CA2227282A1 - Free-flowing granules based on organic acids, preparation of said granules and their use - Google Patents
Free-flowing granules based on organic acids, preparation of said granules and their use Download PDFInfo
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- CA2227282A1 CA2227282A1 CA002227282A CA2227282A CA2227282A1 CA 2227282 A1 CA2227282 A1 CA 2227282A1 CA 002227282 A CA002227282 A CA 002227282A CA 2227282 A CA2227282 A CA 2227282A CA 2227282 A1 CA2227282 A1 CA 2227282A1
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- 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
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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)
- Animal Husbandry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Nutrition Science (AREA)
- Microbiology (AREA)
- Fodder In General (AREA)
- Fats And Perfumes (AREA)
- Glanulating (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- General Preparation And Processing Of Foods (AREA)
- Detergent Compositions (AREA)
- Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Medicinal Preparation (AREA)
- Cereal-Derived Products (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Paints Or Removers (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
Free-flowing granules based on organic acids, preparation of said granules and their use 5 The present invention relates to free-flowing granules consisting of a core and of a coat, wherein the core material contains an organic acid and a porous carrier and the coat has a water-soluble or water-swellable covering material.
10 The present invention furthermore 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 to the use of the granules for the treatment of foods and animal feeds, and to their use in silages.
Short-ch,ain organic acids, such as formic acid, acetic acid or propionic acid, are used in the acidification and preservation of foods an,d animal feeds. The disadvantages of these acids are ~a) their liquid state of aggregation at room temperature, (b) the 20 sharp, pungent odor resulting from the low vapor pressure and (c) their cc,rrosiveness.
Furthermore, the liquid organic acids in concentrated form can be incorporated, for example in animal feeds, only by the consider-25 ably complicated technical procedure.
DE 28 33 727 A1 discloses a particulate, fungicidal materialwhich contains propionic acid and a carrier. This material is in-tended to prevent an increase in the number of mold colonies in 30 stored agricultural harvest products even with an incubation time of several days. However, it has been found that such material is itself not stable when stored (loss of acid), and the maximum amount of propionic acid which can be applied depends to a great extent on the carrier used. In addition, unpleasant odors occur 35 with this material owing to the volatility of the propionic acid.
It is an object of the present invention to provide free-flowing, low-odor granules for the treatment of foods and animal feeds, by means of which the handling properties are substantially improved 40 for the user. Attention was focussed on the preparation of a solid organic acid in the form of an adsorbate which was to dif-fer from simple impregnated products essentially in that it ~a) permits an acid content > 30% by weight in the solid regardless of the carrier and hence has a very high active ingredient con-45 tent and (b) the release of the organic acid from the adsorbateis kept to a mini~l and hence the active ingredient content is 0050/46Ll9 CA 02227282 1998-02-18 maintained. The pulverulent end product should have good storage, flow and processing properties.
We have found that this object is achieved by granules consisting 5 of a core and a coat, wherein the core material contains an organic acid and a porous carrier and the coat has a covering material which is water-soluble or water-swellable at 20 C.
The novel granules have the advantage that the highly pungent 10 acid odor is reduced and, in spite of the solid formulation, the acid content is released from the solid powder in readily and rapidly soluble form.
The present invention furthermore relates to a process for the 15 preparation of granules containing organic acids and porous car-riers, which comprises impregnating the carrier with the liquid organic acid, then agglomerating it with a covering material which solidifies at room temperature, the covering material being added in an amount such that the resultinq granules are coated, 20 and, if required, providing a further odor by adding scents and, if required, ensuring free-flowing properties of the agglomerates by dusting with a finely divided dusting agent.
The liquid organic acid is understood as meaning acids or acid 25 mixtures which are liquid at the processing t~ eratures or are converted into the liquid state by increasing the temperature or dissolving or dispersing in liquids.
In a preferred embodiment, the novel granules have a dusting 30 agent on the surface of the coat. The core contains preferably 30-90, in particular 50-80, % by weight of organic acid. The organic acid preferably consists of one or more Cl-C6-mono- or di-carboxylic acids, in particular formic, acetic and/or propionic acid.
Suitable carriers are porous, organic or inorganic carriers whose particle sizes are from 1 to 1000 ~m, preferably from 5 to 100 ~m. The core may also contain further solids, for example solids suitable as feed supplements, such as calcium propionate.
Water-soluble polymers, organic acids, salts thereof or inorganic salts having a low melting point may be used as the covering ma-terial.
OOSO/46:119 CA 02227282 1998-02-18 Cereal brans, silicates, perlite or silicas, in amounts of from 10 to 70, preferably from 20 to 40, % by weight, based on the weight of the core, are preferably used as the carrier.
