RS20220887A1 - Ultrasonic low temperature synthesis of an advanced multifunctional feed additive based on highly active zinc oxide deposited on inorganic and organic carriers for application in animal feed production - Google Patents

Abstract

The process of synthesis and application of a multifunctional feed additive based on highly active ZnO and inorganic compounds and minerals and organic compounds is described, which has exceptional antimicrobial properties and shows an exceptional effect against diarrhea primarily caused by E.coli. This product also has exceptional nutritional properties as a source of zinc, as well as the ability to adsorb polar mycotoxins. The present invention relates to the ultrasonic low-temperature synthesis and application of highly active zinc oxide which is simultaneously synthesized and firmly bound to the surface of carrier micrometer particles based on natural and synthetic minerals and compounds, or zinc oxide is synthesized by ultrasonic synthesis and subsequently firmly attached to the surface by ultrasound on the supporting micrometer or submicrometer particles based on natural and synthetic minerals and compounds, such as zeolites (natural and synthetic), sepiolites, atapulgite/palygorskites, calcium carbonates and chalks, magnesium carbonates, dolomites, smectites (bentonites, montmorillonite, saponites) and other clays, diatomites, modified and unmodified cellulose and carbohydrates, already widely used and permitted for use as ad for animal feed in the EU and the PRC. These carrier particles are micrometer and/or submicrometer in size, which prevents the dispersion of active synthesized ZnO particles into the air, and also prevents the agglomeration of active ZnO particles and thus allows greater availability of active ZnO, as well as easy mixing into animal feed.

Description

ULTRASONIC LOW TEMPERATURE SYNTHESIS OF AN ADVANCED MULTIFUNCTIONAL ADDITIVE BASED ON HIGHLY ACTIVE ZINC OXIDE DEPOSITED ON INORGANIC AND ORGANIC SUPPORTS FOR APPLICATION IN ANIMAL FEED PRODUCTION

DESCRIPTION OF THE INVENTION

Technical field

The invention belongs to the field of additives for animal feed, based on highly active ZnO and inorganic compounds and minerals and organic compounds, which has exceptional antimicrobial properties and shows an exceptional effect against diarrhea primarily caused by the influence of E.coli bacteria. This product also has exceptional nutritional properties as a source of zinc, as well as the ability to adsorb polar mycotoxins, depending on the type of applied carrier particles. This invention relates to the ultrasonic low-temperature synthesis and application of highly active zinc oxide which is simultaneously synthesized on and tightly bound to the surface, or zinc oxide is synthesized and subsequently firmly bound to the surface of supporting micrometer and/or submicrometer particles based on natural and synthetic minerals and compounds, such as: zeolites (natural and synthetic), sepiolites, attapulgites/palygorskites, calcium carbonates and chalks, magnesium carbonates, dolomites, smectites (bentonites, montmorillonites, saponites) and other clays, diatomite, modified and unmodified cellulose and carbohydrates, which are already widely used and which are allowed for use as animal feed additives in the EU and the People's Republic of China. These carrier particles are micrometer and/or submicrometer in size, which prevents dispersion of active synthesized ZnO particles in the air, and also prevents agglomeration of active ZnO particles, thereby enabling greater availability of active ZnO, as well as enabling easy mixing into animal feed. The invention also belongs to the field of chemical technology and materials in a broader sense because it includes both the application and the production process for its production.

Technical problem

The technical problem that is solved by this invention is the process of ultrasonic low-temperature synthesis and production of a new antibacterial and multifunctional additive for animal feed, based on highly active zinc oxide synthesized and firmly bound on the surface of carrier particles of micrometer and/or submicrometer sizes: zeolite (natural and synthetic), sepiolite, attapulgite/palygorskite, calcium carbonate and chalk, magnesium carbonate, dolomite, smectite (bentonite, montmorillonite and saponite) and other clays, diatomite, modified and unmodified cellulose and carbohydrates, which are allowed for use as animal feed additives in the EU and the People's Republic of China. This is achieved by the production technology based on the synthesis of zinc oxide on the surface of the particles of the mentioned compounds and minerals, or the previous synthesis of zinc oxide and the binding of those particles to the surface of the mentioned compounds and minerals, by dissolving the compounds containing the Zn ion (Zn-acetate, Zn-nitrate, Zn-chloride, Zn-sulfate can be used as a source of zinc) in demineralized water, at temperatures below 90<o>C, by dispersing the carrier particles in the Zn solution at different particle concentration ranges carriers and compounds of zinc sources, during which ion exchange and adsorption of Zn ions occur on the surface of the particles, by adjusting slightly basic conditions (pH between 7 and 9) by adding a base (ammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate can be used as a base source), and by applying an ultrasonic field at frequencies equal to or greater than 20kHz using ultrasonic probes with power between 500 and 3000 W in ultrasonic flow connected reactors in a row of 1 to 4 or more pieces, in a time of 2 to 60 minutes, which synthesizes excellently dispersed zinc oxide, simultaneously synthesized at low temperatures and tightly bound on the surface of the carrier particles, or

