acid" in the form of an adsorbate, which should differ essentially from simple drinking products in that by (a) allowing an acid fraction> 30% by weight in the solid, independent of the carrier material, and thus carrying the highest possible "active ingredient fraction" and (b) limiting the leakage of the organic acid from the adsorbate to a minimum and thus reducing the " Active ingredient content "retained. The powdery end product should have good storage, flow and processing properties.
Diese Aufgabe wird gelost durch ein Granulat, bestehend aus einem Kern und einer Hülle, wobei das Kernmaterial eine organische Saure und eine porösen Trager enthalt und die Hülle ein bei 20°C wasserlösliches oder wasserquellbares Abdeckmittel aufweist.This object is achieved by a granulate consisting of a core and a shell, the core material containing an organic acid and a porous carrier and the shell having a cover agent which is water-soluble or water-swellable at 20 ° C.
Das erfindungsgemaße Granulat hat den Vorteil, daß eine Reduzie¬ rung des stark stechenden Sauregeruchs erreicht wird und der Sau- reanteil trotz Feststofformulierung gut und schnell loslich aus dem Feststoffpulver austritt.The granulate according to the invention has the advantage that a reduction in the strong pungent acid smell is achieved and the acid component, despite the solid formulation, is readily and quickly released from the solid powder.
Die Erfindung betrifft weiterhin ein Verfahren zur Herstellung von Granulaten, enthaltend organische Sauren und poröse Trager- materialien, das dadurch gekennzeichnet ist, daß das Trager¬ material mit der flussigen organischen Saure getrankt wird, an¬ schließend mit einem Abdeckmittel, das bei Raumtemperatur er¬ starrt, agglomeriert wird, wobei das Abdeckmittel in solchem Maße zugegeben wird, daß die entstehenden Granulate gecoatet werden und gegebenenfalls eine weitere Odorierung durch die Zugabe von Riechstoffen erfolgt und gegebenenfalls die Rieselfahigkeit der Agglomerate durch Abpudern mit einem feindispersen Pudermittel sichergestellt wird.The invention further relates to a process for the production of granules containing organic acids and porous carrier materials, which is characterized in that the carrier material is soaked with the liquid organic acid, then with a covering agent which is obtained at room temperature stares, is agglomerated, the covering agent being added to such an extent that the resulting granules are coated and, if appropriate, further odorization is carried out by adding fragrances and, if appropriate, the pourability of the agglomerates is ensured by powdering with a finely dispersed powdering agent.
Unter "flüssiger organischer Saure" werden Sauren oder Sauregemi- sche verstanden, die bei den Verarbeitungstemperaturen flussig sind oder durch Temperaturerhöhung oder Losung bzw. Dispergierung in Flüssigkeiten in flussigem Zustand überfuhrt werden."Liquid organic acid" is understood to mean acids or acid mixtures which are liquid at the processing temperatures or which are converted into liquids by increasing the temperature or dissolving or dispersing them in liquids.
In einer bevorzugten Ausführungsform weist das erfindungsgemaße Granulat ein Puderungsmittel auf der Hüllenoberflache auf. Der Kern enthalt bevorzugt 30-90 Gew.-%, insbesondere 50-80 Gew.-% organische Saure. Die organische Saure besteht vorzugsweise aus einer oder mehreren Ci-Cg-Mono- oder Di-Carbonsäuren, insbesondere Ameisen-, Essig- und/oder Propionsäure.In a preferred embodiment, the granules according to the invention have a powdering agent on the surface of the casing. The core preferably contains 30-90% by weight, in particular 50-80% by weight, of organic acid. The organic acid preferably consists of one or more Ci-Cg-mono- or di-carboxylic acids, especially formic, acetic and / or propionic acid.
Als Trager können poröse, organische oder anorganische Trager¬ materialien eingesetzt werden, deren Partikelgroßen zwischen 1 μm und 1.000 μm, vorzugsweise zwischen 5 μm und 100 μm liegen. Der Kern kann auch noch weitere Feststoffe enthalten, z.B. als Futtermittelzuschlagstoffe geeignete Feststoffe wie Ca-Propionat.Porous, organic or inorganic carrier materials can be used as carriers, the particle sizes of which are between 1 μm and 1,000 μm, preferably between 5 μm and 100 μm. The core can also contain other solids, for example solids suitable as feed additives, such as Ca propionate.
