CZ20022905A3 - Organo-mineral adsorbent of mycotoxins used as ingredient in feeding stuff, process of its preparation and use - Google Patents

Abstract

Organomineral adsorbent of mycotoxins as an animal feed additive, procedure for production and application, is obtained by known processes, technological preparation of zeolitic tuff, containing more than 80% of mineral clinoptilotite/heulandite, three steps comminution, wet classification and water suspended. Suspension 20-50 wt% of zeolitic tuff is mixed in a mixer on 4 000 r/m with addition of organic component -quaternary amine with long carbon chain, the most suitable are dioctadecyldimethyl amine, octadecylthreemethyl amine, octadecyldimethylbenzyl amine and similar compounds, in the amount of 0.5-5 meq/100g of zeolitic tuff. Suspension is filtered, dryed at temperature 80-100 DEG C, desintegrated up to the particle size below 100 micrometers and than packed in powdered state. Adsorbent of mycotoxins possess balanced surface charge and hydrophobicity level and in accordance to mentioned a new active sites, which absorb mycotoxins of different polarities. Organomineral adsorbent of mycotoxins is added to the animal feed directly or through premixes in the amount of 0.2 wt% to feedmix.

Description

Organomineral mycotoxin adsorbent as feed additive, method of production and use

Technical field

The invention relates to an organomineral mycotoxin adsorbent as an additive to feed, to a process for its production and use. According to the International Patent Classification (MPT ⁶ ), it belongs to Class A 23K 1/175, including mineral feed additives.

The technical problem solved by this invention is how to obtain a surface-modified adsorbent by chemically-technological treatment of a zeolite tuff containing over 85% clinoptilolite / heulandite and a strictly controlled amount of a certain organic compound (quaternary amine with long carbon chains). in order to achieve a controlled surface charge and a level of hydrophobicity, which is intended to result in an organomineral adsorbent as a feed additive which simultaneously absorbs mycotoxins of various properties in the animal's digestive tract.

BACKGROUND OF THE INVENTION

A new approach to preventing the effects of mycotoxins, such as the detoxification of mycotoxin-contaminated feed, is aimed worldwide at developing effective adsorbents that are added to animal feed. Their role is to efficiently, selectively and very quickly adsorb mycotoxins in the digestive tract in situ when a mineral adsorbent enters the tract together with contaminated feed. The adsorbent binds mycotoxins directly in the gastric juice electrolyte and in this way reduces their bioavailability, e.g., blocks their resorption in organs and abolishes their toxicity.

From a chemical point of view, mycotoxins represent a wide range of complex organic compounds with different functional groups and hence different properties. Depending on their use, there may optionally be more than one mycotoxin with different properties (polarity, functional groups, anionic or cationic character) and the adsorbent must simultaneously have active centers of different but precisely controlled properties on the surface. Given the complexity of the problem, very intensive research has been carried out in the world, especially in recent years.

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More new products for adsorption of mycotoxins can be found on the world market, usually based on modified clay minerals (HSCAS, Novosil, Myco-ad - USA, Mycofix-Plus, Biomin - Austria, Mycosil - Mexico). By modifying the clay minerals, the surface properties were altered to improve and extend the adsorption efficiency for a wide spectrum of mycotoxins.

Mineral a mycotoxin adsorbent bearing the trade name Min-a-Zel, obtained according to YU-Patent No. 48589, granted to the Institute of Technology of Nuclear and Other Mineral Resources, Belgrade, Yugoslavia, is known as an additive to feed. The patent discloses the chemical-technological treatment of a zeolite tuff containing 85% clinoptilolite, three-stage crushing, activation and grinding with sodium chloride up to a particle size of maximum 60 µm. The powdered product obtained is a mineral adsorbent of mycotoxins from animal feed in the digestive tract. It is added to feed contaminated with mycotoxin in an amount of 0.2 to 0.5% depending on the level of contamination of the feed mixture.