by dissolving compounds containing the Zn ion (Zn-acetate, Zn-nitrate, Zn-chloride, Zn-sulfate can be used as a zinc source) in demineralized water, at temperatures below 90<o>C, using ultrasound and adjusting slightly basic conditions (pH between 7 and 9) by adding a base (ammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate can be used as a base source), and applying an ultrasonic field at frequencies equal to or higher than 20kHz using ultrasonic probes with a power between 500 and 3000 W in ultrasonic flow reactors connected in a row of 1 to 4 or more pieces, in a time of 2 to 60 minutes, during which zinc oxide is synthesized and by subsequent addition and dispersion of carrier particles at different concentration ranges of carrier particles and zinc oxide and additional application of an ultrasonic field at frequencies equal to or higher than 20kHz application ultrasonic probes with a power between 500 and 3000 W in ultrasonic flow reactors connected in a row of 1 to 4 or more pieces, in a time of 2 to 60 minutes, which firmly binds the ZnO particles to the carrier particles,

and thereby preventing the dispersion of active synthesized ZnO particles into the air, whereby a product with extremely high antimicrobial activity is obtained, which can be applied at the maximum permitted zinc concentration in the amount of 150 mg zinc per kilogram of animal feed in the EU, whereby the product shows excellent antimicrobial properties and a reduction in the occurrence of diarrhea, exceptional nutritional properties as a source of zinc microelements, the possibility of polar mycotoxins (alphatoxin) adsorption depending on the type of applied carrier particles, with prevented agglomeration of active ZnO particles, enabling greater availability of active ZnO, as well as easy incorporation into animal feed.

State of the art

Zinc oxide is an additive that is used in the nutrition of animals, especially piglets in the pre-starter and starter phase, in order to reduce the occurrence of diarrhea that occurs when the diet is stopped with milk and when switching to solid food, which results in the immature intestinal mucosal barrier of piglets, the absence of an immune response due to the disappearance of maternal antibodies and the action of pathogenic bacteria, primarily E.coli. The appearance of diarrhea results in slow growth and weight gain, and very often the death of piglets, which all together affects the economy of pig production and breeding. According to the European Directive (Commission implementing decision of June 26, 2017 - Directive 2001/82/EC) which applies from June 26, 2022, the content of zinc in the diet is limited to 150 mg/kg of complete food in animal nutrition (that is, it limits to the maximum allowed content of approximately 186 mg ZnO/kg of food), which is significantly lower than the previously allowed therapeutic concentration of 3000 mg ZnO/kg of complete animal feed, whereby the application of this product obtained by this invention achieves the same antimicrobial effect. In the People's Republic of China, this limit is a maximum of 110 mg Zn/kg feed. Therefore, in order to overcome the difference in effectiveness between the therapeutic dose of 3000 mg of zinc oxide and the permitted dose, it is necessary to produce far more active zinc oxide which, in doses even smaller than permitted, will show an antimicrobial effect and prevent the occurrence of diarrhea, primarily caused by the influence of E.coli bacteria, and if possible have exceptional nutritional properties as a source of zinc microelements, as well as the ability to adsorb polar mycotoxins.

In order to obtain active powders and reduce the use of zinc oxide, various physical and chemical synthesis procedures of nano zinc oxide, porous ZnO, microencapsulated ZnO, enteric coated ZnO are used. Scientific papers and patents indicate that it is possible to synthesize active ZnO nanoparticles that show high antibacterial activity that reduces the occurrence of diarrhea in piglets and improves growth performance, but on the other hand, there is always a potentially negative impact of free zinc oxide nanoparticles on human health (dusting of nanoparticles during the manipulation of workers in production), as well as the potential impact of nanoparticles on the environment.

A detailed review of the ESPACENT patent database and scientific papers dealing with this topic found the following solutions to the technical problem in the form of synthesis and properties of animal feed additives based on zinc oxide, nano zinc oxide, zinc oxide on inorganic supports, as well as for the ultrasonic synthesis of nano zinc oxide: CN113080316A, CN103549162A, CN108975384A, CN101218959A, CN109511786A, CN102335196A, KR20160100038A, US10370789B2. Some of the scientific papers and patents are described and analyzed in more detail below:

Lina Long et al, in their scientific paper "Comparison of porous and nano zinc oxide for replacing high-dose dietary regular zinc oxide in weaning piglets" (PLOS ONE, https://doi.org/10.1371/iournal.pone.0182550, August 8, 2017) examined the influence of nano and porous zinc oxide in the diet of piglets. Nano zinc oxide has shown that its application can have a positive effect on reducing the occurrence of diarrhea, as well as better utilization of zinc as a microelement, with improved growth performance, intestinal morphology, reduced occurrence of diarrhea and intestinal inflammation, as when large doses of commercial zinc oxide are used. The same authors also state that similar results are obtained using porous zinc oxide. However, it should be noted that these positive effects were obtained when using doses of 500 mg of nano and porous zinc oxide per kilogram of animal feed, which exceeds the permitted limits in the EU and the Republic of China.

CN113080316A (Preparation method of antibiotic substitute nano zinc oxide) - The cited patent document describes the preparation method of antibiotic substitute, nano zinc oxide, and the method includes the following steps: addition of surfactant to the zinc source solution, uniform mixing, continuous addition of alkaline solution, mixing, then the solution is placed in a reaction vessel under high pressure (in an autoclave), at a preset temperature and time, where after the end of the reaction, the dispersion is filtered, rinsed with deionized water and dried, at resulting in nano zinc oxide. Surface organic matter can be polymeric organic salts of weak acids and silicates, where it is used as a protective agent, so that the prepared nano-zinc oxide is not easily hydrolyzed in the stomachs of animals. According to this invention, nano zinc oxide is slowly dissolved to obtain nano-particles to ensure antibacterial effect, the reagent used has high biological safety, the prepared finished product has good quality, and nano zinc oxide is added to animal feed as a substitute for antibiotics to fill the gap in the product after the antibiotic has been banned and promote the improvement of the animal husbandry industry.