Als Abdeckmittel können wasserlösliche Polymere, organische Sauren, deren Salze oder niedrig schmelzende anorganische Salze verwendet werden.Water-soluble polymers, organic acids, their salts or low-melting inorganic salts can be used as covering agents.
Als Trager werden bevorzugt Getreidekleien, Silikate, Perlit oder Kieselsauren in Anteilen zwischen 10 Gew.-% und 70 Gew.-%, vor- zugsweise mit 20 bis 40 Gew.-%, bezogen auf das Gewicht des Kerns, verwendet.Cereal bran, silicates, pearlite or silica are preferably used as carriers in proportions between 10% by weight and 70% by weight, preferably 20 to 40% by weight, based on the weight of the core.
Als Abdeckmittel werden bevorzugt Polyethylenglykole, Polyvinyl- pyrrolidone oder organische Sauren und deren Salze von C3 bis C14, vorzugsweise C3 bis C6, insbesondere Zitronensaure, Fumar¬ saure, Bernsteinsaure, Adipinsäure, Benzoesäure und deren Salze oder Aminosäuren und deren Salze, verwendet.Polyethylene glycols, polyvinylpyrrolidones or organic acids and their salts from C3 to C14, preferably C3 to C6, in particular citric acid, fumaric acid, succinic acid, adipic acid, benzoic acid and their salts or amino acids and their salts, are preferably used as covering agents.
In einer bevorzugten Ausführungsform des erfindungsgemaßen Ver- fahrens wird das Tragermaterial in einem Mischer vorgelegt, mit der organischen Saure getränkt und anschließend mit dem Abdeck¬ mittel agglomeriert und gecoatet.In a preferred embodiment of the method according to the invention, the carrier material is placed in a mixer, soaked with the organic acid and then agglomerated and coated with the covering agent.
Die losen und getränkten Tragerstoffpartikeln werden mit dem Ab- deckmittel (Bindeflüssigkeit) gemischt, wobei die Bindeflüssig¬ keit in der Regel aus einer hochkonzentrierten Losung oder Schmelze von wasserlöslichen oder wasserquellbaren Substanzen be¬ steht, die bei Raumtemperatur (20°C) erstarren. Diese Bindeflüs¬ sigkeit wird bevorzugt im erwärmten Zustand auf die getränkten Tragerstoffpartikeln aufgebracht und mit diesen gemischt. Dabei erstarren die Bindeflussigkeiten auf der Oberflache der getränk¬ ten Tragerstoffpartikeln. Durch geeignete Betriebsparameter des Mischers kommt es zur Agglomeration verschiedener Partikeln zu größeren Granulaten.The loose and impregnated carrier particles are mixed with the covering agent (binding liquid), the binding liquid generally consisting of a highly concentrated solution or melt of water-soluble or water-swellable substances which solidify at room temperature (20 ° C.). This binding liquid is preferably applied to the impregnated carrier material particles in the heated state and mixed with them. The binding liquids solidify on the surface of the impregnated carrier particles. Appropriate operating parameters of the mixer result in agglomeration of different particles into larger granules.