5 Preferably used covering materials are polyethylene glycols, polyvinylpyrrolidones or C3-Cl4, preferably C3-C6, organic acids and salts thereof, in particular citric acid, fumaric acid, succinic acid, adipic acid, benzoic acid and salts thereof, or amino acids and salts thereof are preferably used as the covering 10 material.
In a preferred embodiment of the novel process, the carrier is initially taken in a mixer, impregnated with the organic acid and then ags~lomerated and coated with the covering material.
The loose and impregnated carrier particles are mixed with the covering material ~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 tem-20 perature ~20 C). This binding liquid is preferably applied in theheated state to the impregnated carrier particles and mixed with the latt:er. The binding liquids solidify on the surface of the impregnated carrier particles. Suitable operating parameters of the mixer result in agglomeration of different particles to give 25 larger granules.
The size of the granules can be established by process parameters in the mixing as well as by subsequent sieving or milling. The granules preferably have a mean diameter of less than 3 mm, in 30 particu]Lar 0.3-1.3 mm. If required, residual water may be present in the binding liquid used for coating and agglomeration. After the agg:Lomeration process, this water can be bound by a dry and finely divided dusting agent by means of a dusting process. As a result of this dusting process, it is also possible to prevent 35 subsequent adhesion of the agglomerates and in addition, for example, to apply the salt of the organic acid used (eg. sodium propionate or calcium propionate) to the agglomerate. Further-more, a scent or flavor material, eg. vanillin, citral or fruc-tin, can, if required, be added during the dusting step, result-40 ing in an additional odor-masking effect and, for example, ensur-ing that consumption of the animal feed is appealing.
In principle, all nonorganic or inorganic porous carriers are suitable for the preparation of such free-flowing, low-odor 45 agglomerates, provided that they are acid-resistant. Examples are cereal brands, perlite, clay materials, silicates and silicas, the inorganic carriers being preferred since their material properties can be more readily controlled.
Preferably used binding liquids are water-soluble or water-5 swellable substances which solidify at room temperature. This makes it possible to dispense with the subsequent drying step, in which, apart from the solvent and the additional water, the organic acid too would evaporate off in some cases.
10 Particu]arly suitable covering materials Ibinding liquids) for the agg]omeration process and the coating are those which have a softening temperature of more than 30 C, preferably more than 60 C, in order to prevent deformation of the agglomerates at a relatively high storage te~perature. Covering materials which are 15 preferably to be used are those which furthermore do not counter-act the pH-reducing effect of the adsorbed organic acid or, if requirecl, even support or strengthen said effect.
Example-; of suitable binding liquids are highly concentrated, 20 heated sugar solutions or alkali metal/alkaline earth metal formate,'acetate/propionate solutions. As a result of the final dusting step, the residual water content can be taken up. Poly-ethylene glycols having a low melting point, eg. PEG 4000, melts of citr:ic acid, of adipic acid, or fumaric acid or o~ benzoic 25 acid or of salts thereof, highly concentrated solutions of amino acids and mixtures of these acids are preferred as binding liquids. From 5 to B0, preferably from 10 to 25, % by weight, based on the weight of the granules, of binding liquid are used.
30 Suitable dusting agents in addition to the porous carriers them-selves i~re finely divided, milled organic acids or salts thereof, eg. sodium formate, and inorganic salts or Aerosil. < 10, prefer-ably from 0.5 to 5, % by weight of the dusting agents are added.
35 In gene:ral, the porous carrier is initially taken in the mixer, for example an Eirich mixer, and is impregnated with the organic acid with little energy input. In an alternative procedure, how-ever, tlhe liquid is initially taken in the mixer and the carrier is meteced in. In this case, a higher energy input is required.
~0 It is nlecessary to ensure uniform impregnation and to avoid local overmoistening, which leads to formation of lumps. After impregnation is complete, a free-flowing, slightly cohesive heap of particles is present. The viscosity of the binding liquid 45 should be established by an appropriate choice of temperature so that it is less than 1000, preferably less than 100 mPa.s, in order to achieve a fine drop size distribution when spraying the binding liquid. Owing to the temperature difference between the heated binding liquid and the cooler impregnated carrier, the drops of binding liquid initially solidify rapidly in this pre-ferred embodiment. In the further course of the agglomeration 5 process, the temperature of the bed increases by 10-30 C, depend-ing on the type of binding liquid, due to the mechanical and the thermal energy input. Further drops of binding liquid accumulate on the agglomerates already formed and some of these drops coalesce with one another. The energy input increases by about lO 20% during the agglomeration.