CN103549162A (Novel feed additive and preparation method thereof) - The mentioned patent document discloses a new additive for animal feed and the preparation method of a new additive for animal feed. The additive consists of an enteric coated nano zinc oxide particle, wherein the particle contains a nano zinc oxide core grain, a coating layer that passes through the small intestine, a middle layer of nano zinc oxide layer, and a coating layer that passes through the stomach from the inside out. The additive is prepared from two coatings, using nano zinc oxide and coating materials: maltodextrin, hydroxypropylmethylcellulose, ethylcellulose, acrylic resin, croscarmellose and hypromellose. The finished product is used as a feed additive for livestock and poultry to prevent diarrhea in livestock and poultry and to accelerate their growth. The additive adopts nano zinc oxide - the usable amount of nano zinc oxide is less than the commonly used amount of zinc oxide, and the effects in preventing diarrhea and accelerating growth are better than the commonly used zinc oxide due to the specific surface effect and special ionic effect of nano zinc oxide.

CN108975384A (Nanometer zinc oxide and low-temperature preparation method thereof) - The mentioned patent document discloses nanometer zinc oxide and the procedure for its synthesis at low temperatures: 4 to 6 parts of potassium salt, 3 to 4 parts of lithium salt and 2 to 3 parts of sodium salt are mixed, at a temperature of 200 to 500<o>C, where melting occurs. After the reaction has taken place, 1 to 7 parts of zinc salt are added at a temperature of 200 to 500<o>C, then stirred for a long period of time. The resulting solid molten salt is repeatedly cleaned and dried, after which a small nanometer zinc oxide is obtained. Potassium salt, lithium salt and sodium salt have the advantages that the solubility is better, the salts can be easily dissolved in water, the melting point is low, so that the prepared liquid molten salt can be mixed easily and evenly. A liquid fused salt can improve the fluidity of the reactants, and a solid formed fused salt can also separate well and thus avoid agglomeration. The method of preparation provided by the invention can be carried out under low temperature conditions, the zinc salt is directly grown by nucleation in the low temperature molten salt into nanometer zinc oxide. High temperature calcination is not required, so the process is simple. Nanometer zinc oxide prepared by this type of synthesis has a high degree of crystallinity, is uniform in size and has a large specific surface area. With this patent, however, it is obtained at higher temperatures up to 500<o>C.

CN101218959A (Application of nano-zinc oxide as animal feed additives) - This patent proposes a new use of nano-zinc oxide as animal feed additives. As a source of zinc, nanometer zinc oxide has the advantages of high bioavailability, low additive dosage, and hardly reacts with other components. As a feed supplement, nanometer zinc oxide can effectively meet the demand of animals for a source of zinc, promote healthy animal growth, improve feed efficiency, effectively reduce the occurrence of diarrhea in piglets. With a small usage dose, the invention reduces environmental contamination caused by animal excrement. Nanometer zinc oxide promotes growth, improves feed efficiency, replaces antibiotics, eliminates antibiotic residues in animal products, reduces environmental pollution. Although this patent indicates that its application reduces environmental contamination caused by animal excrement, it does not indicate the possibility of endangering human health by possible inhalation of nanoparticles during application, nor the possibility of impacting the environment during product manipulation. It is also not indicated to solve the problem of nanoparticle agglomeration and interference in animal feed.

CN109511786A (Feed additive containing zinc oxide and preparation method of feed additive) - The cited patent describes a feed additive containing zinc oxide and the preparation method of feed additive. The additive is prepared from the components in parts by weight: 400-820 parts of zinc oxide, 100-400 parts of carrier dispersed in water and 80-200 parts of coating fat. Zinc oxide is evenly dispersed on a water-soluble dispersible carrier and then coated with enteric coating ointment. When the food additive is prepared, the dispersible carrier of the prescribed dose is heated and dissolved, then the zinc oxide powder is added, then sufficiently mixed, allowing the zinc oxide to be evenly dispersed on the dispersible carrier, then cooled and then the pellets or particles containing zinc oxide are prepared. The prepared zinc oxide pellets or particles are fed into the enteric coating equipment, the melted fat is sprayed into the coating equipment to perform the enteric coating, after which the feed additive is obtained. For food additives containing zinc oxide, the cost of raw materials is low, the absorption capacity of zinc oxide is high, the absorption effect in the stomach is good, and the release in the intestines is satisfactory.