Die Große der Granulate kann durch Verfahrensparameter beim Mi¬ schen als auch durch nachherige Siebung oder Mahlung eingestellt werden. Die Granulate haben bevorzugt einen mittleren Durchmesser kleiner 3 mm, insbesondere von 0,3-1,3 mm. Gegebenenfalls kann in der Bindeflüssigkeit, die zum Coaten und Agglomerieren dient, restliches Wasser vorhanden sein. Nach dem Agglomerationsvorgang kann dieses Wasser durch einen Abpuderungsvorgang mit einem trok- kenen und feindispersen Puderungsmittel gebunden werden. Durch diesen Abpuderungsvorgang laßt sich auch ein spateres Verkleben der Agglomerate verhindern und zusatzlich z.B. das Salz der ver¬ wendeten organischen Saure (z.B. Natrium- oder Calciumpropionat) auf das Agglomerat aufbringen. Ferner kann beim Abpuderungs- schritt gegebenenfalls ein Riech- oder Geschmacksstoff beigesetzt werden, wie z.B. Vanillin, Citral oder Fructin, wodurch eine zu¬ satzliche geruchsuberdeckende und z.B. die Tierfutteraufnahme attraktivierende Wirkung erzielbar wird.The size of the granules can be set by means of process parameters during mixing and also by subsequent sieving or grinding. The granules preferably have an average diameter of less than 3 mm, in particular 0.3-1.3 mm. If necessary, residual water may be present in the binding liquid used for coating and agglomerating. After the agglomeration process, this water can be bound by a powdering process with a dry and finely dispersed powder. This powdering process also prevents the agglomerates from sticking later and, for example, additionally applies the salt of the organic acid used (for example sodium or calcium propionate) to the agglomerate. Furthermore, when powdering If necessary, a fragrance or flavoring agent is added, such as, for example, vanillin, citral or fructin, as a result of which an additional odor-masking effect and, for example, attracting animal feed intake can be achieved.
Fur die Herstellung von derart rieselfahigen geruchsreduzierten Agglomeraten sind prinzipiell alle bekannten organischen bzw. an¬ organischen porös Trager geeignet, sofern sie säurebeständig sind. Beispiele sind Getreidekleien, Perlit, Tonmaterialien, Silicate und Kieselsauren, wobei den anorganischen Tragern der Vorzug zu geben ist, da deren Stoffeigenschaften besser kontrol¬ liert werden können.In principle, all known organic or inorganic porous carriers are suitable for the production of such free-flowing, odor-reduced agglomerates, provided that they are acid-resistant. Examples are cereal bran, perlite, clay materials, silicates and silicic acids, preference being given to the inorganic carriers, since their material properties can be better controlled.
Bevorzugt eingesetzte Bindeflussigkeiten sind wasserlösliche oder wasserquellbare Substanzen, die bei Raumtemperatur erstarren. Da¬ durch kann auf einen nachfolgenden Trocknungsschritt verzichtet werden, bei dem neben einem Losungsmittel oder dem zusatzlichen Wasser auch z.T. die organische Saure ausdampfen wurde.Preferred binding liquids are water-soluble or water-swellable substances that solidify at room temperature. As a result, there is no need for a subsequent drying step in which, in addition to a solvent or the additional water, in some cases. the organic acid was evaporated.
Besonders geeignete Abdeckmittel (Bindeflussigkeiten) fur den Ag¬ glomerationsprozeß und das Coaten sind solche, die eine Erwei¬ chungstemperatur von über 30°C, vorzugsweise über 60°C aufweisen, um eine Verformung der Agglomerate bei höherer Lagertemperatur zu verhindern. Bevorzugt sind solche Abdeckmittel anzuwenden, die darüberhinaus der pH-Wert absenkenden Wirkung der adsorbierten organischen Saure nicht entgegenwirken oder diese gegebenenfalls noch unterstützen oder verstarken.Particularly suitable covering agents (binding liquids) for the agglomeration process and for coating are those which have a softening temperature of over 30 ° C., preferably over 60 ° C., in order to prevent deformation of the agglomerates at a higher storage temperature. It is preferred to use cover agents which, moreover, do not counteract the pH-lowering action of the adsorbed organic acid or, if appropriate, support or strengthen it.