Finally, a finely divided odor-imparting material may also be added with the dusting agent, as described above. In principle, a large number of scents and flavor materials are suitable for this 15 purpose and can be chosen in accordance with the subsequent use of the agglomerates. The amount of these scents may be < 1, pre-ferably from 0.05 to 0.5, % by weight, based on the granules. The agglomerates thus produced have a low dust content and little odor and their organic acid content is readily water-soluble.
The novel granules are suitable for the treatment of foods and animal feeds and for use in silages. Foods and animal feeds are to be understood in particular as meaning harvest products, such as hay, silage, moist cereals, pulses or grains, as well as milk 25 substitutes, liquid, mixed and mineral feeds, fish silages or fish meal.
Novel granules may contain other additives, for example minerals, VitA i n,5 ~ antibiotics or protein supplements.
Examples (Content of formic acid used = 99%/propionic acid used = 99%) 35 A. Comparative examples Comparative example 1 100 g of wheat bran are initially taken in a household mixer and impregnated with 100 g of formic acid. The acid is reaclily taken up; the product exhibits cohesive behavior but can be easily divided up. It ha~ a strong odor of formic acid.
0050/46]Ll9 CA 02227282 1998-02-18 Comparative example 2 100 g of Sipernat~D (finely divided silica, from Degussa) are init ially taken in a household mixer and impregnated with lO0 g of an acid mixture consisting of equal amounts of formic acid and propionic acid. The acid mixture is readily taken up; a loose, free-flowing product forms. The product has a pungent unpleasant odor of formic acid/propionic acid.
Comparative example 3 lO0 g of perlite are initially taken and are impregnated with the formic acid, similarly to Example l. The acid is readily taken up but the product shows a strong tendency to cake and lS has a strong pungent odor of formic acid.
B. Impregnation, agglomeration and coating tests Example 1 460 g of Sipernat~ ( finely divided silica, from Degussa) are init:ially taken in an Eirich mixer ~RO2 ) and are impregnated with 905 g of formic acid; the formic acid content is then 67%. 200 g of sodium formate melt at 80 C are then sprayed, as t:he binding liquid, from a heated storage contAi rler via a binary nozzle into the mixing space containing lO00 g of this mixt:ure. The resulting agglomerates are dusted with 44 g of Sipt!rnat~l9. The content of free acid is 54%. The resulting procluct is free-f lowing and has little odor .
Example 2 400 g of Sipernat~ are initially taken in an Eirich mixer and are impregnated with lO00 g of formic acid ( formic acid conl:ent: 71%). For agglomeration and coating, 180 g of a con-cenl:rated dextral solution at 80 C are sprayed, as binding liquid, from a heated storage container via a binary nozzle into the mixing space. The resulting agglomerates are dusted Wit}l 45 g of Sipernat~lD and 12 g of citral. The acid content is 1 hen 61% . The resulting agglomerates are free-flowing. The power consumption after the impregnation is ~ 400 W, and thal after coating is ~ 500 W. The speed is increased from 340 rpm to 460 rpm during the agglomeration step.
Exa~lple 3 400 g of Sipernat~ are initially taken in an Eirich mixer and are impregnated with 1100 g of formic acid, similarly to Example 2; the formic acid content is then 71%. 260 g of citric acid melt at 170 C are sprayed, as binding liquid, from a heated storage container via a binary nozzle into the mixing space. The resulting agglomerates are dusted with 44 g of Sipernat~ and 8 g of vanillin. The total acid content is ~ 74%. The resulting agglomerates have a substantially reduced odor of formic acid.
Exarnple 4 8 . 7 kg of Sipernat~ are initially taken in a ploughshare mix-er (Lo 130) and are impregnated with 24 kg of formic acid ( 98~ formic acid content: 71%). For agglomeration and coat-ing, S.S kg of citric acid melt at 170 C are sprayed from a heated storage container via a binary nozzle into the mixing space. The resulting agglomerates are dusted with 650 y of Sip~ernat~ and 24 g of vanillin. The total acid content is ~ 14%. The resulting agglomerates have a substantially reduced odor and are free-flowing.
10 The present invention furthermore 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 to the use of the granules for the treatment of foods and animal feeds, and to their use in silages.
Short-ch,ain organic acids, such as formic acid, acetic acid or propionic acid, are used in the acidification and preservation of foods an,d animal feeds. The disadvantages of these acids are ~a) their liquid state of aggregation at room temperature, (b) the 20 sharp, pungent odor resulting from the low vapor pressure and (c) their cc,rrosiveness.