CN102335196A (Use of supported nano zinc oxide as anti-diarrhea agent for weaned pigs and using method) - The mentioned patent discloses the use of supported nano zinc oxide as an anti-diarrhea agent for piglets and the method of use. Supported zinc oxide, which is used as a means to prevent diarrhea for oversaturation, is a composite material for supporting nano zinc oxide using kaolin or montmorillonite or attapulgite or sepiolite or zeolite as a carrier. Zinc oxide makes up from 10 to 50 percent by weight of the composite material used as a nano zinc oxide carrier. Methods of using supported nano zinc oxide as an antidiarrheal agent for piglets include adding 160 to 800 mg/kg of supported zinc in the form of zinc oxide to piglet feed. Supported nano zinc oxide can significantly reduce the incidence of diarrhea in weaned pigs, improve daily gain, improve the shape of the intestinal mucosa and protect the intestinal mucosa barrier. Pig skin is red and bright, and the effect of supported zinc oxide exceeds the effect of using high-dose commercial zinc oxide, thus zinc oxide consumption is significantly reduced, as well as zinc excretion and environmental pollution. However, the author states that this product contains nano ZnO, where the content of applied zinc oxide is in the range of 10-50%, and that it is added to food to have anti-diarrheal properties in doses of 160 to 800 mg Zn/kg of food, which represents concentrations that exceed the permitted values in the EU and the Republic of China. Also, each of the syntheses of nano ZnO that the author cites in his patent, are syntheses of other authors, which involve subsequent high-temperature treatment at temperatures up to 500<o>C. The author states that the particles are uniformly deposited on the supports, that agglomeration and stability are prevented, but he does not mention that the particles are tightly bound to the surface, which may result in the dispersion of ZnO nanoparticles into the environment during manipulation, and thus an impact on the health of workers and the environment.

KR20160100038A (Method for preparing zinc oxide nanoparticle having porous shell and hollow core by using ultrasonic irradiation) - The cited patent relates to a process for preparing zinc oxide nanoparticles, which includes the steps: (a) dissolving the zinc precursor in a solvent, including dimethyl sulfoxide, to obtain a zinc precursor solution and (b) subjecting the zinc precursor solution obtained from step (a) to ultrasonic irradiation, in order to obtained zinc oxide nanoparticles. The method uses water harmless to the human body and an environmentally friendly solvent, DMSO, and involves a simple process of ultrasonic irradiation in a container. With this method, it is possible to obtain zinc oxide nanoparticles with a high surface area in a highly cost-effective way that does not require a separate cooling system, heating unit and post-processing process. In addition, the obtained zinc oxide nanoparticles have a porous-hollow structure, including many surface pores and a large hollow core, and therefore have a surface area of 30 m<2>/g, significantly improved compared to the 10 m<2>/g surface area of zinc oxide nanoparticles obtained by a related technique. This is the reason for their application in various industrial fields, such as photovoltaic material for solar cells or as a cosmetic material. Therefore, the author of the patent does not state the application as an additive in animal feed, nor as an antimicrobial supplement, nor as a source of Zn.

US10370789B2 (Sonochemical coating of textiles with metal oxide nanoparticles for antimicrobial fabrics) - The mentioned patent refers to a system for the preparation of antimicrobial surfaces coated with metal oxide nanoparticles using a new sonochemical method. These antibacterial surfaces are widely used in medical and other applications. The deposition of metal oxides known to have an antimicrobial effect, namely ZnO, MgO and CuO, can significantly expand the application of textile fabrics, medical devices and other items and significantly extend the period of their use. Using the new sonochemical method disclosed here, uniform deposition of metal oxide nanoparticles is easily achieved. The inventors base this patent on their previous research published in scientific papers such as: The Preparation of Metal - Polymer Composite Materials using Ultrasound Radiation, S. Wizel, R. Prozorov, Y. Cohen, D. Aurbach, S. Margel, A. Gedanken. J. Mater. Res. 13, (1998) 211; Preparation of amorphous magnetite nanoparticles embedded in polyvinylalcohol using ultrasound radiation". R. Vijaykumar, Y. Mastai, A. Gedanken, Y. S. Cohen, Yair Cohen, D. Aurbach, J. Mater. Chem.10 (2000) 1125; Sonochemical Deposition of Silver Nanoparticles on Silica Spheres V. G. Pol, D. Srivastava, O. Palchik, V. Palchik, M. A. Slifkin, A. M. Weiss, A. Gedanken, 18, (2002) 3352; Synthesis and Characterization of Zinc Oxide -PVA Nanocomposite by Ultrasound Irradiation" R. Vijayakumar, R. Elgamiel, O. Palchik, A. Crystal Growth and Design, 250 (2003) Sonochemical Deposition of Silver Nanoparticles on Wool Fibers. L. Haddad, N. Perkas, Y. Gofer, J. Calderon-Moreno, A. Ghule, A. Gedanken. J. Appl. Polym. Sci.104 (2007) 1732. Although these papers and patents study the deposition of different nanoparticles on different substrates using the ultrasound-sonochemical method, they do not consider obtaining either antimicrobial additives for animal feed, or as a source of zinc or a mycotoxin adsorbent, and they do not consider the deposition of zinc oxide on said particles based on natural and synthetic minerals and compounds, such as: zeolites (natural and synthetic), sepiolites, attapulgites/palygorskites, calcium carbonates and chalks, magnesium carbonates, dolomites, smectites (bentonites, montmorillonites, saponites) and other clays, diatomite, modified and unmodified cellulose and carbohydrates, which are already widely used and which are allowed for use as feed additives.

Presentation of the essence of the invention

European feed legislation, according to the European Directive (Commission implementing decision of June 26, 2017 - Directive 2001/82/EC) limits total dietary Zn to a maximum concentration of 150 mg/kg of complete feed - it is limited to 186 mg/kg of zinc oxide per kilogram of feed, which is much below the therapeutic dose of 3000 mg/kg of feed used as an additive for feed.