Als Bindeflüssigkeiten eignen sich beispielsweise hochkonzen- trierte, erhitzte Zuckerlosungen oder Alkali/Erdalkali/-For- miat/-Acetat/-Propionatlosungen. Durch den abschließenden Bepude- rungsschritt kann deren Restwassergehalt aufgenommen werden. Niedrig schmelzende Polyethylenglykole wie z.B. PEG 4000, Schmel¬ zen der Zitronensaure, der Adipinsäure, Fumarsaure oder Benzoe- saure bzw. deren Salze, hochkonzentrierten Losungen von Aminosäu¬ ren oder Mischungen dieser Sauren eignen sich bevorzugt als Bin¬ deflussigkeiten. Man verwendet 5-80 % Bindeflüssigkeit, vorzugs¬ weise jedoch 10 bis 25 Gew.-%, bezogen auf das Gewicht des Granu¬ lats.For example, highly concentrated, heated sugar solutions or alkali / alkaline earth metal / formate / acetate / propionate solutions are suitable as binding liquids. The final watering step allows their residual water content to be absorbed. Low melting polyethylene glycols such as PEG 4000, melts of citric acid, adipic acid, fumaric acid or benzoic acid or their salts, highly concentrated solutions of amino acids or mixtures of these acids are preferably suitable as binary liquids. 5-80% binding liquid is used, but preferably 10 to 25% by weight, based on the weight of the granulate.
Geeignete Puderungsmittel sind neben den porösen Trager¬ materialien selbst feindisperse, gemahlene organische Sauren oder deren Salze, z.B. Na-Formiat, sowie anorganische Salze oder Aerosil. Von den Bepuderungsmitteln werden < 10 %, vorzugsweise zwischen 0,5 und 5 Gew.-% zugegeben. Im allgemeinen wird der poröse Träger im Mischer z.B. einem Ei- rich-Mischer vorgelegt und bei geringen Energieeinträgen mit der organischen Säure getränkt. Man kann jedoch auch so verfahren, daß die Flüssigkeit im Mischer vorgelegt wird und der Träger 5 zudosiert wird. In diesem Fall muß mit höheren Energieeinträgen gearbeitet werden.In addition to the porous carrier materials, suitable powdering agents are themselves finely dispersed, ground organic acids or their salts, for example Na formate, and also inorganic salts or Aerosil. <10%, preferably between 0.5 and 5% by weight, of the powdering agents are added. In general, the porous carrier is placed in the mixer, for example, in an Eichrich mixer and soaked with the organic acid at low energy inputs. However, the procedure can also be such that the liquid is placed in the mixer and the carrier 5 is metered in. In this case, higher energy inputs must be used.
Darauf zu achten ist, eine gleichmäßige Tränkung sicherzustellen und lokale überfeuchtungen, die zur Klumpenbildung führen, zu 0 vermeiden. Nach erfolgter Tränkung liegt im Mischer ein riesel¬ fähiges, leicht kohäsives Haufwerk vor. Die Viskosität der Binde¬ flüssigkeit sollte durch eine entsprechende Temperaturwahl so eingestellt werden, daß sie unterhalb von 1.000 mPas, bevorzugt im Bereich < 100 mPas liegt, um bei der Verdüsung der Bindeflüs-Care must be taken to ensure an even soak and to avoid local over-humidification, which leads to the formation of clumps. After the impregnation has taken place, the mixer has a free-flowing, slightly cohesive pile. The viscosity of the binding liquid should be adjusted by an appropriate temperature selection in such a way that it is below 1,000 mPas, preferably in the range <100 mPas, in order to spray the binding fluids.
15 sigkeit eine feine Tropfengrößenverteilung zu erreichen. Bedingt durch den Temperaturunterschied zwischen erwärmter Bindeflüssig¬ keit und kühleren getränktem Träger erstarren bei dieser bevor¬ zugten Ausführungsform die Bindeflüssigkeitstropfen anfänglich schnell. Im weiteren Verlauf des Agglomerationsprozesses steigt15 liquid to achieve a fine droplet size distribution. Due to the temperature difference between heated binding liquid and cooler soaked carrier, the binding liquid drops initially solidify rapidly in this preferred embodiment. As the agglomeration process progresses
20 die Temperatur der Schüttung durch den mechanischen und den ther¬ mischen Energieeintrag je nach Art der Bindeflüssigkeit um 10-30°C an. Auf den bereits gebildeten Agglomeraten lagern sich weitere Bindeflüssigkeitstropfen an, die zum Teil miteinander koalisie¬ ren. Der Energieeintrag steigt während der Agglomeration um ca.20 the temperature of the bed due to the mechanical and thermal energy input depending on the type of binding fluid by 10-30 ° C. Further binding liquid drops are deposited on the agglomerates that have already formed, some of which coalesce with one another. The energy input increases during agglomeration by approx.