Mycotoxin mineral adsorbent with improved properties obtained by the method of published Yugoslav patent application No. P-177/98 (Applicant Institute of Technology of Nuclear and Other Mineral Raw Materials, Belgrade, Yugoslavia) is also known as an animal feed additive. The patent discloses a process for producing mineral adsorbents using a three-stage crushing of zeolite tuff containing 85% clinoptilolite up to a particle size of 150 µm, then with potassium chloride depending on the variable potassium content of the raw tuff, activated and ground up to a particle size of 60 µm maximum . The obtained material is wet-sieved in a centrifuge by separating particles below 10 µm and stored as a 25% suspension in water for the next application. If the 25% suspension is filtered, dried and milled, then the mineral mycotoxin adsorbent is obtained as a powder. As an animal feed additive, it is mixed in the feed mixture in an amount of from 0.3 to 0.5%.

Both mycotoxin mineral adsorbents according to YU Patent No. 488586 and YUppatent Application No. P177 / 98 have been shown to be good mycotoxin adsorbents for molecules belonging to the polar toxin family (aflatoxins and others) by more than 90%, while lower polarity mycotoxins (zearalenone) , ochratoxin A, T-2 toxin) were 30 to 50% adsorbed.

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SUMMARY OF THE INVENTION

Mycotoxins, secondary metabolites produced by fungi, are highly toxic to numerous animal species (pigs, cattle, sheep, horses, dogs, cats, rabbits), laboratory animals and humans. Mycotoxicoses are diseases caused by the consumption of food contaminated by mycotoxins, they are not contagious but cannot be treated by any treatment. Commonly known mycotoxicoses of domestic animals are aflatoxicosis, ochratoxicosis, zearalenone toxicosis and trichothecene toxicosis. Worldwide, it is estimated that more than 25% of cereals are contaminated with mycotoxins. Because the absorption of mycotoxins is very rapid in meat, milk and eggs, their presence in animal food is toxic not only to animals but also to humans.

The essence of the invention consists in the controlled modification of the surface charge properties by modifying processes with organic compounds - radicals, on a zeolite tuff treated by previously known processes, three-stage grinding and wet sorting to a 25% suspension.

This is achieved by adding a controlled amount of the selected long chain quaternary amine to a concentration of clinoptilolite / heulandite tuff at a certain concentration, allowing the formation of an organomineral complex having different properties from the starting material (surface charge, hydrophobicity level, etc.).

A zeolite tuff containing more than 80% clinoptilolite / heulandite mineral, prepared by known grinding, wet screening and 25% suspension techniques, achieves an equilibrium of exchangeable cations, maintaining a negative surface charge as a result of isomorphic substitution of Al ^{3+ by} bivalent cations (Ca ²⁺ or Mg ² *). Such a surface adsorbs polar mycotoxins. Another organic modification of zeolite tuff affects the exchange of surface charge and changes in the level of adsorption for less polar mycotoxins, especially for zearalenone (96%), ochratoxin A (96%) and T-2 toxin (85%). At the same time, the adsorption level for aflatoxins does not drop (99%). As for ergot alkaloids, it adsorbs over 80% on the inorganic form but over 90% on the organically modified analogue.

This can be explained as follows: the obtained organomineral mycotoxin adsorbent - the organozeolite has not only a hydrophilic negative surface charge as the boundary phase, but it is partly converted to hydrophobic, which results in better adsorption of the less polar mycotoxin molecules. At the same time, this leads to a partial exchange of surface charge from negative to positive, which is controlled by the amount of organic compound added to the modification used. The positive charge on the surface now represents new active centers also for the adsorption of polar molecules having anionic character.

The presence of the organic phase used for the modification is limited not only to obtain the desired properties of the product (surface charge, hydrophobicity), but also in terms of the amounts that are allowed for consumption by living organisms since they become toxic above a certain concentration.

The novel controlled surface charge and controlled hydrophobicity mycotoxin organomineral adsorbent of the present invention is obtained as a slurry reaction product by known processes from a preformed and processed mineral component - zeolite tuff containing> 80% clinoptilolite / heulandite mineral and high molecular weight quaternary amine weight.

Organomineral mycotoxin additive, organozeolite, is the result of an ion exchange reaction between inorganic cations on the surface of zeolite tuff (Ca ²⁺ , Mg ²⁺ , Na ⁺ , K ⁺ ) and a long-chain quaternary amine such as dioctadecyl (dimethyl) amine, octadecyl (trimethyl) amine, octadecyl (dimethyl) benzylamine or similar amines. Quart! The amine is exchanged quantitatively and completely irreversibly with the inorganic cations on the outer surface of the zeolite tuff. The quaternary amine molecule is too large to seal into the structural channels of the zeolite tuff and the internal exchange sites remain free to react with smaller cations such as inorganic cations.

I. Characteristics of mineral component - zeolite tuff

1) Particle size distribution:

100% below 150 pm% below 63 μιτι% below 20 μΓη

4 4 4 · ·· 4 ·

0 0 4 0 · 0 · 0 0 0 0 · 00 · 00 ··· 4 · · · · · · 4 · · · 44 · · · · · · ·

2) Chemical composition:

SiO2 63 to 68 wt. MgO 0.8 to 1.5 wt. AI2O3 11 to 14 wt. Na2O 0.8 to 1.5 wt. Fe ₂ O ₃ 0.8 to 2.5 wt. K ₂ O 1.0 to 2.0 wt. MnO 0.01 to 0.03 wt. Loss on ignition 10.5 to 14.5 wt

CaO 2.5 to 4.5 wt.

3) Heavy metals

Pb max 30 ppm Cr max 10 ppm Coll max 20 ppm CD max 5 ppm

4) Cation exchange capacity 160 ± 10 milliequiv. / 100 g

5) Acid stability (by dissolved Al) at pH 3 max 50 ppm Al at pH 2,5 max 100 ppm Al

6) Accompanying minerals

No erionite traces are allowed.

The presence of fibrous minerals: asbestos, sepiolite is undesirable.

II. Organic component

An organic additive, e.g. an organic compound, is prepared as a dispersion in hot distilled water. The organic component is a quaternary amine with long carbon chains, usually dioctadecyl (dimethyl) amine, octadecyl (trimethyl) amine, octadecyl (dimethyl) benzylamine or the like are used.

The organic component is added in an amount of 0.5 to 5.0 milliquivents. / 100 g of prepared mineral component - zeolite tuff, containing at least 80% of clinoptilolite / heulandite mineral. The type of amine as well as its amount depends on

ΦΦ · φ · »φ φ φ φ φ φ φ φ · · · · φ φ · · · * · · · φ φ φ φ φ φ φ φ φ φ φ φ be adsorbed. The organomineral adsorbent is prepared according to the following example:

DETAILED DESCRIPTION OF THE INVENTION

Example 1

In the process for producing this organomineral mycotoxin adsorbent, a zeolite tuff containing at least 80% clinoptilolite / heulandite mineral by known technological processes, such as three-stage crushing to a maximum of 100 μπι, wet screening and prepared as a 20-50% slurry weight, and mixed (at least 4000 rpm) or better in a turbo mixer. After this, the activator-organic component is added in an amount of 0.5 to 5.0 milliequivents. per 100 g of mineral component dispersed in hot distilled water. The solid: liquid ratio is from 1: 1 to 1: 5.

The organic component is a long carbon chain quaternary amine, typically dioctadecyl (dimethyl) amine, octadecyl (trimethyl) amine, octadecyl (dimethyl) benzylamine or the like. The type of amine and the amount to be administered depend on the type and quantity of mycotoxins to be adsorbed.

After completion of the reaction, depending on the zeolite tuff content, the obtained suspension is filtered (20%) and the filter cake is dried directly (50%) in a box dryer at a temperature of 80 ° C to 100 ° C. After drying, the cake is ground in a knife mill up to particles below 100 µm. The product obtained is an organomineral mycotoxin adsorbent in powder form and is adjuvanted for application.

With such an organic modification of the obtained organomineral adsorbent, a well-balanced surface charge is achieved which allows adsorption of a wide spectrum of mycotoxins of different polarity. The amine is bound to the zeolite tuff by a cation exchange of naturally exchangeable cations (Ca ²⁺ ) that are found on the surface of the zeolite tuff. By having a balanced content of exchangeable cations, the organomineral mycotoxin adsorbent has a controlled surface charge and a controlled level of hydrophobicity. The organomineral mycotoxin adsorbent, which is hydrophobic, can be readily mixed into various compositions such as premixes or compound feeds. The organomineral mycotoxin adsorbent adsorbs the following mycotoxins in vitro without desorption:

% aflatoxin B1 94% zearalenone 96% ochratoxin A 82% T-2 toxin 50% DAS · · · · · · · · · · · · · · · · · · · · · · · · · % Ergosin% ergocornin 98% ergocristin 98% ergocriptin% ergotamine

The obtained organomineral mycotoxin adsorbent does not adsorb vitamins (A, D, E, group B), amino acids and does not affect the usefulness of microelements (Cu, Zn, Mn, and Co); does not adsorb P, N and Ca.

The obtained organomineral mycotoxin adsorbent, when applied in powder form, is added to the animal feed directly or via premixtures in an amount of 0.2% by weight without any harmful effects. to prevent the intoxication of mycotoxins present in animal feed. Quantity 0.2 wt. % of this mycotoxin adsorbent is sufficient to prevent intoxication of animals that consume zearalenone-containing food up to 10 mg / kg. At the same time the presence of 0.2 wt. % of this adsorbent in the compound feed has no negative effect on health and production results and could be used to prevent it. This should be emphasized because when animals are poisoned by mycotoxins, there is no method of detoxifying animals with either adsorbent or medicaments. Organomineral mycotoxin adsorbent prevents intoxication only when mycotoxin-decontaminated feed is present in the mass. This organomineral adsorbent will bind mycotoxins in the gastrointestinal tract of animals before they are resorbed because the adsorption rate of mycotoxins on the adsorbent is higher than the rate of resorption even with zearalenone, for which 50% of the initial amount has been shown to be resorbed in less than 5 minutes while 99% less than 1 hour.

In order to prevent mycotoxin intoxication, it is essential that the adsorbent be present in the animal feed as a preventive additive, since in the case of animal intoxication, eg by resorption of mycotoxins in the body, detoxification is impossible in such cases. Later addition of the organomineral adsorbent would prevent only further animal poisoning.

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Example 2 (in vivo application)

The results of the application of the organomineral adsorbent mycotoxin were obtained in three pigs on piglets (5 - 25 kg):

I. pig, number of pigs in experimental group 123 and control group 115 pigs;

II. pig, both control and experimental group - 200 pigs and

III. pig pig 35 for both groups.

In pig farms I. and II. the experimental group was fed with 0.2% organomineral adsorbent and in pig III. 0.1% adsorbent was added. The control group was fed the same feed but without adsorbent. The feed contained 5-7 mg / kg zearalenone. All other conditions were identical.

The results obtained show:

1) The presence of 0.2% organomineral adsorbent has a major effect on the health of pigs:

- the number of sick pigs in the experimental group was significantly lower than in the control group (less than 7% of pigs, less than 40% of pigs);

- the number of dead pigs was lower in the experimental group than in the control group (less than 7% of pigs, less than 66% of pigs).

2) Addition of 0.1% (pigs III) and more 0.2% (pigs I and II) of organomineral adsorbent to animal feed affects the production parameters:

- pigs with a feed containing 0,2% mineral adsorbent had a 10% increase in daily feeding (I. pig), by 4,4% in pig II. and 10.7% in pig farm III. (0.1% adsorbent);

- feed conversion in the experimental group is 14% lower (pig farm I), 4% in pig farm II. and by 2% in pig farm III.

