MXPA98001399A - Granulos de flow libre, based on organic acids, preparation of these granules and your emp - Google Patents

Abstract

In free-flowing granules, consisting of a core and a coating, the core material contains an organic acid and a porous carrier and this coating has a cover material, which is water-soluble or water-swellable, at a temperature of twenty

Description

FREE FLOW GRANULES, BASED ON ACID ORORGANIC. PREPARATION OF THESE GRANULES AND THEIR EMPLOYMENT The present invention relates to free-flowing granules, consisting of a core and a coating, wherein the core material contains an organic acid and a porous carrier and the coating has a water-swellable or water-soluble coating material. The present invention also relates to a process for the preparation of free-flowing, low-odor granules based on organic acids, preferably formic, acetic and / or propionic acid, and the use of granules in the treatment of food and animal fodder and its use in silages. Short-chain organic acids, such as formic acid, acetic acid or propionic acid, are used in the acidification and preservation of animal feed and forage. The disadvantages of these acids are: (a) their liquid state of aggregate at room temperature, (b) the sharp acrid smell that results from the low vapor pressure and (c) their corrosivity. Likewise, liquid organic acids, in concentrated form, can be incorporated, for example, in animal feeds, only by considerably complicated technical procedures.

DE 28 33 727 A1 discloses a fungicidal, particulate material, which contains propionic acid and a carrier. This material is intended to prevent an increase in the number of fungal colonies in stored agricultural harvest products, even with an incubation time of several days. However, it has been found that this material is not itself stable when stored (acid loss), and the maximum amount of propionic acid that can be applied depends, to a large extent, on the carrier used. In addition, unpleasant odors occur with this material due to the volatility of propionic acid. It is an object of the present invention to provide low-odor, free-flowing granules for the treatment of feed and animal fodder, by means of which the handling properties are substantially improved for the user. Attention is focused on the preparation of a solid organic acid, in the form of an adsorbate, which differs from the simple impregnated products essentially in that (a) it allows an acid content > 30% by weight in the solid, independently of the carrier and thus has a very high content of active ingredient and (b) the release of the organic acid from the adsorbate is kept to a minimum and thus the content of the active ingredient is maintained. The powdery final product must have good storage, flow and process properties. We have found that this object is achieved by granules consisting of a core and a coating, in which the core material contains an organic acid and a porous carrier and the coating has a shell material which is soluble or swellable in water at 20 ° C. . The novel granules have the advantage that the highly pungent acid odor is reduced and, in spite of the solid formulation, the acid content is released from the solid powder in soluble form easily and quickly. The present invention also relates to a process for the preparation of granules containing organic acids and porous carriers, which comprise the impregnation of the carrier with the liquid organic acid, then the agglomeration with the cover material, which solidifies at room temperature , this cover material is added in an amount such that the resulting granules are coated and, if required, provide a subsequent odor by adding perfumes and, if required, ensuring the free-flowing properties of the agglomerates by dusting with an agent finely divided from dedusting.

Liquid organic acid is understood to mean acids or acid mixtures that are liquid at process temperatures or are converted into the liquid state by increasing the temperature or by dissolving or dispersing in liquids. In a preferred embodiment, the novel granules have a dedusting agent on the surface of the coating. The core preferably contains 30 to 90, in particular 50 to 80% by weight of the organic acid. This organic acid preferably consists of one or more C 1 -Cg mono- or di-carboxylic acids, in particular formic, acetic and / or propionic acids. Suitable carriers are porous carriers, organic or inorganic, whose particle size is from 1 to 1000 μm, preferably from 5 to 100 μm. The core may also contain additional solids, for example, solids suitable as feed supplements, such as calcium propionate. Water-soluble polymers, organic acids, their salts or inorganic salts having a low melting point can be used as the cover material. The cereal, silicates, perlite or silicates bran, in amounts of 10 to 70, preferably 20 to 40% by weight, based on the weight of the core, are preferably used as the carrier. Preferred roofing materials are polyethylene glycols, polyvinylpyrrolidones or C3-C14 organic acids, preferably C and their salts, in particular citric acid, fumaric acid, succinic acid, adipic acid, benzoic acid and its salts, or amino acids and its salts are preferably used as the cover material. In a preferred embodiment of the novel process, the carrier is initially taken in a mixer, impregnated with the organic acid and then agglomerated and coated with the cover material. The particles of the carrier, loose and impregnated, are mixed with the cover material (binder liquid), this binder liquid generally consists of a highly concentrated solution or a soluble or water-swellable melt, which solidifies at room temperature (202C) . This binder liquid is preferably applied in the heated state to the impregnated carrier particles and mixed with the latter. The binder liquids solidify on the surface of the impregnated carrier particles. Adequate operating parameters of the mixer result in the agglomeration of different particles to supply larger granules. The size of the granules can be established by the parameters of the process in the mixture, as well as by the sieving or subsequent grinding. The granules preferably have an average diameter of less than 3 mm, in particular 0.3 1.3 mm. If required, residual water may be present in the binder liquid used for coating and agglomeration. After the agglomeration process, this water can be bound by a dedusting agent, dry and finely divided, by means of a dedusting process. As a result of this dedusting process, it is also possible to prevent the subsequent adhesion of the agglomerates and in addition, for example, to apply the salt of the organic acid used (for example sodium propionate or calcium propionate) to the agglomerate. Also, if required, a perfume or flavor material, for example vanilla, citral or fructin, may be added during the dedusting step, which results in an additional effect that masks the odor and, for example, ensures that it is pleasant the consumption of forage by the animal. In principle, all porous carriers, non-organic or inorganic, are suitable for the preparation of such free-flowing, low-odor agglomerates, provided they are resistant to acids. Examples are cereal bran, perlite, clay materials, silicates and silicas, inorganic carriers are preferred, since their material properties can be controlled more easily. Preferred binder liquids are water-soluble or swellable substances that solidify at room temperature. This makes it possible to distribute them with the subsequent drying stage, in which, apart from the solvent and the additional water, the organic liquid, in some cases, would evaporate and separate. Particularly suitable cover materials (binding liquids) for the agglomeration process and the cover are those having a softening temperature of more than 30sc, preferably more than 60SC, in order to prevent the deformation of the agglomerates at a temperature of relatively high storage. Coating materials which are preferably used are those which also do not counteract the pH-reducing effect of the organic acid adsorbed or, if required, still support or promote this effect. Examples of suitable binder liquids are highly concentrated heated sugar solutions, or alkali metal / alkaline earth metal for acetate / propionate solutions. As a result of the final dedusting step, the residual water content can be captured. Polyethylene glycols having a low melting point, for example PEG 400, melts of citric acid, adipic acid or fumaric acid or benzoic acid or their salts, highly concentrated solutions of amino acids and mixtures of these acids, they are preferred as binder liquids. From 5 to 80, preferably from 10 to 25% by weight, based on the weight of the granules, of the binder liquid are used. Suitable dedusting agents, in addition to the porous carriers themselves, are finely divided, ground organic acids or their salts, for example the sodium format and the inorganic salts of Aerosil. They add <10, preferably 0.5 to 5% by weight of the dedusting agents. In general, the porous carrier is initially taken in the mixer, for example an Eirich mixer, and impregnated with the organic acid with little energy input. In an alternative procedure, however, the liquid is initially taken into the mixer and the carrier is dosed. In this case, a higher energy input is required. It is necessary to ensure a uniform impregnation and avoid local over-wetting, which leads to the formation of lumps. After completing the impregnation, a quantity of free, slightly cohesive luxury of particles is presented. The viscosity of the binder liquid must be established by an appropriate selection of the temperature, so it is less than 1000, preferably less than 100 mPa.s, in order to achieve a fine distribution of droplet size when the binder liquid is sprayed. Due to the difference in temperature between the heated binder liquid and the colder impregnated carrier, the drops of the binder liquid initially solidify rapidly in this preferred embodiment. In the further course of the agglomeration process, the bed temperature increases by 10-3O ^ C, depending on the type of binder liquid, due to the entry of mechanical and thermal energy. Subsequent drops of the binding liquid accumulate on the already formed agglomerates and some of these drops coalesce with each other. The energy input increases by approximately 20% during the agglomeration. Finally, a finely divided, odor-imparting material can also be added with the dedusting agent, as described above. In principle, a large number of perfume and flavor materials are suitable for this purpose and can be selected according to the subsequent use of the agglomerates. The amount of these perfumes can be < 1, preferably from 0.05 to 0.5% by weight, based on the granules. The agglomerates thus produced have a low dust content and low odor and their organic acid content is easily soluble in water. The novel granules are suitable for the treatment of food and animal fodder and for use in silages. Animal feed and fodder are, in particular, harvest products, such as hay, silages, wet cereals, legumes or grains, milk substitutes, liquid, mixed and mineral foods, fish silages or fish flour. The novel granules may contain other additives, for example minerals, vitamins, antibiotics or protein supplements.

Examples (Formic acid content used = 99% and propionic acid used = 99%). A. Comparative Examples Comparative Example 1 100 g of wheat bran were initially taken in a domestic mixer and impregnated with 100 g of formic acid. The acid was easily taken; the product exhibits a cohesive behavior, but can be easily divided. It has a strong smell of formic acid. Comparative Example 2 00 g of Sipernat® (finely divided silica, from Degussa) were initially taken in a domestic mixer and impregnated with 100 g of an acid mixture consisting of equal amounts of formic acid and propionic acid. L? Acid mixture was easily captured; a loose, free-flowing product was formed. The product has an unpleasant acrid smell of formic acid / propionic acid. Comparative Example 3 100 g of perlite was initially taken and impregnated with formic acid, similarly to Example 1. The acid was easily taken, but the product showed a strong tendency to form masses and had a strong pungent odor of formic acid. B. Impregnation, agglomeration and coating tests Example 1 460 g Sipernat® (finely divided silica, from Degussa) were initially taken in an Eirich mixer (R02) and impregnated with 905 g of formic acid; the content of the formic acid is then 67%. 200 g of molten sodium format at 802C were then sprayed, like the binder liquid, from a heated storage vessel, by means of a binary boguilla, into the mixing space containing 1000 g of this mixture. The resulting agglomerates were dedusted with 44 g of Sipernat®. The free acid content is 54%. The resulting product was free flowing and had little odor. Example 2 400 g of Sipernat® were initially taken in an Eirich mixer and impregnated with 1000 g of formic acid (formic acid content: 71%). For the agglomeration and coating, 180 g of a concentrated dextral solution, at 8 oo, were sprayed as the binder liquid, from a heated storage vessel, by means of a binary nozzle into the mixing space. The resulting agglomerates were dedusted with 45 g of Sipernat® and 12 g of citral. The acid content is after 61%. The resulting agglomerates are free flowing. The energy consumption, after impregnation, is «400 W and that after coating is« 500. The speed was increased from 340 to 460 rpm during the agglomeration stage. Example 3 400 g of Sipernat® were initially taken in an Eirich mixer and impregnated with 1100 g of formic acid, similarly to Example 2; the content of formic acid is then 71%. 20 g of citric acid melted at 170 ° C were sprayed, as the binder liquid, from a heated storage vessel, by means of a binary nozzle, into the mixing space. The resulting agglomerates were dedusted with 44 g of Sipernat® and 8 g of vanilla was added. The total acid content of "74%. The resulting agglomerates had a substantially reduced odor of formic acid. EXAMPLE 4 8.7 kg of Sipernat® were initially taken in a mixer (Lo 130) of plow type and impregnated with 24 kg of formic acid (98%) (formic acid content: 71%). For the agglomeration and coating, 5.5 kg of citric acid melted at 170sc was sprayed from a heated storage vessel by means of a binary nozzle into the mixing space. The resulting agglomerates were dedusted with 650 g of Sipernat® and 24 g of vanilla were added. The total acid content is «74%. The resulting agglomerates had a substantially reduced odor and were free flowing.

Claims (11)

1. CLAIMS 1. Free-flowing granules, consisting of a core and a coating, in which the core material contains an organic acid and a porous carrier and the coating has a shell material, which is soluble or swellable in water at a 20SC temperature.
2. 2. Granules, as claimed in claim 1, wherein the coating additionally has a dedusting agent on the surface.
3. 3. Granules, as claimed in the claim 1, in which the core contains from 30 to 90% by weight of organic acids.
4. 4. Granules, as claimed in claim 1, in which the organic acid is a mono- or di-carboxylic acid, C1-C6, or a mixture of these carboxylic acids.
5. 5. Granules, as claimed in claim 1, in which the carrier used is a porous carrier, organic or inorganic, with particle sizes of 1 to 1000 μm, preferably 5 to 100 μm.
6. 6. Granules, as claimed in claim 1, wherein the cover material used is a water soluble polymer, an organic acid, a salt thereof, or an inorganic salt having a low melting point.
7. 7. Granules, as claimed in the claim 5, in which the carrier used is a cereal bran, a silicate, the pearlite or a silica, in an amount of 10 to 70, preferably 20 to 40% by weight.
8. 8. Granules, as claimed in the claim 6, in which the cover material used is polyethylene glycol, a polyvinyl pyrrolidone or a C3-C14 organic acid, preferably C3-C6, or a salt thereof, in particular citric acid, fumaric acid, succinic acid, adipic acid, acid benzoic, sorbic acid or one thereof, or an amino acid or a salt thereof.
9. 9. A process for the preparation of granules containing organic acids and porous carriers, which comprises impregnating the carrier with a liquid organic acid, then agglomerating it with a liquefied cover material, which solidifies at room temperature, this cover material is added in an amount such that the resulting granules are coated, and, if required, subsequently supplying an odor agent by the addition of perfumes, if required, ensuring the free-flowing properties of the agglomerates by dusting with a finely dedusting agent divided.
10. 10. A method, as claimed in claim 9, in which the carrier is initially taken in a mixer, impregnated with the organic acid and then agglomerated and coated with the cover material.
11. 11. The use of granules, as claimed in claim 1, for the treatment and preservation with acid of food and animal fodder, and in silages.