25 20 % an.25 20%.
Abschließend kann mit dem Bepuderungsmittel, wie oben darge¬ stellt, zusätzlich ein feindisperses Odorierungsmittel zugegeben werden. Hierfür eignen sich prinzipiell eine Vielzahl von Riech-Finally, a finely dispersed odorant can be added with the powdering agent, as shown above. In principle, a large number of olfactory
30 und Geschmacksstoffen, die je nach späterer Verwendung des Agglo- merats ausgewählt werden können. Der Anteil dieser Riechstoffe kann < 1 Gew.-%, bevorzugt von 0,05 bis 0,5 Gew.-%, bezogen auf das Granulat, betragen. Die so erzeugten Agglomerate sind staubarm, geruchsreduziert und ihr organischer Säureanteil ist30 and flavors that can be selected depending on the later use of the agglomerate. The proportion of these fragrances can be <1% by weight, preferably from 0.05 to 0.5% by weight, based on the granules. The agglomerates produced in this way are low in dust, reduce odor and their organic acid content is
35 leicht wasserlöslich.35 slightly water soluble.
Die erfindungsgemäßen Granulate eignen sich zur Behandlung von Lebens- und Futtermitteln, sowie zur Anwendung in Silagen. Unter Lebens- und Futtermittel sind insbesondere zu verstehen Erntepro- 40 dukte wie Heu, Silage, Feucht-Getreide, Hülsen- oder Körner¬ früchte, aber auch Milchaustausch-, Flüssig-, Misch- und Mineral¬ futter, Fischsilagen oder Fischmehl.The granules according to the invention are suitable for the treatment of food and feed, and for use in silages. Food and animal feed are to be understood in particular as crop products such as hay, silage, moist cereals, legumes or cereal fruits, but also milk exchange, liquid, mixed and mineral feed, fish silages or fish meal.
Die erfindungsgemäßen Granulate können noch andere Additive ent- 45 halten, wie z.B. Mineralien, Vitamine, Antibiotika oder Protein- Zusatzstoffe. BeispieleThe granules according to the invention can also contain other additives, such as minerals, vitamins, antibiotics or protein additives. Examples
(Gehalt der eingesetzten Ameisensaure = 99 %/Propionsäure = 99 %)(Content of formic acid used = 99% / propionic acid = 99%)
A. VergleichsbeispieleA. Comparative Examples
Vergleichsbeispiel 1Comparative Example 1
In einem Haushaltsmischer werden 100 g Weizenkleie vorgelegt und mit 100 g Ameisensaure getrankt. Die Saure wird bereit¬ willig aufgenommen; das Produkt zeigt ein kohasives Verhal¬ ten, laßt sich jedoch leicht zerteilen. Es weist starken Ameisensauregeruch auf.100 g of wheat bran are placed in a household mixer and soaked in 100 g of formic acid. The acid is readily absorbed; the product shows a cohesive behavior, but can be easily divided. It has a strong smell of formic acid.
Vergleichsbeispiel 2Comparative Example 2
In einem Haushaltsmischer werden 100 g Sipernat® (hoch¬ disperse Kieselsaure, Fa. Degussa) vorgelegt und 100 g einer Sauremischung, bestehend aus gleichen Teilen Ameisensaure und Propionsäure, getrankt. Die Sauremischung wird bereitwillig aufgenommen; es entsteht ein lockeres, rieselfahiges Produkt. Das Produkt hat stechend - stinkenden Ameisensaure/Pro- pionsauregeruch.In a household mixer, 100 g of Sipernat ® (hoch¬ disperse silica, Fa. Degussa) are charged and 100 g of an acid mixture consisting of equal parts of formic acid and propionic acid, soaked. The acid mixture is readily absorbed; a loose, free-flowing product is created. The product has a pungent - smelly formic acid / propionic acid smell.
