SK22898A3 - Pourable organic acid-based granulates, 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

Wettable granular base of organic acids, process for its production and its use

Technical field

The invention relates to a wettable granulate consisting of a core and a sheath, wherein the core material comprises an organic acid and a porous carrier and the sheath then a water-soluble or water-swellable substance forming a cover layer.

The invention further relates to a process for the production of wettable, not too odorous granules based on organic acids, in particular formic, acetic and / or propionic acid, furthermore, the granulate is used for the treatment of food and feed as well as for use in silage.

BACKGROUND OF THE INVENTION

Short-chain organic acids, such as formic, acetic or propionic acid, are used in the process of acidifying and preserving food and feed. The disadvantages of these acids are (a) their liquid consistency at room temperature, (b) the sharp, unpleasant odor resulting from the low vapor pressure and (c) their corrosivity.

Liquid organic acids in concentrated form can be incorporated into feed only at high technical expense.

DE 28 33 727 A1 discloses a particulate fungicidal material comprising propionic acid and a carrier. This material will also prevent, even in the case of a few days incubation period, the growth of fungal colonies in stored agricultural harvest products. However, it has been shown that this material is not stable upon further storage (loss of acid) and that the maximum amount of propionic acid that can be applied depends largely on the carrier used. In addition, this material releases a very unpleasant odor as a result of the propionic acid being converted into a vapor state.

SUMMARY OF THE INVENTION

Accordingly, the present invention has been based on the object of providing wettable, odorless granules suitable for the treatment of food and feed which exhibit substantially improved handling properties. At the forefront of the effort was the production of a "solid organic acid" in the form of adsorbate, which would differ from simple saturation products by (a) allowing an acid fraction of more than 30% by weight. in the solid, independently of the carrier, thereby carrying as high an "active ingredient fraction" and (b) the organic acid output from the adsorbate would be kept to a minimum, thereby maintaining the "active substance content". The powdered final product should then exhibit good shelf life, flowability and further processing properties.

This object is achieved by a granulate consisting of a core and a sheath, wherein the core material comprises an organic acid and a porous carrier and sheath, then a substance which is water-soluble or swellable at 20 ° C to form a coating layer on the granules.

The granulate of the present invention has the advantage that the unpleasant odor of the acid is greatly reduced and that the acid fraction, despite the solid phase, dissolves easily and rapidly and is released from the solid powder.

The present invention further relates to a process for the production of granules containing organic acids and porous carriers, which comprises the carrier being saturated with a liquid organic acid, subsequently treated with a coating agent which solidifies at room temperature, which is added in birds quantities. to ensure that the resulting granules are completely covered with the coating and optionally to provide further odorization by the addition of fragrances and the wettability of the agglomerates by treatment with a finely dispersed dusting composition.

The term "liquid organic acid" refers to mixtures of acids which are liquid at the processing temperature or which pass into liquids in the liquid state when the temperature is raised or dissolved or dispersed.

In one preferred embodiment, the granulate of the present invention comprises a dust on the surface of the package. The core then contains 30 to 90 wt%, mostly 50 to 80 wt%. organic acid.

This is mostly formed from one or more C 6 -C 8 mono- or di-carboxylic acids, in particular formic, acetic and / or propionic acid.

As carriers, a porous, organic or inorganic material can be used, the particles of which have a particle size ranging from 1 µm to 1000 µm, mostly from 5 µm to 100 µm.

The core may also contain other solids, for example solids suitable as feed additives, such as Ca-propionate.

Preferred as coating agent are polyethylene glycols, polyvinylpyrrolidones or organic acids and their salts of C ₃ to C ₁₄ , most preferably C ₃ to C ₆ , especially citric, fumaric, succinic, adipinic, benzoic and their salts or amino acids, and salts thereof.

In one preferred embodiment of the present invention, the carrier is placed in a mixer, saturated with an organic acid, and then agglomerated and coated.

The loose and saturated carrier particles are mixed with a coating (the so-called binder liquid), which mostly consists of a highly concentrated solution or a melt of water-soluble or water-swellable substances which solidify at room temperature (20 ° C). This binder liquid is preferably applied in the heated state to the saturated carrier particles and is combined with them. The binder liquid solidifies on the surface of the saturated carrier particles. Due to the appropriate operating parameters of the mixer, the various particles are agglomerated and larger granules are formed.