Furthermore, the liquid organic acids in concentrated form can be incorporated, for example in animal feeds, only by the consider-25 ably complicated technical procedure.
DE 28 33 727 A1 discloses a particulate, fungicidal materialwhich contains propionic acid and a carrier. This material is in-tended to prevent an increase in the number of mold colonies in 30 stored agricultural harvest products even with an incubation time of several days. However, it has been found that such material is itself not stable when stored (loss of acid), and the maximum amount of propionic acid which can be applied depends to a great extent on the carrier used. In addition, unpleasant odors occur 35 with this material owing to the volatility of the propionic acid.
It is an object of the present invention to provide free-flowing, low-odor granules for the treatment of foods and animal feeds, by means of which the handling properties are substantially improved 40 for the user. Attention was focussed on the preparation of a solid organic acid in the form of an adsorbate which was to dif-fer from simple impregnated products essentially in that it ~a) permits an acid content > 30% by weight in the solid regardless of the carrier and hence has a very high active ingredient con-45 tent and (b) the release of the organic acid from the adsorbateis kept to a mini~l and hence the active ingredient content is 0050/46Ll9 CA 02227282 1998-02-18 maintained. The pulverulent end product should have good storage, flow and processing properties.
We have found that this object is achieved by granules consisting 5 of a core and a coat, wherein the core material contains an organic acid and a porous carrier and the coat has a covering material which is water-soluble or water-swellable at 20 C.
The novel granules have the advantage that the highly pungent 10 acid odor is reduced and, in spite of the solid formulation, the acid content is released from the solid powder in readily and rapidly soluble form.
The present invention furthermore relates to a process for the 15 preparation of granules containing organic acids and porous car-riers, which comprises impregnating the carrier with the liquid organic acid, then agglomerating it with a covering material which solidifies at room temperature, the covering material being added in an amount such that the resultinq granules are coated, 20 and, if required, providing a further odor by adding scents and, if required, ensuring free-flowing properties of the agglomerates by dusting with a finely divided dusting agent.
The liquid organic acid is understood as meaning acids or acid 25 mixtures which are liquid at the processing t~ eratures or are converted into the liquid state by increasing the temperature or dissolving or dispersing in liquids.
In a preferred embodiment, the novel granules have a dusting 30 agent on the surface of the coat. The core contains preferably 30-90, in particular 50-80, % by weight of organic acid. The organic acid preferably consists of one or more Cl-C6-mono- or di-carboxylic acids, in particular formic, acetic and/or propionic acid.
Suitable carriers are porous, organic or inorganic carriers whose particle sizes are from 1 to 1000 ~m, preferably from 5 to 100 ~m. The core may also contain further solids, for example solids suitable as feed supplements, such as calcium propionate.
Water-soluble polymers, organic acids, salts thereof or inorganic salts having a low melting point may be used as the covering ma-terial.
OOSO/46:119 CA 02227282 1998-02-18 Cereal brans, silicates, perlite or silicas, in amounts of from 10 to 70, preferably from 20 to 40, % by weight, based on the weight of the core, are preferably used as the carrier.
5 Preferably used covering materials are polyethylene glycols, polyvinylpyrrolidones or C3-Cl4, preferably C3-C6, organic acids and salts thereof, in particular citric acid, fumaric acid, succinic acid, adipic acid, benzoic acid and salts thereof, or amino acids and salts thereof are preferably used as the covering 10 material.
In a preferred embodiment of the novel process, the carrier is initially taken in a mixer, impregnated with the organic acid and then ags~lomerated and coated with the covering material.
The loose and impregnated carrier particles are mixed with the covering material ~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 tem-20 perature ~20 C). This binding liquid is preferably applied in theheated state to the impregnated carrier particles and mixed with the latt:er. The binding liquids solidify on the surface of the impregnated carrier particles. Suitable operating parameters of the mixer result in agglomeration of different particles to give 25 larger granules.
The size of the granules can be established by process parameters in the mixing as well as by subsequent sieving or milling. The granules preferably have a mean diameter of less than 3 mm, in 30 particu]Lar 0.3-1.3 mm. If required, residual water may be present in the binding liquid used for coating and agglomeration. After the agg:Lomeration process, this water can be bound by a dry and finely divided dusting agent by means of a dusting process. As a result of this dusting process, it is also possible to prevent 35 subsequent adhesion of the agglomerates and in addition, for example, to apply the salt of the organic acid used (eg. sodium propionate or calcium propionate) to the agglomerate. Further-more, a scent or flavor material, eg. vanillin, citral or fruc-tin, can, if required, be added during the dusting step, result-40 ing in an additional odor-masking effect and, for example, ensur-ing that consumption of the animal feed is appealing.