This invention relates in one part to a multifunctional feed additive based on highly active zinc oxide synthesized and firmly bound on the surface of particles based on natural and synthetic minerals and compounds, such as: zeolites (natural and synthetic), sepiolites, attapulgites/palygorskites, calcium carbonates and chalks, magnesium carbonates, dolomites, smectites (bentonites, montmorillonites, saponites) and other clays, diatomite, modified and unmodified cellulose and carbohydrates, which are already widely used and which are allowed for use as animal feed additives, which shows exceptional antimicrobial properties against the E.coli bacteria, as well as the ability to prevent diarrhea in piglets, and is also an additive that shows nutritional properties as a source of zinc and the possibility of adsorbing polar mycotoxins such as alphatoxins, depending on the type of applied carrier particles.

In the second part, this invention relates to the production technology of highly active zinc oxide, which is realized by the production technology based on ultrasonic or sonochemical low-temperature synthesis of zinc oxide on the surface of the particles of the mentioned compounds and minerals, i.e. the synthesis of highly active zinc oxide and its binding to the surface of the carrier particles.

Disadvantages of the application of known solutions indicated in the State of the art chapter consist in the fact that zinc oxide nanoparticles are used, which are either synthesized at elevated temperatures, or are used in concentrations higher than 160 mg Zn per kilogram of food, which exceeds the permitted values in the EU and the People's Republic of China. Also indicated patent solutions do not show multifunctional properties, as well as that some do not indicate the prevention of possible dispersion of ZnO nanoparticles into the environment during product manipulation and thus the impact on the health of workers by inhalation and the impact on the environment. Further, some patent solutions do not indicate solving the problem of agglomeration of nanoparticles and the possibility of mixing ZnO nanoparticles in animal feed, as well as some solutions do not show the possibility of application as an additive in animal feed, but of application in photocatalysis, photonic systems or the application of antimicrobial properties in textile applications.

The advantage of this invention compared to the prior art:

- The application of an ultrasonic field, i.e. a sonochemical procedure, enables the simultaneous or successive synthesis of highly active zinc oxide and its firm binding to the surface of the carrier particle;

- Application of ultrasonic field and sonochemical reaction enables low temperature synthesis of ZnO at temperatures below 90<o>C

- Carrier particles used in food production and permitted for use on which ZnO is synthesized are used,

- Carrier particles that are micrometer and/or submicrometer in size prevent dispersion of active synthesized active ZnO particles into the air

- The agglomeration of active ZnO particles is prevented and thus the greater availability of active ZnO is enabled - It is possible to easily mix additives into animal feed

- The product produced in this way shows excellent antimicrobial properties and a reduction in the occurrence of diarrhea in the maximum allowed concentration of 150 mg Zn per kg of food in the EU, exceptional nutritional properties as a source of zinc microelements, as well as the possibility of polar mycotoxins (alphatoxins) adsorption depending on the type of applied carrier particles.

Detailed description of the invention

This invention describes the production technology of highly active zinc oxide, which is realized by the production technology based on ultrasonic or sonochemical low-temperature synthesis of zinc oxide on the surface of particles based on natural and synthetic minerals and compounds, or the previous synthesis of zinc oxide and its binding to the surface of carrier particles of said compounds and minerals, such as: zeolites (natural and synthetic), sepiolites, attapulgites/palygorskites, calcium carbonates and chalks, magnesium carbonates, dolomites, smectites (bentonites, montmorillonites, saponites) and other clays, diatomite, modified and unmodified cellulose and carbohydrates, which are already widely used and which are allowed for use as feed additives.

The synthesis itself consists in dissolving and mixing compounds containing the Zn ion, where Zn-acetate, Zn-nitrate, Zn-chloride, Zn-sulfate can be used as a source of zinc, in demineralized water preheated at temperatures from 30 to 90<o>C. Then, with stirring, a certain amount of carrier particles is added to the Zn solution, and the dispersion is stirred for 30 seconds to 60 minutes in order to perform ion exchange in the crystal lattice, i.e. adsorption of zinc ions on the surface of the carrier particles, using different concentration ranges of carrier particles and zinc source compounds. Then, the dispersion-solution is passed through an ultrasonic field for the purpose of better homogenization for 2 to 30 minutes. Then, with mixing, a base is added for up to 5 minutes until slightly basic pH conditions between 7 and 9 are reached, where ammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate can be used as a base source. Then the solution-dispersion is pumped through ultrasonic flow reactors with probes, where by applying an ultrasonic field at frequencies equal to or greater than 20kHz power between 500 and 3000 W bound in a row of 1 to 4 or more pieces, in a time of 2 to 60 minutes, excellently dispersed zinc oxide and firmly bound on the surface of the carrier particles is synthesized.