The size of the granulate can be selected by the parameters of the mixing process as well as by subsequent sieving or milling. Generally, the granules have a mean diameter of less than 3 mm, preferably from 0.3 to 1.3 mm. Optionally, residual water may be present in the binder liquid for coating and agglomeration. After agglomeration, the water may be bound by a dry and finely dispersed powder. Later agglomeration of the agglomerates can also be prevented by this process and, subsequently, the salt of the inorganic acid used (e.g. sodium or calcium propionate) may be applied to the final agglomerate. In addition, an aromatic or flavoring agent such as vanillin, citrate or fructin may optionally be added to provide an overlapping odor effect and increase feed intake.

For the production of such wettable, odorless agglomerates, in principle all known organic and / or non-odorous agglomerates are suitable. inorganic porous carriers when resistant to acids. Examples are cereal bran, perlite, clay, silicates and silicic acid, with an inorganic carrier always being preferred because its substance properties can be better controlled.

Preferred binder liquids are water-soluble or water-swellable substances which solidify at room temperature. As a result, it is possible to dispense with subsequent drying, in which the organic acid would also evaporate in addition to the solvent or water.

A particularly suitable substance for forming the covering layer (binder liquid) for the sintering and covering process is a substance having a softening temperature of 30 ° C and above, in particular 60 ° C, thereby preventing the agglomerates from deforming at a higher storage temperature. Preferably, therefore, such substances are used to form a coating which, in addition, does not counteract or enhance or intensify the pH-lowering effect of the adsorbed organic acid.

Highly concentrated, heated sugar solutions or alkaline or alkaline earth solutions, formate, acetate or propionate are particularly suitable as binder fluids. Low melting point polyethylene glycols such as PEG 4000, citric acid, adipic acid, furmaric or benzoic acid melts, respectively. salts thereof, highly concentrated amino acid solutions or mixtures of these acids are suitable as binder fluids. 5 to 80 wt. % of a binder liquid, in particular 10 to 25 wt. These data refer to the weight of the granulate.

Suitable dusting agents are, in addition to porous carriers, finely dispersed, ground organic acids or salts thereof, for example Na-formate, as well as inorganic salts or aerosols. Of the dusting compositions, less than 10%, in particular amounts ranging from 0.5 to 5% by weight, are added.

In general, the porous support is placed in a mixer and saturated with organic acid at low energy inputs. Of course, it is also possible to pour liquid into the mixer and then to add the carrier. In this case, however, higher energy inputs are used.

Care should be taken to ensure uniform saturation and to avoid local moistening, which could result in undesirable lumps. After the saturation process is completed, a wettable, cohesive raw material composed of accumulated particles is wettable in the mixer for further processing. The viscosity of the binder liquid should be adjusted to be less than 1000 mPas, preferably less than 100 mPas, by suitable temperature selection, so as to achieve a fine droplet size distribution when spraying the binder liquid through the nozzle. In this embodiment, the temperature difference between the heated binder liquid and the colder saturated carrier determines the rapid initial solidification of the binder liquid droplets. Thus, in the further course of the sintering process, the pouring temperature is increased by 10 to 30 ° C due to mechanical or thermal energy input depending on the type of binder liquid. Additional droplets of binder liquid are deposited on the forming agglomerates, which are somewhat bonded together. Energy input increases by about 20% during the agglomeration process.

Finally, a dispersing deodorant can be added together with the dusting composition as mentioned above. In principle, a wide variety of fragrances and flavorants are suitable for this purpose, which may be selected due to the later use of the agglomerate.

The proportion of these fragrances may be less than 1% by weight, but should preferably range from 0.05 to 0.5% by weight. This applies to the granulate. The agglomerates thus produced do not dust, odor and their organic acid fraction is readily soluble in water.

The granulates produced according to the present invention are suitable for the treatment of food and feed as well as for use in silage. The term 'food and feed' means in particular harvested products such as hay, silage, wet cereals, pulses and cereals, but also dairy substitutes, liquid, combined and mineral feed, fish silage or fish meal. The granules produced according to the present invention may contain other additives such as minerals, vitamins, antibiotics or protein additives.

Examples (Formic acid content = 99% / propionic acid = 99%).

A. Comparative Examples

Comparative Example 1

In a home mixer, 100 g of wheat bran is saturated with 100 g of formic acid. The bran acid soak up very easily. The whole product exhibits strong cohesion, but is easy to separate and decompose. It smells strongly of formic acid.

