DE19531782A1 - Free-flowing granules based on organic acids, process for their preparation and their use - Google Patents

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 DEG C.

Description

The present invention relates to a free-flowing granulate, consisting of a core and a shell, the core material contains an organic acid and a porous carrier and the Cover a water-soluble or water-swellable covering agent points.

The invention further relates to a method of manufacture free-flowing, odor-reduced granules based on organic Acids preferably formic, acetic and / or propionic acid, so how to use the granules to treat food and Animal feed, as well as for use in silages.

Short chain organic acids such as formic acid, acetic acid or Propionic acid is found in the acidification and preservation of Le Food and feed application. Disadvantages of these acids are (a) their liquid state at room temperature, (b) that of the sharp, pungent smell resulting from the low vapor pressure and (c) their corrosiveness.

Furthermore, the liquid organic acids are more concentrated Form only through considerable technical effort, for example in Incorporate feed.

DE 28 33 727 A1 describes a particulate, fungicidal we kendes known material, the propionic acid and a carrier material contains. This material is also intended for incubation for several days the number of mold colonies in the case of stored farmers crop products do not increase. But it has happened shows that such material itself is not stable in storage (Säu loss) and the maximum amount of propionic acid applied depends heavily on the substrate used. In addition occur with this material by volatilizing the propionic acid unpleasant smells.

The present invention was therefore based on the object free-flowing, low-odor granules for the treatment of food and to provide feed with which the hand performance properties for the user are significantly improved. The main focus was the production of a "solid organi "acid" in the form of an adsorbate, which is essentially should differ from simple impregnation products in that  by (a) independent of an acid content <30 wt .-% in the solid gig of the carrier material and thus the highest possible "Active ingredient portion" carries and (b) the leakage of the organic Acid from the adsorbate is kept to a minimum and thus the "Active ingredient content" retained. The powdered end product should have good storage, flow and processing properties.

This task is solved by a granulate consisting of a Core and a shell, the core material being an organic Contains acid and a porous carrier and the shell one at 20 ° C has water-soluble or water-swellable covering agent.

The granules according to the invention have the advantage that a reduction the strong pungent acid smell is reached and the acidity The proportion of solids is good and quickly soluble despite the solid formulation emerges from the solid powder.

The invention further relates to a method of manufacture of granules containing organic acids and porous carriers materials, which is characterized in that the carrier material is soaked in the liquid organic acid closing with a covering agent that he at room temperature stares, is agglomerated, the covering to such an extent it is added that the resulting granules are coated and optionally a further odorization by adding Fragrance occurs and, if necessary, the flowability of the Agglomerates by powdering with a finely dispersed powder is ensured.

Under "liquid organic acid" are acids or acid mixtures understood that liquid at processing temperatures are or by increasing the temperature or solution or dispersion be transferred into liquids in a liquid state.

In a preferred embodiment, the invention Granulate a powder on the surface of the shell. Of the Core preferably contains 30-90% by weight, in particular 50-80% by weight organic acid. The organic acid preferably consists of one or more C₁-C₆ mono- or di-carboxylic acids, in particular Formic, acetic and / or propionic acid.

Porous, organic or inorganic carriers can be used as carriers materials are used whose particle sizes are between 1 µm and 1,000 microns, preferably between 5 microns and 100 microns.  

The core can also contain other solids, e.g. B. as Feed additives suitable solids such as Ca propionate.

Water-soluble polymers, organic Acids, their salts or low-melting inorganic salts be used.

Cereal bran, silicates, pearlite or are preferred as carriers Silica in proportions between 10 wt .-% and 70 wt .-%, before preferably with 20 to 40 wt .-%, based on the weight of the Kerns used.

Polyethylene glycols, polyvinyl are preferred as covering agents pyrrolidones or organic acids and their salts from C3 to C14, preferably C3 to C6, especially citric acid, fumar acid, succinic acid, adipic acid, benzoic acid and their salts or amino acids and their salts.

In a preferred embodiment of the Ver driving the carrier material is placed in a mixer with impregnated with the organic acid and then with the cover medium agglomerated and coated.

The loose and soaked carrier particles are removed with the Ab opacifying agent (binding liquid) mixed, the binding liquid usually from a highly concentrated solution or Melt of water-soluble or water-swellable substances stands that solidify at room temperature (20 ° C). These binding rivers liquid is preferred when heated on the soaked Carrier particles applied and mixed with them. Here the binding liquids solidify on the surface of the drink carrier particles. By suitable operating parameters of the Mixer causes different particles to agglomerate larger granules.