In principle, all nonorganic or inorganic porous carriers are suitable for the preparation of such free-flowing, low-odor 45 agglomerates, provided that they are acid-resistant. Examples are cereal brands, perlite, clay materials, silicates and silicas, the inorganic carriers being preferred since their material properties can be more readily controlled.
Preferably used binding liquids are water-soluble or water-5 swellable substances which solidify at room temperature. This makes it possible to dispense with the subsequent drying step, in which, apart from the solvent and the additional water, the organic acid too would evaporate off in some cases.
10 Particu]arly suitable covering materials Ibinding liquids) for the agg]omeration process and the coating are those which have a softening temperature of more than 30 C, preferably more than 60 C, in order to prevent deformation of the agglomerates at a relatively high storage te~perature. Covering materials which are 15 preferably to be used are those which furthermore do not counter-act the pH-reducing effect of the adsorbed organic acid or, if requirecl, even support or strengthen said effect.
Example-; of suitable binding liquids are highly concentrated, 20 heated sugar solutions or alkali metal/alkaline earth metal formate,'acetate/propionate solutions. As a result of the final dusting step, the residual water content can be taken up. Poly-ethylene glycols having a low melting point, eg. PEG 4000, melts of citr:ic acid, of adipic acid, or fumaric acid or o~ benzoic 25 acid or of salts thereof, highly concentrated solutions of amino acids and mixtures of these acids are preferred as binding liquids. From 5 to B0, preferably from 10 to 25, % by weight, based on the weight of the granules, of binding liquid are used.
30 Suitable dusting agents in addition to the porous carriers them-selves i~re finely divided, milled organic acids or salts thereof, eg. sodium formate, and inorganic salts or Aerosil. < 10, prefer-ably from 0.5 to 5, % by weight of the dusting agents are added.
35 In gene:ral, the porous carrier is initially taken in the mixer, for example an Eirich mixer, and is impregnated with the organic acid with little energy input. In an alternative procedure, how-ever, tlhe liquid is initially taken in the mixer and the carrier is meteced in. In this case, a higher energy input is required.
~0 It is nlecessary to ensure uniform impregnation and to avoid local overmoistening, which leads to formation of lumps. After impregnation is complete, a free-flowing, slightly cohesive heap of particles is present. The viscosity of the binding liquid 45 should be established by an appropriate choice of temperature so that it is less than 1000, preferably less than 100 mPa.s, in order to achieve a fine drop size distribution when spraying the binding liquid. Owing to the temperature difference between the heated binding liquid and the cooler impregnated carrier, the drops of binding liquid initially solidify rapidly in this pre-ferred embodiment. In the further course of the agglomeration 5 process, the temperature of the bed increases by 10-30 C, depend-ing on the type of binding liquid, due to the mechanical and the thermal energy input. Further drops of binding liquid accumulate on the agglomerates already formed and some of these drops coalesce with one another. The energy input increases by about lO 20% during the agglomeration.
Finally, a finely divided odor-imparting material may also be added with the dusting agent, as described above. In principle, a large number of scents and flavor materials are suitable for this 15 purpose and can be chosen in accordance with the subsequent use of the agglomerates. The amount of these scents may be < 1, pre-ferably from 0.05 to 0.5, % by weight, based on the granules. The agglomerates thus produced have a low dust content and little odor and their organic acid content is readily water-soluble.
The novel granules are suitable for the treatment of foods and animal feeds and for use in silages. Foods and animal feeds are to be understood in particular as meaning harvest products, such as hay, silage, moist cereals, pulses or grains, as well as milk 25 substitutes, liquid, mixed and mineral feeds, fish silages or fish meal.
Novel granules may contain other additives, for example minerals, VitA i n,5 ~ antibiotics or protein supplements.
Examples (Content of formic acid used = 99%/propionic acid used = 99%) 35 A. Comparative examples Comparative example 1 100 g of wheat bran are initially taken in a household mixer and impregnated with 100 g of formic acid. The acid is reaclily taken up; the product exhibits cohesive behavior but can be easily divided up. It ha~ a strong odor of formic acid.
0050/46]Ll9 CA 02227282 1998-02-18 Comparative example 2 100 g of Sipernat~D (finely divided silica, from Degussa) are init ially taken in a household mixer and impregnated with lO0 g of an acid mixture consisting of equal amounts of formic acid and propionic acid. The acid mixture is readily taken up; a loose, free-flowing product forms. The product has a pungent unpleasant odor of formic acid/propionic acid.