Comparative Example 2

In a home mixer, 100 g of Sipernate (highly disperse silica, Degussa) is saturated with 100 g of an acid mixture consisting of equal parts of formic acid and propionic acid. This acid mixture is well accepted by Sipernat. A wettable product is formed, which smells strongly of formic and propionic acid.

Comparative Example 3

As in Example 1, 100 g of Perlite are saturated with formic acid. Perlite absorbs it very well, but the resulting product has a tendency to stick and strongly smells of formic acid.

B. Saturation, agglomeration and coating experiments.

Example 1

In an Eirich mixer (R2), 460 g of Sipernate (highly disperse silica, Degussa) was saturated with 905 g of formic acid. Subsequently, the formic acid content was 67%. To 1000 g of this mixture, 200 g of Na-formate melt at 80 ° C was added as a binder liquid from a heated collector via a pneumatic spray nozzle. The resulting agglomerates were dusted with 44 g of Sipernate. The free acid content was 54%. The resulting product is wettable and exhibits reduced odor.

Example 2

In an Eirich mixer, 400 g of Sipernate was saturated with 1000 g of formic acid (formic acid content: 71%). In order to agglomerate and coat the agglomerates formed, 180 g of a concentrated grape sugar solution at 80 ° C were fed into the mixing space from the heated pantograph via a spray pneumatic nozzle as a binder liquid. The resulting agglomerates are wettable. The power consumption after saturation is ¢ 400 W, after coating 500 W. The number of revolutions during agglomeration increased from 340 upm to 460 upm.

Example 3

As in Example 2, 1100 g of formic acid were saturated in an Eirich mixer with 400 g of Sipernate. The formic acid content was then 71%. As a binder liquid, 260 g of citric acid melt at 170 ° C were fed from the collector via a pneumatic spray nozzle into the mixing space. The resulting agglomerates were then dusted with 44 g of Sipernate and 8 g of vanillin. The total acid content was 74%. The resulting agglomerates show a significantly reduced formic acid odor.

Example 4

In a rotary mixer (Lo 130), 8.7 kg of Sipernate was saturated with 24 kg of formic acid (98%) (formic acid content: 71%).

For the actual agglomeration and coating of the resulting agglomerates, 5.5 kg of citric acid melt at 170 [deg.] C. were fed from the collector into the mixing space via a pneumatic spray nozzle. The resulting agglomerates were dusted with 650 g

Sipemate and 24 g vanillin. The total acid content was 74%. The resulting agglomerates show a significantly lower odor and are well wettable.

Claims (11)

A wettable granulate consisting of a core and a shell, characterized in that the core material comprises an organic acid and a porous carrier and a shell, then a skin forming material which is soluble or swellable at 20 ° C. The granulate according to claim 1, characterized in that the coating additionally has a fine dust on the surface. The granulate according to claim 1, characterized in that the core comprises 30 to 90 wt. organic acid. Granulate according to claim 1, characterized in that the organic acid is a C 1 -C 6 mono or dicarboxylic acid or a mixture of both such carboxylic acids. Granulate according to claim 1, characterized in that porous, organic or inorganic materials are used as carrier, the particles of which have a particle size of from 1 gm to 1000 μπι, in particular from 5 μιτι to 100 μm. Granulate according to claim 1, characterized in that water-soluble polymers, organic acids, their salts or inorganic salts of low melting point are used as coating agents. The granulate according to claim 5, characterized in that cereal bran, silicates, perlite or silicic acid in proportions from 10 to 70% by weight, preferably from 20 to 40% by weight, are used as carrier. Granulate according to claim 6, characterized in that polyethylene glycols, polyvinylpyrrolidones or organic acids and their salts from C ₃ to C ₁₄ , preferably from C ₃ to C ₆ , in particular citric acid, are used as coating agents. fumaric, amber, adipinic, benzoic, sorbic and their salts or amino acids and their salts. 9. A process for the preparation of granules containing organic acids and porous carriers, characterized in that the carriers are saturated with organic acid in a liquid state, subsequently treated with a liquefied coating composition solidifying at room temperature, then agglomerated, the coating composition being added in an amount such that the resulting granules could be completely coated and then optionally odorized by the addition of fragrances and the wettability of the agglomerates is ensured by dusting with a finely dispersed powdered composition. Process according to claim 9, characterized in that the carrier is saturated with an organic acid in the mixer and then agglomerated with a coating composition and coated with a coating layer. Use of the granulate according to claim 1 for acidifying and preserving food and feed, as well as for use in silage.