EA000874B1 - Pourable organic acid-based granulates - Google Patents

Abstract

1. A pourable granulate comprising an organic acid applied on a porous carrier, characterized in that said granulates are coated with a casing, said casing comprises a covering agent which is water-soluble at 20 degree C or can swell in water. 2. A pourable granulate according to claim 1, characterized in that the casing further comprising a powdering means on its serface. 3. A pourable granulate according to claim 1, characterized in that the core comprises 30-90 wt. % of an organic acid. 4. A pourable granulate according to claim 1, characterized in that the organic acid is mono- or dicarbonic having 1 to 6 carbon atoms or a mixture of such carbonic acids. 5. A pourable granulate according to claim 1, characterized in that porous organic or inorganic materials are used as a carrier the particle size of which is 1-1000 mμm, preferably 5-100 mμm. 6. A pourable granulate according to claim 1, characterized in that water-soluble polymers, organic acids, salts thereof or low-melting inorganic salts are used as a casing material. 7. A pourable granulate according to claim 5, characterized in that grain siftings silicates, perlite or silicic acids amounting from 10 wt. % to 70 wt. %, preferably from 20 wt. % to 40 wt.% are used as a carrier. 8. A pourable granulate according to claim 6, characterized in that polyethylenglykole, polyvinylpyrrolidone, or organic acids, containing from 3 to 14 carbon atoms, preferably from 3 to 6 carbon atoms, particularly citric, fumaric, succinic, adipic, benzoic, sorbic acids and salts threof, or amonoacids and salts thereof.

Description

This invention relates to a granular granulate, the granules of which consist of a core and a shell, the core material containing organic acid and a porous carrier, and the shell is a coating substance soluble or swelling in water.

Short-chain organic acids, such as formic, acetic or propionic acids, are used in acidifying and canning food and feed. The disadvantages of these acids are (a) a liquid state of aggregation at room temperature, (c) a sharp, irritating odor caused by low vapor pressure of the acid, and (c) their ability to cause corrosion.

In addition, liquid organic acids in a concentrated form can be made, for example, in feed, only having overcome significant technical difficulties.

According to DE 28 33 727 A1, a fine material is known which acts as a fungicide that contains propionic acid and a carrier material. In the presence of this material, the number of mold colonies in agricultural products stored in the warehouse does not increase during a multi-day incubation period. However, it has been established that a material of this kind is itself unstable during storage (loss of acid), and the greatest amount of propionic acid that can be applied depends strongly on the carrier material used. In addition, this material detects an unpleasant odor associated with the evaporation of propionic acid.

Therefore, before this invention was the goal - the creation of bulk granules with a faint odor for the treatment of food and feed, which are significantly improved in performance. At the same time, the production of solid organic acid in the form of an adsorbate, which differs significantly from simple impregnation products, was in the foreground in that (a) allows obtaining an acid concentration of> 30 wt.% In a solid matter regardless of the carrier material and thus allows a higher proportion of the active substance and (b) the release of the organic acid from the adsorbate is minimized and, thus, the active substance content is preserved. Powdered final product has good operational properties for storage, flowability and processing.

This goal is achieved with the help of a granulate, the granules of which consist of a core and a shell, the core material containing organic acid and a porous carrier, and the shell consists of a coating substance soluble or swelling in water at 20 ° C.

The granulate according to the invention has the advantage that the reduction of the highly caustic odor of the acid is achieved, and the proportion of acid in it, despite the solid-phase decoration, dissolves well and quickly and is released from the solid powder.

By liquid organic acid, organic acids or mixtures of acids are meant, which, at processing temperatures, are liquid or can be converted to a liquid state when dissolved or dispersed in a liquid.

The granulate, which is the subject of the invention, in its preferred form of implementation contains on the surface of the shell a powdering agent. The core preferably contains 30-90 wt.%, Especially 50-80 wt.% Organic acids. The organic acid is preferably one or more monoic dicarboxylic acids with 1-6 carbon atoms, especially formic, acetic and / or propionic acid.

As a carrier, porous organic or inorganic carrier materials can be used, the particle size of which is from 1 to 1,000 μm, preferably from 5 to 100 μm.

The core may include other solids, for example, such a solid substance characteristic of feed additives, such as calcium propionate.

As a coating material, water-soluble polymers, organic acids and their salts or low-melting inorganic salts can be used.

Grain bran, silicates, perlite or silicic acids are preferably used as carriers in an amount of from 10 to 70 wt.%, Preferably from 20 to 40 wt.%, Calculated on the weight of the core.

Polyethylene glycol, polyvinylpyrrolidone or organic acids containing from 3 to 1 4 carbon atoms, preferably from 3 to 6 carbon atoms, especially citric, fumaric, succinic, adipic and benzoic acids and their salts, or amino acids and their salts are preferably used as the coating material. .