The synthesis can also take place in another way, by dissolving and mixing compounds containing the Zn ion, where Zn-acetate, Zn-nitrate, Zn-chloride, Zn-sulfate can be used as a source of zinc, in demineralized water preheated at temperatures from 30 to 90<o>C. Then the solution is passed through an ultrasonic field for better homogenization for 2 to 30 minutes. Then, with mixing, a base is added for up to 5 minutes until slightly basic pH conditions between 7 and 9 are reached, where ammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate can be used as a base source. Then the solution is pumped through ultrasonic flow reactors with probes, where by applying an ultrasonic field at frequencies equal to or greater than 20kHz power between 500 and 3000 W tied in a row of 1 to 4 or more pieces, in a time of 2 to 60 minutes, perfectly dispersed zinc oxide is synthesized. Then, with stirring, a certain amount of carrier particles is added to the Zn solution, and the dispersion is mixed for 30 seconds to 60 minutes, using different concentration ranges of carrier particles and synthesized zinc oxide. Then this dispersion is additionally treated by applying an ultrasonic field at frequencies equal to or higher than 20kHz using ultrasonic probes with a power between 500 and 3000 W in ultrasonic flow reactors connected in a row of 1 to 4 or more pieces, in a time of 2 to 60 minutes, which firmly binds the ZnO particles to the carrier particles.

After ultrasonic treatment, the dispersion can be separated from the liquid phase and dried in several ways: - passing through a filter press, washing with demineralized water and after removing the filter cake, the filter cake is dried in a dryer and then deagglomerated in different types of dispersers or mills; - by filtration through strip or drum vacuum filters where the solid phase is separated from the liquid phase and washed with demineralized water, and then dried on flash-dryers where the product is dried and asked at the same time; - spraying in spray dryers, where the product is dried and granulated at the same time.

In this way, a product is obtained in which the active synthesized ZnO particles are prevented from dispersing into the air, with extremely high antimicrobial activity, which can be applied at the maximum permitted zinc concentration in the amount of 150 mg of zinc per kilogram of animal feed in the EU, where the product shows excellent antimicrobial properties and reduction of the occurrence of diarrhea, exceptional nutritional properties as a source of zinc microelements, which shows the possibility of adsorption of polar mycotoxins (alphatoxins) depending on the type of applied carrier particles, and which due to prevented agglomeration of active ZnO particles enables greater availability of active ZnO, as well as easy mixing in animal feed.

The invention is illustrated, but not limited, by the following examples, which those skilled in the art should not consider limiting the claims.

Example 1.

In 100 ml of demineralized water, heated to 60<o>C, 0.5 g of Zn-acetate dihydrate was dissolved with stirring and then 5 g of natural zeolite (with over 70% clinoptilolite mineral content and particle size below 40 micrometers) was added for 5 minutes. The solution-dispersion was then exposed to an ultrasonic field (20kHz, 100W/cm<2>) for 5 minutes. After that, about 0.15 ml of ammonium hydroxide (concentration 25-30%) was added until slightly basic conditions of pH 8.5 were reached. The dispersion was again treated with an ultrasonic probe for 5 minutes. The dispersion is then filtered, washed with deionized water, and the filter cake is then dried at temperatures from 100 to 150<o>C for an hour and lightly crushed in an oven, resulting in highly active ZnO powder deposited and tightly bound on natural zeolite particles.

Example 2.

In 100 ml of demineralized water, heated to 60<o>C, 0.5 g of Zn-acetate dihydrate was dissolved with stirring and then 5 g of natural sepiolite clay (with about 40 to 50% sepiolite minerals and 20 to 30% smectite minerals and particle size below 40 micrometers) was added for 5 minutes. The solution dispersion was then exposed to an ultrasonic field (20kHz, 100W/cm<2>) for 5 minutes. After that, ammonium hydroxide (concentration 25-30%) was added until slightly basic conditions of pH 8.5 were reached. The dispersion was again treated with an ultrasonic probe for 5 minutes. The dispersion is then filtered, washed with deionized water, and the filter cake is then dried at temperatures from 100 to 150<o>C for an hour and lightly crushed in a mortar, resulting in highly active ZnO powder deposited and firmly bound on sepiolite clay particles.

Example 3.

100 l of demineralized water, heated to 60<o>C, was poured into a 150 l stirred and heated reactor, 500 g of Zn-acetate dihydrate was dissolved with stirring, and then 5 kg of natural zeolite (with over 70% clinoptilolite mineral content and particle size below 40 micrometers) was added for 5 minutes. The solution-dispersion was then exposed to an ultrasonic field with two sequentially connected flow ultrasonic probes (20kHz and power 1000W each) in an ultrasonic reactor for 10 minutes. After that, about 180 ml of ammonium hydroskide (concentration 25-30%) was added until slightly basic conditions of pH 8 were reached with stirring for 2 minutes. The dispersion was again treated with ultrasonic probes for 20 minutes. The dispersion was then filtered through a laboratory filter press, the filter cake was rinsed with deionized water in the filter press, and the filter cake was then dried at temperatures from 100 to 150<o>C for two hours and lightly crushed in a mortar, resulting in highly active ZnO powder deposited and tightly bound on natural zeolite particles.

Example 4.

In 200 ml of demineralized water, heated to 60<o>C, 2 g of Zn-acetate dihydrate was dissolved with stirring and then 10 g of CaCO<3> (Omya GCC with particle size below 4 micrometers) was added with stirring for 5 minutes. The solution-dispersion was then exposed to an ultrasonic field (20kHz, 100W/cm<2>) for 5 minutes. After that, ammonium hydroxide (concentration 25-30%) was added until slightly basic conditions of pH 8 were reached. The dispersion was again treated with an ultrasonic probe for 5 minutes. The dispersion is then filtered, washed with deionized water, and the filter cake is then dried at temperatures from 100 to 150<o>C for an hour and lightly crushed in an oven, resulting in highly active ZnO powder deposited and firmly bound on CaCO3 particles.

Example 5.

In 200 ml of demineralized water, heated to 60<o>C, 7.2 g of Zn-acetate dihydrate was dissolved with stirring and then 15 g of natural zeolite (with over 70% clinoptilolite mineral content and particle size below 40 micrometers) was added with stirring for 5 minutes. The solution-dispersion was then exposed to an ultrasonic field (20kHz, 100W/cm<2>) for 3 minutes. After that, about 4 ml of ammonium hydroxide (concentration 25-30 %) was added until slightly basic conditions of pH 8.5 were reached. The dispersion was again treated with an ultrasonic probe for 5 minutes. The dispersion is then filtered, washed with deionized water, and the filter cake is then dried at temperatures from 100 to 150<o>C for an hour and lightly crushed in an avan, resulting in a more concentrated highly active ZnO powder deposited and tightly bound on natural zeolite particles.

Example 6.

In 100 ml of demineralized water, heated to 60<o>C, 7.2 g of Zn-acetate dihydrate was dissolved with stirring and then 15 g of synthetic zeolite 4A (Alumina BiH with a particle size below 4 micrometers) was added with stirring for 5 minutes. The solution-dispersion was then exposed to an ultrasonic field (20kHz, 100W/cm<2>) for 3 minutes. After that, ammonium hydroxide (concentration 25-30%) was added until slightly basic conditions of pH 7.5 were reached. The dispersion was again treated with an ultrasonic probe for 5 minutes. The dispersion was then filtered, washed with deionized water, and the filter cake was then dried at temperatures from 100 to 150<o>C for an hour and lightly crushed in an oven, resulting in a more concentrated highly active ZnO powder deposited and firmly bound on the particles of synthetic zeolite 4A.

Example 7.

10 l of demineralized water, heated to 60<o>C, was poured into a 20 l stirred reactor, 1456 g of Zn-acetate dihydrate was dissolved with stirring, and then 3 kg of synthetic zeolite 4A (Alumina BiH with a particle size below 4 micrometers) was added for 10 minutes. The solution-dispersion was then exposed to an ultrasonic field with two sequentially connected flow ultrasonic probes (20kHz and power 1000W each) in an ultrasonic reactor for 10 minutes. After that, ammonium hydroxide (concentration 25-30%) was added until slightly basic conditions of pH 8 were reached with stirring for 2 minutes. The dispersion was again treated with ultrasonic probes for 10 minutes. The dispersion was then filtered through a laboratory filter press, the filter cake was washed with deionized water in the filter press, and the filter cake was then dried at temperatures from 100 to 150<o>C for two hours and lightly crushed in an avan, whereby a concentrated highly active ZnO powder was obtained deposited and firmly bound on the particles of synthetic zeolite 4A.

Example 8.

50 l of demineralized water heated to 60<o>C was poured into a 100 l stirred reactor, 675 g of Zn-acetate dihydrate was dissolved with stirring for 5 minutes. The solution was then exposed to an ultrasonic field in an ultrasonic probe (20kHz and power 1000W) in an ultrasonic reactor for 5 minutes. After that, ammonium hydroxide (concentration 25-30%) was added until slightly basic conditions of pH 8 were reached with stirring for 2 minutes. The dispersion was again treated with an ultrasonic probe for 40 minutes. 3 kg of natural zeolite was then added to the dispersion, with mixing with a mechanical mixer, and then the dispersion was treated again with an ultrasonic probe for 15 minutes. The dispersion was then filtered through a laboratory filter press, the filter cake was washed with deionized water in a filter press, and the filter cake was then dried at temperatures from 100 to 150<o>C for two hours and gently deagglomerated in a mill, whereby a concentrated highly active ZnO powder deposited and tightly bound on natural zeolite particles was obtained.

Example 9.

45 l of demineralized water heated to 60<o>C was poured into a 100 l stirred reactor, 880 g of Zn-acetate dihydrate was dissolved with stirring for 5 minutes. The solution is then exposed to an ultrasonic field in an ultrasonic probe (20kHz and power 1000W each) in an ultrasonic reactor for 5 minutes. After that, ammonium hydroxide (concentration 25-30%) was added until slightly basic conditions of pH 8 were reached with stirring for 2 minutes. The dispersion was again treated with an ultrasonic probe for 40 minutes. 2.2 kg of CaCO3 was then added to the dispersion, while stirring with a mechanical stirrer, and then the dispersion was again treated with an ultrasonic probe for 10 minutes. The dispersion was then filtered through a laboratory filter press, the filter cake was washed with deionized water in the filter press, and the filter cake was then dried at temperatures from 100 to 150<o>C for two hours and gently deagglomerated in a mill, whereby a concentrated highly active ZnO powder deposited and firmly bound on CaCO3 particles was obtained.

Method of industrial or other application of the invention

As described according to the invention, the procedure for obtaining a multifunctional additive based on highly active zinc oxide deposited on inorganic and organic compounds and minerals by low-temperature ultrasonic synthesis and its application for the production of animal feed is relatively simple and affordable for production and application in industry, whereby a product with exceptional multifunctional properties is obtained, which is easily mixed into animal feed, which is an advantage in mass food production.

Claims (10)

Patent claims 1. Multifunctional feed additive based on highly active zinc oxide deposited on inorganic and organic compounds and minerals, characterized by the fact that it is produced by low-temperature ultrasonic synthesis. 2. The multifunctional food additive described in claim 1, characterized by the fact that the multifunctionality is reflected in simultaneous antibacterial properties in order to prevent diarrhea, a source of zinc as a microelement and the possibility of adsorption of polar mycotoxins such as alphatoxin depending on the type of applied carrier particles. 3. Inorganic and organic compounds and minerals described in claim 1, characterized by the fact that they represent carrier particles of micrometer and/or submicrometer sizes consisting of the following compounds and minerals: zeolites (natural and synthetic), sepiolites, attapulgites/palygorskites, calcium carbonates and chalks, magnesium carbonates, dolomites, smectites (bentonites, montmorillonites, saponites) and other clays, diatomite, modified and unmodified cellulose and carbohydrates, which are already widely used and which are allowed for use as feed additives. 4. As a chemical compound for the synthesis from claim 1, characterized in that Zn-acetate, Zn-nitrate, Zn-chloride, Zn-sulfate in different concentrations can be used as a source of zinc. 5. As a chemical compound for the synthesis from claim 1, characterized in that ammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate can be used as a source of base to change the pH value of the solution. 6. Low-temperature ultrasonic synthesis from claims 1, 3, 4 and 5, indicated by the fact that the synthesis consists in dissolving with stirring the compounds containing the Zn ion in demineralized water preheated at temperatures from 30 to 90<o>C, in which, after dissolving with stirring, a certain amount of carrier particles is added, and the dispersion is stirred for 30 seconds to 60 minutes in order to carry out ion exchange in crystal lattice, i.e. adsorption of zinc ions on the surface of the carrier particles, using different concentration ranges of the carrier particles and zinc source compounds, and then the dispersion-solution is passed through ultrasonic reactors with probes for better homogenization for 2 to 30 minutes, to which a base is added with stirring for up to 5 minutes until slightly basic pH conditions between 7 and 9 are reached, and then the solution-dispersion is circulated by a pump through the ultrasonic flow reactors with probes where the application of an ultrasonic field at frequencies equal to or greater than 20kHz power between 500 and 3000 W bound in a row of 1 to 4 or more pieces, in a time of 2 to 60 minutes, synthesizes excellently dispersed zinc oxide and firmly bound on the surface of the carrier particles. 7. Low-temperature ultrasonic synthesis from claims 1, 3, 4 and 5, indicated by the fact that the synthesis consists in dissolving with mixing the compounds containing the Zn ion in demineralized water preheated at temperatures from 30 to 90<o>C, the solution is then treated with an ultrasonic field in ultrasonic probes for 1 to 10 minutes, and then a base is added with stirring for up to 5 minutes until a slight basic pH conditions between 7 and 9, and then the dispersion is pumped through ultrasonic flow reactors with probes, where using an ultrasonic field at frequencies equal to or greater than 20kHz power between 500 and 3000 W, tied in a row of 1 to 4 or more pieces, in a time of 2 to 60 minutes, zinc oxide is synthesized, and after that, carrier particles are added to the zinc oxide dispersion with mixing, whereby use different ranges of carrier particle concentrations and of synthesized zinc oxide, and then the dispersion of zinc oxide and the carrier is pumped through ultrasonic flow reactors with probes, where by applying an ultrasonic field at frequencies equal to or greater than 20kHz power between 500 and 3000 W, tied in a row of 1 to 4 or more pieces, in a time of 2 to 60 minutes, well-dispersed zinc oxide is firmly attached to the surface of the carrier particles. 8. Synthesized highly active zinc oxide deposited on inorganic and organic compounds and minerals from claims 1, 3, 4, 5, 6, 7, characterized by the fact that after ultrasonic synthesis, the dispersion is separated from the liquid phase and dried in several ways, by passing through a filter press, washed with demineralized water and after removing the filter cake, the filter cake is dried in a dryer and then dispersed in different types of dispersers or mills. or the dispersion is separated by filtration through strip or drum vacuum filters where the solid phase is washed with demineralized water and then dried in flash-dryers where the product is dried and asked at the same time, or the dispersion is dried by spraying in spray dryers where the product is dried and granulated at the same time. 9. Multifunctional additive for animal feed based on highly active zinc oxide deposited on inorganic and organic compounds and minerals from requirements 1, 2, 3, indicated by the fact that it can be applied up to the maximum permitted concentration of 150 mg zinc per kilogram of animal feed in the EU, whereby the product shows excellent antimicrobial properties and reduction of the occurrence of diarrhea, exceptional nutritional properties as a source of zinc microelements, which shows the possibility of adsorption of polar mycotoxins (alphatoxin) depending on the type of applied carrier particles. 10. Multifunctional additive for animal feed based on highly active zinc oxide deposited on inorganic and organic compounds and minerals from claims 1, 2, 3, 6, 7, 9, characterized in that the carrier particles are of micrometer and/or submicrometer size, which makes it difficult to disperse active synthesized ZnO particles in the air, that there is no agglomeration of active ZnO particles, which enables greater availability of active ZnO, as well as easy mixing in food for animals.