Example 3 (in vivo application)

Studies on pigs for fattening (25-100 kg) showed an addition of 0.1% or 0.2% of an organomineral mycotoxin adsorbent in feed containing 5.5 mg / kg zearalenone.

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Both pigs, both experimental and control groups, each had 70 pigs. For the experimental group, 0.1% adsorbent was added to the feed. The feed material contained 5.2 mg / kg zearalenone.

In the Pig II. 0.2% adsorbent was added to the experimental group (122 fattening pigs) and the control group had 114 pigs. The feed material contained 5.5 mg / kg zearalenone.

In porcine I, the experimental group of pigs for fattening had a 2.36% increase in feed per day compared to the control group. Feed conversion was 2.6% lower in the experimental group. In the Pig II. the increase was 3% higher and at the same time the feed conversion was 7% lower.

Claims (3)

PATENT CLAIMS 1. Organomineral mycotoxin adsorbent as feed additive, obtained by the technological processing of a pre-prepared zeolite tuff which is inert to amino acids, vitamins, microelements and non-resorptive in the body, characterized in that a mineral component - zeolite tuff having at least 80% clinoptilolite mineral heulandite, contains an organic component from the group of long-chain quaternary amines in an amount of from 0.5 to 5 milli-equivalents per 100 g of a mineral component - zeolite tuff, having the following properties: chemical composition - SiO ₂ 63-68 wt%; Al ₂ O ₃ 11-14 wt%; Fe ₂ O ₃ 0.8 to 2.5 wt%; MnO 0.01 to 0.03 wt%; CaO 2.5 to 4.5 wt .; MgO 0.8 to 1.5 wt%; Na ₂ 0 0.8-1.5 wt%; K ₂ O 1.0 to 2.0 wt%; annealing loss of 10.5 to 14.5 wt%; heavy metals: Pb max 30 ppm; Crmax 10 ppm; Sb max 20 ppm; Cd max 5 ppm; cation exchange capacity: 160 + 10 milliequiv. / 100 g; acid stability expressed in dissolved Al: at pH 3 max 50 ppm Al; at pH 2.5 max 100 ppm Al; particle size below 100 µm, with an amine bound to the mineral component - zeolite tuff by cation exchange with naturally exchangeable cations (typically Ca ²⁺ ), which are located on the outside of the zeolite tuff; in this way, the organomineral adsorbent has a controlled surface charge and a controlled level of hydrophobicity, making it a very effective adsorbent of mycotoxins of different polarities. A process for the production of an organomineral mycotoxin adsorbent according to claim 1, wherein the zeolite tuff is pre-prepared and processed in a known manner by three-stage crushing, wet screening and suspended in water, characterized in that as a mineral component - zeolite tuff containing over 80% mineral clinoptilolite / heulandite, having a particle size below 100 µm in aqueous and a suspension of 20 to 50 wt. mixed in the reactor with a stirrer at 4000 rpm with the addition of an organic component represented by a long-chain quaternary amine such as dioctadecyl (dimethyl) amine, octadecyl (trimethyl) amine, octadecyl (dimethyl) benzylamine and the like, in an amount of 0.5 to 5.0 milliquiv. per 100 g of zeolite tuff mineral component depending on the type and amount of mycotoxins to be adsorbed, the organic component being dispersed in hot distilled water at a solid: liquid ratio of 1: 1 to 1: 5; the suspension obtained is filtered (20%), the filter cake is dried (directly dried 50%) in a box dryer at a temperature of 80 to 100 ° C up to a humidity of 10%, after which it is dried the cake is comminuted to particles below 100 µm and then adjusted in powder form as an organomineral mycotoxin adsorbent according to claim 1. Use of an organomineral mycotoxin adsorbent of various properties, having a balanced content of exchangeable cations, a controlled surface charge and a controlled level of hydrophobicity, with a broad spectrum of mycotoxin adsorption and being in powder form as feed additive, directly or in premix form, in an amount of 0.2 % wt. feed mixtures to prevent animal intoxication with mycotoxins present in the feed, without harmful effects.