Comparative example 3 lO0 g of perlite are initially taken and are impregnated with the formic acid, similarly to Example l. The acid is readily taken up but the product shows a strong tendency to cake and lS has a strong pungent odor of formic acid.
B. Impregnation, agglomeration and coating tests Example 1 460 g of Sipernat~ ( finely divided silica, from Degussa) are init:ially taken in an Eirich mixer ~RO2 ) and are impregnated with 905 g of formic acid; the formic acid content is then 67%. 200 g of sodium formate melt at 80 C are then sprayed, as t:he binding liquid, from a heated storage contAi rler via a binary nozzle into the mixing space containing lO00 g of this mixt:ure. The resulting agglomerates are dusted with 44 g of Sipt!rnat~l9. The content of free acid is 54%. The resulting procluct is free-f lowing and has little odor .
Example 2 400 g of Sipernat~ are initially taken in an Eirich mixer and are impregnated with lO00 g of formic acid ( formic acid conl:ent: 71%). For agglomeration and coating, 180 g of a con-cenl:rated dextral solution at 80 C are sprayed, as binding liquid, from a heated storage container via a binary nozzle into the mixing space. The resulting agglomerates are dusted Wit}l 45 g of Sipernat~lD and 12 g of citral. The acid content is 1 hen 61% . The resulting agglomerates are free-flowing. The power consumption after the impregnation is ~ 400 W, and thal after coating is ~ 500 W. The speed is increased from 340 rpm to 460 rpm during the agglomeration step.
Exa~lple 3 400 g of Sipernat~ are initially taken in an Eirich mixer and are impregnated with 1100 g of formic acid, similarly to Example 2; the formic acid content is then 71%. 260 g of citric acid melt at 170 C are sprayed, as binding liquid, from a heated storage container via a binary nozzle into the mixing space. The resulting agglomerates are dusted with 44 g of Sipernat~ and 8 g of vanillin. The total acid content is ~ 74%. The resulting agglomerates have a substantially reduced odor of formic acid.
Exarnple 4 8 . 7 kg of Sipernat~ are initially taken in a ploughshare mix-er (Lo 130) and are impregnated with 24 kg of formic acid ( 98~ formic acid content: 71%). For agglomeration and coat-ing, S.S kg of citric acid melt at 170 C are sprayed from a heated storage container via a binary nozzle into the mixing space. The resulting agglomerates are dusted with 650 y of Sip~ernat~ and 24 g of vanillin. The total acid content is ~ 14%. The resulting agglomerates have a substantially reduced odor and are free-flowing.
Claims (11)
1. Free-flowing granules consisting of a core and of a coat, wherein the core material contains an organic acid and a porous carrier and the coat has a covering material which is water-soluble or water-swellable at 20°C.
2. Granules as claimed in claim 1, wherein the coat additionally has a dusting agent on the surface.
3. Granules as claimed in claim 1, wherein the core contains 30-90% by weight of organic acids.
4. Granules as claimed in claim 1, wherein the organic acid is a C1-C6-mono- or dicarboxylic acid or a mixture of such carboxylic acids.
5. Granules as claimed in claim l, wherein the carrier used is a porous, organic or inorganic carrier whose particle sizes are from 1 to 1000 µm, preferably from 5 to 100 µm.
6. Granules as claimed in claim 1, wherein the covering material used is a water-soluble polymer, an organic acid, a salt thereof or an inorganic salt having a low melting point.
7. Granules as claimed in claim 5, wherein the carrier used is a cereal bran, a silicate, perlite or a silica, in an amount of from 10 to 70, preferably from 20 to 40, % by weight.
8. Granules as claimed in claim 6, wherein the covering material used is polyethylene glycol, a polyvinylpyrrolidone or a C3-C14, preferably C3-C6, organic acid or a salt thereof, in particular citric acid, fumaric acid, succinic acid, adipic acid, benzoic acid, sorbic acid or a salt thereof or an amino acid or a salt thereof.
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 covering material which solidifies at room temperature, the covering material being added in an amount such that the resulting granules are coated, and, if required, providing a further odor by adding scents and, if required, ensuring free-flowing properties of the agglomerates by dusting with a finely divided dusting agent.
10. A process as claimed in claim 9, wherein the carrier is initially taken in a mixer, impregnated with the organic acid and then agglomerated and coated with the covering material.