The size of the granules can be determined by process parameters in the Mi set as well as after screening or grinding will. The granules preferably have an average diameter less than 3 mm, in particular from 0.3-1.3 mm. If necessary, in the binding liquid used for coating and agglomerating, remaining water. After the agglomeration process this water can be powdered with a troc no finely dispersed powder. By this powdering process can also be glued later prevent the agglomerates and additionally z. B. the salt of ver used organic acid (e.g. sodium or calcium propionate) apply to the agglomerate. Furthermore, when powdering  If necessary, a fragrance or flavoring was added be such. As vanillin, citral or fructin, which creates a additional odor-covering and z. B. animal feed intake attractive effect can be achieved.

For the production of such free flowing odor-reduced In principle, agglomerates are all known organic or other organic porous carrier suitable, provided they are acid-resistant are. Examples are cereal bran, pearlite, clay materials, Silicates and silicas, the inorganic carriers of Preference should be given because their material properties are better controlled can be lated.

Binding liquids which are preferably used are water-soluble or water-swellable substances that solidify at room temperature. There can do without a subsequent drying step be in addition to a solvent or the additional Water also z. T. would evaporate the organic acid.

Particularly suitable covering agents (binding liquids) for the Ag The glomerating process and the coating are those that need an extension chung temperature of over 30 ° C, preferably above 60 ° C, to deform the agglomerates at a higher storage temperature prevent. Such cover means are preferred to use moreover, the pH-lowering effect of the adsorbed do not counteract organic acid or this if necessary still support or strengthen.

For example, highly concentrated are suitable as binding liquids heated sugar solutions or Alkali / Erdalkali / -For miat / acetate / propionate solutions. By the final bepude ration step, their residual water content can be recorded. Low melting polyethylene glycols such as B. PEG 4000, Schmel zen of citric acid, adipic acid, fumaric acid or benzoin acid or its salts, highly concentrated solutions of amino acid Ren or mixtures of these acids are preferably suitable as a bin fluids. 5-80% binding liquid is used, preferably however, 10 to 25 wt .-%, based on the weight of the granu lats.

In addition to the porous carrier, suitable powdering agents are materials themselves finely dispersed, ground organic acids or their salts, e.g. B. Na formate, and inorganic salts or Aerosil. Of the powdering agents <10% are preferred between 0.5 and 5 wt .-% added.  

In general, the porous support in the mixer z. B. an egg rich mixer and with low energy inputs with the organic acid soaked. However, you can also do this that the liquid is placed in the mixer and the carrier is metered. In this case, higher energy inputs are required be worked.

Care should be taken to ensure an even impregnation and local over-humidification, which lead to the formation of clumps avoid. After soaking, there is a trickle in the mixer capable, slightly cohesive pile. The viscosity of the bandage liquid should be selected by a suitable temperature be set to be below 1,000 mPas, preferred In the range <100 mPas, in order to atomize the binding fluids to achieve a fine droplet size distribution. Conditionally due to the temperature difference between it heats up liquid The cooler and cooler soaked carrier freezes before this preferred embodiment, the binding liquid drops initially fast. As the agglomeration process progresses the temperature of the bed by the mechanical and ther Mix energy input by 10-30 ° C depending on the type of binding liquid on. More are stored on the agglomerates that have already formed Drops of binding fluid that partially koalisie with each other ren. The energy input increases during agglomeration by approx. 20%.

Finally, with the powdering agent, as shown above provides, a finely dispersed odorant added will. In principle, a large number of olfactory and flavors depending on the later use of the Agglo merats can be selected. 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 so produced are low dust, reduced odor and their organic acid content is easily water soluble.

The granules according to the invention are suitable for the treatment of Food and feed, as well as for use in silages. Under Food and animal feed are to be understood in particular harvest pro Products such as hay, silage, wet grain, pods or grains fruits, but also milk exchange, liquid, mixed and mineral feed, fish silage or fish meal.

The granules according to the invention can ent other additives hold such. B. minerals, vitamins, antibiotics or protein Additives.  

Examples (Content of formic acid used = 99% / propionic acid = 99%) A. Comparative Examples Comparative Example 1

100 g of wheat bran are placed in a household mixer and soaked with 100 g of formic acid. The acid gets ready accepted willingly; the product shows a cohesive behavior ten, but can be easily divided. It shows strong Formic acid smell.

Comparative Example 2

100 g Sipernat® (high disperse silica, from Degussa) and 100 g of a Acid mixture consisting of equal parts of formic acid and Propionic acid, soaked. The acid mixture becomes readily available recorded; a loose, free-flowing product is created. The product has stinging - smelly formic acid / pro Pionic acid smell.

Comparative Example 3

Analogously to Example 1, 100 g of perlite are introduced and with of the formic acid. The acid is readily absorbed the product tends to stick and stick smells strongly of formic acid.

B. impregnation, agglomeration and coating tests example 1

In the Eirich mixer (RO2) 460 g Sipernat® (highly disperse Silica, from Degussa) and with 905 g of ants acid soaked; the formic acid content is then included 67%. To 1,000 g of this mixture are used as a binding liquid 200 g Na formate melt at 80 ° C from a heated Feed container into the mixing room via a two-fluid nozzle gloomy. The resulting agglomerates are 44 g Powdered Sipernat®. The free acid content is included 54%. The resulting product is free-flowing and odorless induced.  

Example 2

400 g of Sipernat® were placed in the Eirich mixer and mixed with Soaked 1,000 g of formic acid (formic acid content: 71%). To the Agglomerating and coating become 180 g as a binding liquid a concentrated glucose solution at 80 ° C from one heated storage tank via a two-fluid nozzle in the Mixing room injected. The resulting agglomerates are with 45 g powdered Sipernat® and 12 g Citral. The acidity is then 61%. The resulting agglomerates are good free-flowing. The power consumption is included after soaking ≈ 400 W, after coating at ≈ 500 W. The speed was from 340 rpm to 460 rpm during the agglomeration step raised.

Example 3

Analogously to Example 2, 400 g of Sipernat® were in the Eirich mixer submitted and impregnated with 1,100 g of formic acid; the ants acidity is then 71%. As a binding liquid 260 g of citric acid melt at 170 ° C from a be heated storage container through a two-fluid nozzle in the Mi injected foam. The resulting agglomerates are with 44 g powdered Sipernat® and 8 g vanillin. The total acidity salary is ≈ 74%. The resulting agglomerates are in the Formic acid smell significantly reduced.

Example 4

8.7 kg of Sipernat® are placed in a ploughshare mixer (Lö 130) submitted and soaked with 24 kg of formic acid (98%) (Formic acid content: 71%). For agglomeration and coating who the 5.5 kg citric acid melt at 170 ° C from a heated storage container through a two-fluid nozzle into the mixing room injected. The resulting agglomerates weigh 650 g Powdered Sipernat® and 24 g vanillin. The total acidity is around 74%. The resulting agglomerates smell significantly reduced and free-flowing.

Claims (11)

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 cover agent at 20 ° C. 2. Granules according to claim 1, characterized in that the Cover an additional powder on the surface points. 3. Granules according to claim 1, characterized in that the Core contains 30-90 wt .-% organic acid. 4. Granules according to claim 1, characterized in that the or ganic acid is a C₁-C₆ mono- or di-carboxylic acid or Mixture of such carboxylic acids. 5. Granules according to claim 1, characterized in that as Carrier porous, organic or inorganic carrier materials are used whose particle sizes are between 1 µm and 1,000 microns, preferably between 5 microns and 100 microns. 6. Granules according to claim 1, characterized in that as Ab opacifying agents water-soluble polymers, organic acids, their Salts or low melting inorganic salts are used will. 7. Granules according to claim 5, characterized in that as Carrier cereal bran, silicates, perlite or silicas in Shares between 10 wt .-% and 70 wt .-%, preferably with 20 to 40 wt .-% can be used. 8. Granules according to claim 6, characterized in that as Ab opacifying agents polyethylene glycols, polyvinylpyrrolidones or or ganic acids and their salts from C3 to C14, preferably C3 to C6, especially citric acid, fumaric acid, amber acid, adipic acid, benzoic acid, sorbic acid and their salts or amino acids and their salts.   9. Process for the production of granules containing orga African acids and porous carrier materials, characterized records that the carrier material with the liquid organi acid is soaked, then liquefied with a covering agent that solidifies at room temperature agglomerates riert, with the covering agent added to such an extent is that the resulting granules are coated and ge if necessary, another odorization by adding Fragrance occurs and if necessary the flowability the agglomerates by powdering with a finely dispersed powder medium is ensured. 10. The method according to claim 9, characterized in that the Carrier material is placed in a mixer with the orga African acid soaked and then with the masking agent is agglomerated and coated. 11. Use of the granules according to claim 1 for acid treatment and preservation of food and feed, as well as for Use in silage.