Vergleichsbeispiel 3Comparative Example 3
Analog zu Beispiel 1 werden 100 g Perlit vorgelegt und mit der Ameisensaure getrankt. Die Saure wird bereitwillig aufge¬ nommen, das Produkt neigt jedoch stark zum Verkleben und riecht stark stechend nach Ameisensaure.Analogously to Example 1, 100 g of pearlite are introduced and soaked in formic acid. The acid is readily absorbed, but the product tends to stick and smells strongly of formic acid.
B. Trankungs-, Agglomerations- und CoatingversucheB. Tranking, agglomeration and coating attempts
Beispiel 1example 1
Im Eirich-Mischer (R02) wurden 460 g Sipernat® (hochdisperse Kieselsaure, Fa. Degussa) vorgelegt und mit 905 g Ameisen¬ saure getrankt; der Ameisensauregehalt liegt anschließend bei 67 %. Zu 1.000 g dieser Mischung werden als Bindeflüssigkeit 200 g Na-Formiat-Schmelze bei 80°C aus einem beheiztenIn an Eirich mixer (R02) 460 g Sipernat ® (fumed silica, from Degussa.) Was charged with 905 g of formic acid soaked; the formic acid content is then 67%. For 1,000 g of this mixture, 200 g of Na formate melt at 80 ° C from a heated as a binding liquid
Vorlagebehalter über eine Zweistoffduse in den Mischraum ein¬ gedust. Die entstandenen Agglomerate werden mit 44 g Sipernat® abgepudert. Der Gehalt an freier Saure liegt bei 54 %. Das entstandene Produkt ist rieselfahig und geruchsre- duziert. Beispiel 2Storage container sprayed into the mixing room via a two-fluid nozzle. The resulting agglomerates are powdered with 44 g of Sipernat ® . The free acid content is 54%. The resulting product is free-flowing and odor-reduced. Example 2
Im Eirich-Mischer wurden 400 g Sipernat® vorgelegt und mit 1.000 g Ameisensäure getränkt (Ameisensäuregehalt: 71 %) . Zum Agglomerieren und Coaten werden als Bindeflüssigkeit 180 g einer konzentrierten Traubenzuckerlösung bei 80°C aus einem beheizten Vorlagebehälter über eine Zweistoffdüse in den Mischraum eingedust. Die entstandenen Agglomerate werden mit 45 g Sipernat® und 12 g Citral abgepudert. Der Säuregehalt liegt dann bei 61 %. Die entstandenen Agglomerate sind gut rieselfähig. Die Leistungsaufnahme liegt nach dem Tränken bei •» 400 W, nach dem Coaten bei - 500 W. Die Drehzahl wurde von 340 upm auf 460 upm während des Agglomerationsschrittes ange¬ hoben.400 g of Sipernat ® were placed in the Eirich mixer and impregnated with 1,000 g of formic acid (formic acid content: 71%). For agglomeration and coating, 180 g of a concentrated glucose solution at 80 ° C are sprayed into the mixing chamber via a two-fluid nozzle as a binding liquid. The resulting agglomerates are powdered with 45 g Sipernat ® and 12 g Citral. The acidity is then 61%. The resulting agglomerates are easy to pour. The power consumption after soaking is 400 W, after coating it is 500 W. The speed was increased from 340 rpm to 460 rpm during the agglomeration step.
Beispiel 3Example 3
Analog zu Beispiel 2 wurden im Eirich-Mischer 400 g Sipernat® vorgelegt und mit 1.100 g Ameisensäure getränkt; der Ameisen- Säuregehalt liegt anschließend bei 71 %. Als Bindeflüssigkeit werden 260 g Zitronensäureschmelze bei 170°C aus einem be¬ heizten Vorlagebehälter über eine Zweistoffdüse in den Mi¬ schraum eingedust. Die entstandenen Agglomerate werden mit 44 g Sipernat® und 8 g Vanillin abgepudert. Der Gesamtsäure- gehalt liegt bei * 74 %. Die entstandenen Agglomerate sind im Ameisensäure-Geruch deutlich reduziert.Analogously to Example 2 were charged with 400 g of Sipernat ® in an Eirich mixer and impregnated with 1.100 g of formic acid; the ants' acidity is then 71%. 260 g of citric acid melt are injected into the mixing chamber at 170 ° C. as a binding liquid from a heated storage container through a two-component nozzle. The resulting agglomerates are powdered with 44 g Sipernat ® and 8 g vanillin. The total acidity is * 74%. The resulting agglomerates are significantly reduced in the smell of formic acid.
Beispiel 4Example 4
In einem Pflugscharmischer (Lö 130) werden 8,7 kg Sipernat® vorgelegt und mit 24 kg Ameisensäure (98 %) getränkt (Ameisensäuregehalt: 71 %) . Zum Agglomerieren und Coaten wer¬ den 5,5 kg Zitronensäureschmelze bei.l70°C aus einem beheiz¬ ten Vorlagebehälter über eine Zweistoffdüse in den Mischraum eingedust. Die entstandenen Agglomerate werden mit 650 g8.7 kg of Sipernat ® are placed in a ploughshare mixer (Lö 130) and soaked with 24 kg of formic acid (98%) (formic acid content: 71%). For agglomeration and coating, 5.5 kg of citric acid melt are injected into the mixing chamber from a heated storage container at 170 ° C. via a two-component nozzle. The resulting agglomerates weigh 650 g
Sipernat® und 24 g Vanillin abgepudert. Der Gesamtsäuregehalt liegt bei * 74 .. Die entstandenen Agglomerate sind im Geruch deutlich reduziert und gut rieselfähig. Powdered Sipernat ® and 24 g vanillin. The total acidity is * 74 .. The resulting agglomerates are significantly reduced in smell and easy to pour.

Claims

Patentansprüche claims
1. Rieselfähiges Granulat, bestehend aus einem Kern und einer Hülle, dadurch gekennzeichnet, daß das Kernmaterial eine or¬ ganische Säure und einen porösen Träger enthält und die Hülle ein bei 20°C wasserlösliches oder wasserquellbares Abdeckmit¬ tel aufweist.1. Free-flowing granules consisting of a core and a shell, characterized in that the core material contains an organic acid and a porous carrier and the shell has a water-soluble or water-swellable covering agent.
2. Granulat nach Anspruch 1, dadurch gekennzeichnet, daß die2. Granules according to claim 1, characterized in that the
Hülle zusätzlich ein Puderungsmittel auf der Oberfläche auf¬ weist.Shell additionally has a powder on the surface.
3. Granulat nach Anspruch 1, dadurch gekennzeichnet, daß der Kern 30-90 Gew.-% organische Säure enthält.3. Granules according to claim 1, characterized in that the core contains 30-90 wt .-% organic acid.
4. Granulat nach Anspruch 1, dadurch gekennzeichnet, daß die or¬ ganische Säure eine Ci-Cβ-Mono- oder Di-Carbonsäure oder ein Gemisch solcher Carbonsäuren ist.4. Granules according to claim 1, characterized in that the organic acid is a Ci-Cβ-mono- or di-carboxylic acid or a mixture of such carboxylic acids.
5. Granulat nach Anspruch 1, dadurch gekennzeichnet, daß als Träger poröse, organische oder anorganische Trägermaterialien eingesetzt werden, deren Partikelgrößen zwischen 1 μm und 1.000 μm, vorzugsweise zwischen 5 μm und 100 μm liegen.5. Granules according to claim 1, characterized in that porous, organic or inorganic carrier materials are used as carriers, the particle sizes of which are between 1 μm and 1,000 μm, preferably between 5 μm and 100 μm.
6. Granulat nach Anspruch 1, dadurch gekennzeichnet, daß als Ab¬ deckmittel wasserlösliche Polymere, organische Säuren, deren Salze oder niedrig schmelzende anorganische Salze verwendet werden.6. Granules according to claim 1, characterized in that water-soluble polymers, organic acids, their salts or low-melting inorganic salts are used as covering agents.