11. Use of granules as claimed in claim 1 for acid treatment and preservation of foods and animal feeds, and in silages.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19531782.3 | 1995-08-30 | ||
| DE19531782A DE19531782A1 (en) | 1995-08-30 | 1995-08-30 | Free-flowing granules based on organic acids, process for their preparation and their use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2227282A1 true CA2227282A1 (en) | 1997-03-06 |
Family
ID=7770678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002227282A Abandoned CA2227282A1 (en) | 1995-08-30 | 1996-08-26 | Free-flowing granules based on organic acids, preparation of said granules and their use |
Country Status (19)
| Country | Link |
|---|---|
| EP (1) | EP0847243A1 (en) |
| JP (1) | JPH11511969A (en) |
| KR (1) | KR19990044266A (en) |
| CN (1) | CN1193892A (en) |
| AU (1) | AU706207B2 (en) |
| BR (1) | BR9609990A (en) |
| CA (1) | CA2227282A1 (en) |
| CZ (1) | CZ49998A3 (en) |
| DE (1) | DE19531782A1 (en) |
| EA (1) | EA000874B1 (en) |
| GE (1) | GEP20002062B (en) |
| HU (1) | HUP9802322A3 (en) |
| IL (1) | IL122355A (en) |
| NO (1) | NO980861D0 (en) |
| NZ (1) | NZ316933A (en) |
| PL (1) | PL325169A1 (en) |
| SK (1) | SK22898A3 (en) |
| TR (1) | TR199800344T1 (en) |
| WO (1) | WO1997007687A1 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19710127A1 (en) * | 1997-03-12 | 1998-09-17 | Herbert Dr Widulle | Purification of drinking water to reduce the germ content |
| DE19933906A1 (en) * | 1999-07-22 | 2001-01-25 | Eckhard Eltz | Blower assembly to conserve the edible characteristics of stored animal feed suitable for use on small farms |
| DE10055390A1 (en) * | 2000-11-09 | 2002-05-29 | Nutrinova Gmbh | Use of an acid preparation as a feed additive in livestock rearing |
| HUP0500084A3 (en) * | 2002-01-08 | 2005-08-29 | Can Technologies Inc Minnetonk | Encapsulation by coating with a mixture of lipids and hydrophobic, high melting point compounds |
| KR100451545B1 (en) * | 2002-03-18 | 2004-10-06 | 김유용 | The product method of mixing compound containing hydrochloric acid and scoria, mixing compound and feed |
| DE10231891A1 (en) * | 2002-07-12 | 2004-01-22 | Basf Ag | Coated formulation containing sodium, potassium, cesium and/or ammonium diformate is used in premix for animal feed or additive, as performance and/or growth promoter; acidifier; preservative or silage or in fertilizer |
| SE528410C2 (en) * | 2004-06-30 | 2006-11-07 | Kemira Grow How Ab | Antimicrobial acidifying feed product and process for its preparation |
| TW200635959A (en) * | 2005-02-04 | 2006-10-16 | Basf Ag | Water swellable material |
| DE102006021392B4 (en) * | 2006-05-08 | 2013-06-27 | Ligrana Gmbh | composition |
| DE102007031039A1 (en) * | 2007-07-04 | 2009-01-08 | Süd-Chemie AG | Process for the careful refining of vegetable oils with natural bleaching earth |
| DE102021115047A1 (en) | 2021-06-10 | 2022-12-15 | André Brendler | Carboxylic acid loaded salt carrier and the process for the preparation thereof |
| LU500270B1 (en) | 2021-06-10 | 2022-12-12 | Lucas Brendler | Carboxylic Acid Loaded Salt Carrier and the Method for Producing thereof |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL149989B (en) * | 1967-03-08 | 1976-07-15 | Philips Nv | GRANULAR PREPARATION. |
| CH484625A (en) * | 1969-04-03 | 1970-01-31 | Libavia Ag | Process for the production of granulated animal feed |
| AR206283A1 (en) * | 1971-01-27 | 1976-07-15 | Chinoin Gyogyszer Es Vegyeszet | A COMPOSITION FOR THE PRESERVATION OF PRODUCTS OF ANIMAL OR PLANT ORIGIN |