In the preferred form of the proposed method, the carrier material is loaded into the mixer, impregnated with organic acids and finally agglomerated with the coating material and coated with it.

Unbound and impregnated particles of the carrier material are mixed with the coating material (binding liquid), while the binding liquid is usually a highly concentrated solution or melt of water-soluble or water-swellable substances that solidifies at room temperature (20 ° C). This binding fluid is preferably applied in a heated state to the impregnated particles of the carrier material and mixed with them. When this binding fluid hardens on the surface of the impregnated particles of the material of the carrier. With the inherent parameters of the mixer, agglomeration of different particles into large granules takes place.

The sizes of the granules are set both with the help of the parameters of the method of processing, and during the subsequent sieving or grinding. Granules have a preferred average diameter of less than 3 mm, especially from 0.3 to 1.3 mm. If necessary, the binding fluid that serves to agglomerate and coat may contain excess water. This water can be bound after the agglomeration process using the dusting process with a dry and finely powdered agent. This process of dusting prevents the subsequent agglomeration of agglomerates, and additionally allows you to apply on the agglomerate, for example, a salt of a used organic acid (for example, sodium or calcium propionate). Further, at the stage of dusting, if necessary, an odorous or flavoring substance is applied, such as vanillin, citral or fructin, as a result, an additional interruption of unpleasant odor is achieved and, for example, when animals receive feed, an attractive effect is achieved.

For the production of such loose agglomerates with a weak odor, in principle, all known organic, respectively, inorganic porous carriers are suitable if they are resistant to acids, for example, grain bran, perlite, ceramic materials, silicates and silicic acids, and inorganic carriers are preferred, since their real characteristics are better controlled.

Preferred binding fluids used include water-soluble or water-swellable substances, which harden at room temperature. This avoids the subsequent drying stage, in which along with the evaporation of the solvent or excess water, the organic acid can partially evaporate.

Especially preferred for the process of agglomeration and coating of granules are such coating substances (binding liquids), in which the softening temperature exceeds 30 ° C, preferably 60 ° C, which avoids deformation of the agglomerates at elevated storage temperatures. Preferably, such coating substances are used which, along with this, do not counteract the pH-lowering effect of the adsorbed acid, or this effect is supported or enhanced under certain conditions.

Highly concentrated, heated sugar solutions or alkaline / alkaline earth / -formate / -acetate / -propionate solutions are suitable as binding liquids. The final stage of dusting binds the residual amount of water in them. Fusible polyethylene glycols, for example, PEG4000, melts of citric, adipic, fumaric or benzoic acids, respectively, their salts, highly concentrated solutions of amino acids or mixtures of these acids are preferred as binding liquids. Binding liquids are used in an amount of from 5 to 80%, but preferably from 10 to 25% by weight, based on the weight of the granulate.

Suitable powders, along with porous carrier materials, are finely dispersed, ground organic acids or their salts, for example, sodium formate, as well as inorganic salts or aerosil. The powdering agent is added in an amount of <10%, preferably from 0.5 to 5% by weight.

As a rule, the porous carrier is loaded into the mixer, for example, the Iriha mixer, and impregnated with organic acid at low power consumption. You can, however, do this; First, the liquid is poured into the mixer, and then the carrier is metered. In this case, energy costs increase.

Care should be taken to ensure uniform impregnation and no local waterlogging that leads to the formation of lumps. After carrying out the impregnation in the mixer is a loose, easily cohesive mass. The viscosity of the binding fluid is set using an appropriate temperature selection so that it is below 1000 mPa · s, preferably in the region of <100 mPay, so that when the binding liquid is sprayed through the nozzle, small droplets form. With this preferred form of implementation, the droplets initially quickly solidify due to the difference in temperature between the heated binding fluid and the colder impregnated carrier. With the further course of the sintering process, the temperature of the mixture increases as a result of mechanical and thermal energy input by 10–30 ° C, depending on the type of binding fluid. On the already formed agglomerates, further drops of binding fluid fall, which partially stick together. Energy consumption increases during agglomeration by 20%.

Finally, using a powdering substance as described above, add fine odor material. For this purpose, in principle, a large number of odorous and flavoring substances, which are chosen depending on the further use of the agglomerate, are suitable. The proportion of these odorous substances is <1 wt.%, Preferably from 0.05 to 0.5 wt.% In terms of granulate. The agglomerates obtained in this way contain little dust, have a weakened odor, and the organic acid contained in them is easily soluble in water.

The granulates of the invention are suitable for the processing of food and feed, as well as in silos. Food and feed should, in particular, be understood as harvest products such as hay, silage, wet grain, legumes or grain crops, as well as milk-substitute, liquid, mixed and mineral feed, fish silos and fish meal.

The granulates of the invention may contain other additives, such as, for example, minerals, vitamins, antibiotics, or protein supplements.

Examples (Concentration of formic acid used = 99% / propionic acid = 99%).

A. Examples for comparison.

Comparison Example 1.

100 g of wheat bran are loaded into a household mixer and 100 g of formic acid are impregnated with them. Acid is quickly absorbed, the product detects cohesive behavior, however, it is easily separated. It detects a strong smell of formic acid.

Comparison Example 2.

In a household mixer load 1 00 g sipernat ^to (highly dispersed silicic acid, Fa.Degussa) and impregnate it with 100 g of a mixture of acids consisting of equal proportions of formic and propionic acids. The mixture of acids is easily absorbed; the friable, loose product is formed. The product has a sharp unpleasant smell of formic / propionic acid.

Comparative Example 3.

Similarly, with example 1, download 1 00 g of perlite and impregnated with formic acid. Acid is absorbed, however, the product has a strong tendency to stick together and has a strong pungent smell of formic acid.

B. Experiments on impregnation, agglomeration and the formation of the shell.

Example 1

460 g of sipernate ^R (highly dispersed silicic acid, Fa.Degussa) are loaded into an Irihah mixer (RO2) and 905 g of formic acid are impregnated; as a result, the formic acid content is about 67%. In 1000 g of this mixture, which is in the mixing chamber, 200 g of sodium formate melt as a binding liquid is sprayed from a heated container through a binary nozzle. The resulting agglomerates powder 44 g of sipernate ^{R The} resulting product is free-flowing and has a weakened odor.

Example 2

400 g of sipernate ^R are loaded into the Iriha mixer and impregnated with 1000 g of formic acid (the content of formic acid is 71%). For agglomerating and coating as a binding liquid, 180 g of a concentrated solution of grape sugar is sprayed at a temperature of 80 ° C in the mixing chamber. Spraying is made from a heated container through a binary nozzle. The resulting agglomerates powder 45 g of sipernate ^R and 12 g of citral. The acid content is about 61%. The resulting agglomerates have good flowability. Power consumption after impregnation is 400 W, and after the formation of the shell 500 watts. The speed during the agglomeration stage is increased from 340 rpm to 460 rpm.

Example 3

Analogously to example 2, 400 g of sipernate ^R are loaded into Iriha's mixer and 1100 g of formic acid are impregnated; the content of formic acid in the end is 71%. As a binding fluid in the mixing chamber, 260 g of a melt of citric acid are sprayed at 170 ° C through a binary nozzle from a heated tank. The resulting agglomerates are powdered with 44 g of sipernate ^R and 8 g of vanillin.

The total amount of acid is about 74%. The smell of formic acid in the formed agglomerates is significantly weakened.

Example 4

8.7 kg of sipernate ^R are loaded into a share mixer (Lo 130) and 24 kg of formic acid (98%) are impregnated (the content of formic acid is 71%). For agglomeration and shell formation, 5.5 kg of citric acid melt at 1–70 ° C is taken, which is sprayed in a mixing chamber from a heated container through a binary nozzle. The resulting agglomerates powder 650 g of sipernate ^R and 24 g of vanillin. The total acid content is about 73%. The resulting agglomerates have a significantly reduced odor and good flowability.

Claims (8)

CLAIM one . A granular granulate whose granules contain an organic acid supported on a porous carrier, characterized in that the granules are coated with a coating that consists of a coating substance that is soluble or swells at water at 20 ° C. 2. The granular granulate according to claim 1, characterized in that the shell further comprises a powdery substance on the surface. 3. The granular granulate according to claim 1, characterized in that the core contains 30-90 wt.% Organic acid. 4. The granular granulate according to claim 1, characterized in that the organic acid is a mono- or dicarboxylic acid with 1-6 carbon atoms or a mixture of such carboxylic acids. 5. The granular granulate according to claim 1, characterized in that the carrier is used porous organic or inorganic carrier materials, the particle size of which is 1-1000 microns, preferably 5-100 microns. 6. The granular granulate according to claim 1, characterized in that water-soluble polymers, organic acids, their salts or low-melting inorganic salts are used as the shell material. 7. The granular granule according to claim 5, characterized in that grain bran, silicates, perlite or silicic acids are used as a carrier in an amount of from 10 to 70 wt.%, Preferably from 20 to 40 wt.%. 8. The granular granule according to claim 6, characterized in that polyethylene glycol, polyvinylpyrrolidone or organic acids containing from 3 to 14 carbon atoms, preferably from 3 to 6 carbon atoms, especially citric, fumaric, succinic, adipic, benzoic, sorbic acid and their salts, or amino acids and their salts.