7. Granulat nach Anspruch 5, dadurch gekennzeichnet, daß als Träger Getreidekleien, Silikate, Perlit oder Kieselsäuren in Anteilen zwischen 10 Gew.-% und 70 Gew.-%, vorzugsweise mit 20 bis 40 Gew.-%, verwendet werden.7. Granules according to claim 5, characterized in that cereal bran, silicates, perlite or silicas are used as carriers in proportions between 10% by weight and 70% by weight, preferably 20 to 40% by weight.
8. Granulat nach Anspruch 6, dadurch gekennzeichnet, daß als Ab¬ deckmittel Polyethylenglykole, Polyvinylpyrrolidone oder or¬ ganische Säuren und deren Salze von C3 bis C14, vorzugsweise C3 bis C6, insbesondere Zitronensäure, Fumarsaure, Bernstein- säure, Adipinsäure, Benzoesäure, Sorbinsäure und deren Salze oder Aminosäuren und deren Salze, verwendet werden. 8. Granules according to claim 6, characterized in that as covering agents polyethylene glycols, polyvinylpyrrolidones or organic acids and their salts from C3 to C14, preferably C3 to C6, especially citric acid, fumaric acid, succinic acid, adipic acid, benzoic acid, sorbic acid and their salts or amino acids and their salts.
9. Verfahren zur Herstellung von Granulaten, enthaltend orga¬ nische Säuren und poröse Trägermaterialien, dadurch gekenn¬ zeichnet, daß das Trägermaterial mit der flüssigen organi¬ schen Säure getränkt wird, anschließend mit einem verflüssig- ten Abdeckmittel, das bei Raumtemperatur erstarrt, agglome¬ riert wird, wobei das Abdeckmittel in solchem Maße zugegeben wird, daß die entstehenden Granulate gecoatet werden und ge¬ gebenenfalls eine weitere Odorierung durch die Zugabe von Riechstoffen erfolgt und gegebenenfalls die Rieselfähigkeit der Agglomerate durch Abpudern mit einem feindispersen Puder¬ mittel sichergestellt wird.9. A process for the production of granules containing organic acids and porous carrier materials, characterized in that the carrier material is impregnated with the liquid organic acid, then agglomerated with a liquefied covering agent which solidifies at room temperature The covering agent is added to such an extent that the resulting granules are coated and, if necessary, further odorization is carried out by adding fragrances and if necessary the pourability of the agglomerates is ensured by powdering with a finely dispersed powdering agent.
10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, daß das Trägermaterial in einen Mischer vorgelegt wird, mit der orga- nischen Säure getränkt und anschließend mit dem Abdeckmittel agglomeriert und gecoatet wird.10. The method according to claim 9, characterized in that the carrier material is placed in a mixer, soaked with the organic acid and then agglomerated and coated with the covering agent.
11. Verwendung des Granulats gemäß Anspruch 1 zur Säurebehandlung und Konservierung von Lebens- und Futtermitteln, sowie zur Anwendung in Silagen. 11. Use of the granules according to claim 1 for acid treatment and preservation of food and feed, and for use in silages.
EP96930104A 1995-08-30 1996-08-26 Pourable organic acid-based granulates, process for their preparation and their use Withdrawn EP0847243A1 (en)

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GEP20002062B (en) 2000-05-10
CN1193892A (en) 1998-09-23
EA000874B1 (en) 2000-06-26
NO980861L (en) 1998-02-27
EA199800229A1 (en) 1998-12-24
AU706207B2 (en) 1999-06-10
DE19531782A1 (en) 1997-03-06
PL325169A1 (en) 1998-07-06
CA2227282A1 (en) 1997-03-06
AU6928696A (en) 1997-03-19
CZ49998A3 (en) 1998-08-12
NZ316933A (en) 1999-01-28
KR19990044266A (en) 1999-06-25
JPH11511969A (en) 1999-10-19
IL122355A (en) 2000-08-31
IL122355A0 (en) 1998-04-05
BR9609990A (en) 1999-07-06
SK22898A3 (en) 1998-12-02
HUP9802322A3 (en) 2001-08-28
WO1997007687A1 (en) 1997-03-06
NO980861D0 (en) 1998-02-27
HUP9802322A2 (en) 1999-01-28
TR199800344T1 (en) 1998-05-21
MX9801399A (en) 1998-05-31

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