| CH613607A5 (en) * | 1975-06-11 | 1979-10-15 | Lonza Ag | Ensiling agent and process for preparation thereof |
| US4199606A (en) * | 1977-09-22 | 1980-04-22 | Bland Bobby | Propionic acid on a carrier material as a preservative |
| DE3103623A1 (en) * | 1979-08-03 | 1982-09-16 | Siegfried Dr. 8069 Sünzhausen Moser | Mineral-rich supplementary feed and use thereof |
| IT1185550B (en) * | 1985-04-12 | 1987-11-12 | Dox Al Italia Spa | NON-DUSTY MIXTURES OF FLOURS OR FLOURS WITH ACTIVE INGREDIENTS FOR MANGIMISTICS |
| IT1229930B (en) * | 1988-10-14 | 1991-09-16 | Dox Al Italia Spa | PROCEDURE FOR THE PREPARATION OF MIXTURES FOR FOOD AND FOOD USE INCLUDING ACTIVE SUBSTANCES UNIFORMLY DISTRIBUTED |
| US5082675A (en) * | 1989-07-29 | 1992-01-21 | Bp Chemicals Limited | Ensiling composition |
| DE4117399A1 (en) * | 1990-06-14 | 1992-01-09 | Micro Plus Konzentrate Gmbh | Agent for conditioning granular fodder material - is mixt. of molasses and e.g. dextrin additive, forming film which inhibits dust formation |
| DE4217971C1 (en) * | 1992-05-30 | 1993-10-21 | Boehringer Ingelheim Vetmed | Process and fluid bed apparatus for granulating and / or wrapping |
| EP0612843A1 (en) * | 1993-02-22 | 1994-08-31 | Unilever N.V. | Granular acidic cleaners |
| IT1265290B1 (en) * | 1993-12-17 | 1996-10-31 | Dox Al Italia Spa | MIXTURES WITH A HIGH CONTENT OF ACTIVE SUBSTANCES SUITABLE TO BE DISTRIBUTED HOMOGENEOUSLY IN ANIMAL FEED. |
-
1995
- 1995-08-30 DE DE19531782A patent/DE19531782A1/en not_active Withdrawn
-
1996
- 1996-08-26 CA CA002227282A patent/CA2227282A1/en not_active Abandoned
- 1996-08-26 CN CN96196578A patent/CN1193892A/en active Pending
- 1996-08-26 WO PCT/EP1996/003757 patent/WO1997007687A1/en not_active Application Discontinuation
- 1996-08-26 HU HU9802322A patent/HUP9802322A3/en unknown
- 1996-08-26 JP JP9509846A patent/JPH11511969A/en active Pending
- 1996-08-26 NZ NZ316933A patent/NZ316933A/en unknown
- 1996-08-26 PL PL96325169A patent/PL325169A1/en unknown
- 1996-08-26 IL IL12235596A patent/IL122355A/en not_active IP Right Cessation
- 1996-08-26 SK SK228-98A patent/SK22898A3/en unknown
- 1996-08-26 TR TR1998/00344T patent/TR199800344T1/en unknown
- 1996-08-26 AU AU69286/96A patent/AU706207B2/en not_active Ceased
- 1996-08-26 KR KR1019980701502A patent/KR19990044266A/en not_active Application Discontinuation
- 1996-08-26 GE GEAP19964214A patent/GEP20002062B/en unknown
- 1996-08-26 CZ CZ98499A patent/CZ49998A3/en unknown
- 1996-08-26 EA EA199800229A patent/EA000874B1/en not_active IP Right Cessation
- 1996-08-26 BR BR9609990A patent/BR9609990A/en not_active Application Discontinuation
- 1996-08-26 EP EP96930104A patent/EP0847243A1/en not_active Withdrawn
-
1998
- 1998-02-27 NO NO980861A patent/NO980861D0/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| CN1193892A (en) | 1998-09-23 |
| KR19990044266A (en) | 1999-06-25 |
| NO980861L (en) | 1998-02-27 |
| CZ49998A3 (en) | 1998-08-12 |
| AU706207B2 (en) | 1999-06-10 |
| EA000874B1 (en) | 2000-06-26 |
| AU6928696A (en) | 1997-03-19 |
| HUP9802322A2 (en) | 1999-01-28 |
| BR9609990A (en) | 1999-07-06 |
| EP0847243A1 (en) | 1998-06-17 |
| TR199800344T1 (en) | 1998-05-21 |
| SK22898A3 (en) | 1998-12-02 |
| PL325169A1 (en) | 1998-07-06 |
| GEP20002062B (en) | 2000-05-10 |
| JPH11511969A (en) | 1999-10-19 |
| IL122355A (en) | 2000-08-31 |
| MX9801399A (en) | 1998-05-31 |
| IL122355A0 (en) | 1998-04-05 |
| EA199800229A1 (en) | 1998-12-24 |
| NO980861D0 (en) | 1998-02-27 |
| DE19531782A1 (en) | 1997-03-06 |
| WO1997007687A1 (en) | 1997-03-06 |
| HUP9802322A3 (en) | 2001-08-28 |
| NZ316933A (en) | 1999-01-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |