RU2304397C1 - Method for producing of feed additive (versions) and feed additive (versions) - Google Patents

Abstract

FIELD: production of feed additives which may be used as biologically active feed additives in poultry farming, animal farming, fur farming, and fish industry.

SUBSTANCE: method involves processing extracts of coniferous greens; performing microgranulation of neutralized coniferous greens extract using water-soluble polymeric matrix-binder in the form of aqueous solution and combining said matrix-binder with said extract; introducing drops of resultant mixture into aqueous solution of cross-linking agent; using sodium alginate or complex of protein-anion polysaccharide consisting of gelatin and sodium alginate as polymeric matrix-binder, and water-soluble calcium salts as cross-linking agent providing production of water-insoluble matrix of microgranules. Dried granules produced contain the following components, wt% (on conversion to dry substance): coniferous greens extracts 70-90; polymeric matrix-binder 9-25; cross-linking agent (on conversion to calcium ion Ca²⁺) 0.04-0.10. According to another version of method and version of feed additive produced by method, polymeric matrix-binder is complex of protein-anion polysaccharide containing gelatin and sodium alginate, and cross-linking agent contains water-soluble ferric salts providing production of water-insoluble microgranules matrix. Resultant dried granules contain the following components, wt% (on conversion to dry substance): coniferous greens extracts 70-90; polymeric matrix-binder 9-25; cross-linking agent (on conversion to iron ion Fe³⁺) 0.05-0.5.

EFFECT: simplified process and reduced costs for producing of feed additive.

9 cl, 3 tbl, 11 ex

Description

The invention relates to the field of obtaining feed additives and can be used as biologically active feed additives in diets in poultry, livestock, fur farming, fish farming.

A known method of producing products from wood coniferous herbs, for example, natural coniferous extract, chlorophyll-carotene paste and coniferous vitamin flour (RU 2041646, A23K 1/00, 1992.12.30). The method provides a two-stage extraction of green wood fir and pine. This increases the yield of extractive substances, while preserving biologically active substances from destruction, and allows more efficient use of waste wood greens.

The obtained extracts can be further used in the diets of birds, animals, fur animals.

A known method of processing coarse plant materials, in particular needles, into highly nutritious feeds with a high protein content (RU 2088106, A23K 1/12, 1995.03.24). The essence of the method is as follows. The coniferous-branch mass (HVM) is crushed into particles 5 × (4-6) cm in size, then it is processed in a dispersant plant for 7-10 minutes, separated into phases, the solid phase of the HVM is inoculated with the fungus strain Pleurotus ostreatus (Fr), cultivation lead for 16 days.

However, the coniferous feed additive has a specific coniferous smell and an unpleasant burning taste, which must be masked so that animals can consume these substances without hindrance. In addition, the problem is the dosage of pasty substances and their uniform distribution in dry feed, given their viscous consistency.

In order to mask the smell and taste of coniferous herbs extracts, as well as for the convenience and uniformity of their dosage at low concentrations, microencapsulation of these products was carried out.

It is known to microencapsulate extracts of coniferous herbs (RU No. 2021736, 1993.07.15, A23K 1/00, 1/14) in a shell containing gelatin and tanning agent, in the following ratio of ingredients, wt.%: Coniferous herb extract 75.0-92.0 , gelatin 5.0-20.0, tanning agent 0.5-5.0.

In this patent, the water-insoluble product of the extraction of coniferous greens with the help of organic solvents (gasoline) is used as the main biologically active substance (BAS) after separation of waxes from the extracts and removal of the solvent and essential oils. Microencapsulation is carried out by forming in an aqueous medium a shell of a water-soluble polymer - gelatin on the surface of the particles (core) of coniferous green concentrate, previously dispersed in an aqueous medium to a size of 100-2000 microns. This is followed by the steps of tanning the shell, washing the capsules, isolating the microcapsules, and drying. The resulting microencapsulated preparation is stable in the acidic environment of gastric juice, but is easily hydrolyzed in the alkaline intestinal environment, where the absorption of biologically active substances occurs. This drug is effective, as shown by examples of improving the quality of skin products on minks, as well as on increasing the growth of meat products in chickens.

However, the known method, despite the positive result from the use of microencapsulation, has a number of significant limitations and disadvantages:

- the technological process is expensive due to its multi-stage and duration of stages in time;

- the presence of a large amount of wastewater that requires disposal, since they cannot be reused;

- a large variation in the basic physical and chemical parameters of the raw material (due to seasonality, the nature of the raw material and the area of growth), which requires constant adjustment of the process at the stages of emulsion formation and the formation of microcapsule shells.

The objectives of the present invention are to address the above disadvantages of the technological process of obtaining a feed additive.

The tasks are solved as follows.

Option 1. A method of obtaining a feed additive includes processing extracts of coniferous herbs and differs in that microgranulation of a neutralized extract of coniferous herbs is carried out using a water-soluble polymer matrix binder in the form of an aqueous solution, which is combined with the above extract, and then the resulting mixture is introduced dropwise into an aqueous solution a cross-linking agent, while sodium alginate or a protein-anionic polysaccharide-type complex consisting of gelatin and sodium alginate, and as a cross-linking agent, water-soluble calcium salts (calcium ions) are used to provide an insoluble matrix of microgranules, and the obtained dried granules contain the following components, wt.% (in terms of dry matter):

Coniferous extracts 70-90 Polymer matrix binder 9-25 Crosslinking agent (in terms of calcium ion Ca ²⁺ ) 0.04-0.10

Option 2. A method of obtaining a feed additive includes processing extracts of coniferous herbs and differs in that microgranulation of a neutralized extract of coniferous herbs is carried out using a water-soluble polymer matrix binder in the form of an aqueous solution, which is combined with the above extract, and then the resulting mixture is introduced dropwise into an aqueous solution a crosslinking agent, while a protein-anionic polysaccharide complex consisting of gelatin and alginate is used as a polymer matrix binder sodium, and as the crosslinking agent are water-soluble salts of iron (iron ions), providing the obtainment of an insoluble matrix of microgranules, wherein the obtained dried granules contain the following components, mass% (based on dry substance).:

Coniferous extracts 70-90 Polymer matrix binder 9-25 Crosslinking agent (in terms of iron ion Fe ³⁺ ) 0.05-0.50.

The feed additive obtained by the method of option 1 contains a biologically active substance - extracts of coniferous herbs and is characterized in that it contains the following components, wt.% (In terms of dry matter):

Coniferous extracts 70-90 Polymer matrix binder 9-25 Crosslinking agent (in terms of calcium ion Ca ²⁺ ) 0.04-0.10.

In addition, the polymer matrix binder contains sodium alginate or sodium alginate with gelatin, in the following ratio of components, wt.%:

Sodium Alginate 9-25 Gelatin 0-10

and as a crosslinking agent, water-soluble or partially water soluble calcium salts.

In addition, the polymer matrix binder contains sodium alginate or sodium alginate with gelatin, taken in a mass ratio of 4: 1 to 3: 2.

In addition, water-soluble or partially water-soluble salts of calcium and various inorganic acids — calcium dichloride, calcium glycerophosphate, as well as organic acids such as aliphatic, such as calcium acetate, hydroxy acids, for example lactic, gluconic, are used as a source of calcium ions of Ca ²⁺ aromatic, for example, benzoic, salicylic, acetyl-o-salicylic, in the concentrations necessary to ensure that in the bath with a solution of a crosslinking agent the concentration of calcium ions Ca ²⁺ in the range of 0.4-1.0 wt.%.

The feed additive obtained by the method of option 2 contains a biologically active substance - extracts of coniferous herbs and is characterized in that it contains the following components, wt.% (In terms of dry matter):

Coniferous extracts 70-90 Polymer matrix binder 9-25 Crosslinking agent (in terms of iron ion Fe ³⁺ ) 0.05-0.50

In addition, the polymer matrix binder contains sodium alginate with gelatin, taken in a mass ratio of 4: 1 to 3: 2, in the following ratio of components, wt.%:

Sodium Alginate 6-18 Gelatin 2-12,

and as a crosslinking agent, water-soluble or partially water soluble iron salts.

In addition, water-soluble or partially water-soluble salts of iron and inorganic acids, for example, hydrochloric, sulfuric, including mixed salts of the type of alum, are used as a source of iron ions Fe ³⁺ in the concentrations necessary to provide the concentration in the bath with a solution of a crosslinking agent iron ions Fe ³⁺ in the range of 0.5-5.0 wt.%.

In the proposed method as extracts of coniferous herbs can be used extracts obtained from herbs of various coniferous species using different extractants. The obtained extracts are converted into a water-soluble form by neutralizing them with an aqueous solution of sodium hydroxide to a pH of 8-10 and thereby turning them into water-containing pastes. The main ingredients for the feed additive in these pastes are chlorophyll and chlorophyll derivatives, carotene and carotenoids, flavanoids, polyprenols, as well as vitamins K, C, P, B vitamins, tocopherol (provitamin E).

Microgranulation of the neutralized coniferous extract is carried out using a water-soluble polymer matrix binder, which is combined with the specified extract, and then the combined system, which is a mixture of the neutralized extract of coniferous herbs and the polymer matrix binder in the form of an aqueous solution, is introduced into the aqueous solution of a crosslinking agent.

There are two options for implementing the method of obtaining a feed additive.

In the first embodiment, either an aqueous sodium alginate solution or a protein-anionic polysaccharide-type complex consisting of gelatin and sodium alginate taken in a weight ratio of 4: 1 to 3: 2 is used as a water-soluble polymer matrix binder, and a crosslinking agent is used water soluble calcium salts. The latter provide the production of an insoluble polymer matrix of microgranules due to the reaction between the calcium ion Ca ²⁺ and the carboxyl groups of sodium alginate.

It was found that the process of interaction of the calcium ion Ca ²⁺ with acid groups proceeds almost instantly, creating a barrier on the surface of the microgranule that prevents further deeper penetration of Ca ^{2+ ions} into the microgranule and the formation of a more densely crosslinked network structure. Under the conditions of granule formation, gelatin plays the role of a regulator of the rate of decay of microgranules in the gastrointestinal tract (GIT).

As a source of calcium ions, Ca ²⁺ uses water-soluble or partially water-soluble salts of calcium and various inorganic acids, such as calcium dichloride, calcium glycerophosphate, as well as organic acids such as aliphatic (e.g. calcium acetate), hydroxy acids (e.g. lactic , gluconic), aromatic (for example, benzoic, salicylic, acetyl-o-salicylic) in such concentrations as to ensure that in the bath with a solution of a crosslinking agent the concentration of calcium ions Ca ²⁺ in the range of 0.4-1.0 wt.%. It is possible to repeatedly use solutions of calcium salts with adjusting the concentration of calcium ions, which ensures a virtually waste-free process.

In the second embodiment, a protein-anionic polysaccharide type complex consisting of gelatin and sodium alginate taken in a weight ratio of 4: 1 to 3: 2 is used as a water-soluble polymer matrix binder, and water-soluble iron salts are used as a crosslinking agent. In the case of using iron salts as a crosslinking agent, the crosslinking of the polymer matrix is carried out due to the interaction of iron ions with the functional groups of gelatin.

At the same time, the rate of crosslinking by iron ions is lower than when crosslinking the matrix due to the interaction of sodium alginate with calcium ions, which makes it possible to control the depth of crosslinking to control the final properties of microgranules and process conditions.

From a physiological point of view, microgranulation of a feed additive ensures the efficiency of its preservation in the environment of gastric juice (at pH ~ 1.5 in the presence of pepsin) for no more than 1 hour, so that biologically active substances are not destroyed, and, conversely, due to complete destruction in medium of duodenal juice (at pH ~ 7.5 in the presence of pancreatin) for no more than 3 hours (to ensure absorption of the supplement through the intestinal wall).

The behavior of the microgranulated feed supplement based on extracts of coniferous herbs was tested at a temperature of 37 ° C in the environment of gastric and intestinal juices. The data are shown in table 1.

Table 1
The behavior of microgranular feed additives in the environment of gastric and intestinal juices (in vitro) Gastric juice extract The granules remain intact for 1 hour. The surrounding juice remains clear and colorless. Intestinal extract Within 50 minutes, the granules are completely destroyed. The surrounding juice begins to turn green from the very beginning of the aging process.

The proposed invention is illustrated by examples.

Table 2 shows the compositions obtained using various water-soluble calcium salts with a different mass ratio between the coniferous green extract and the polymer matrix binder, as well as with a different mass ratio between sodium alginate and gelatin in the binder composition, feed additive formulations, reflecting variations as the content of components in the microspheres, as well as the nature and content of calcium salts used for the spatial crosslinking of the polymer matrix, which are included in the precipitation bath.

table 2 Components The content of components, wt.% Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Coniferous green extract (in terms of dry matter) 80 80 85 85 75 75 80 Sodium Alginate (dry matter) 15.94 11.98 8.93 11.95 14.97 24.93 15.95 Gelatin (dry matter) 3.99 7.98 5.97 2.98 9.98 0 3.99 Crosslinking agent (in terms of the content of Ca ^{2+ ion} 0,07 0.04 0.10 0,07 0.05 0,07 0.06 The composition of the bath with calcium salts Name of salts The content of calcium salt, wt.% / Content of Ca ^{2+ ion} , wt.% Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Calcium Dichloride CaCl ₂ 2.0 / 0.72 Calcium glycerophosphate CaPO ₃ -O-C ₃ H ₅ (OH) ₂ 3.60 / 0.72 Calcium Acetate (CH ₃ COO) ₂ Ca 1.6 / 0.4 Calcium Benzonate (C ₆ H ₅ COO) ₂ Ca 3.52 / 0.5 Calcium gluconate ((CH ₂ OHCHOH) ₄ COO) ₂ Ca 7.6 / 0.7 Calcium Lactate (CH ₃ CHOHCOO) ₂ Ca 5.56 / 1.0 Calcium Acetylsalicylate (CH ₃ -O-CO-C ₆ H ₄ -COO) ₂ Ca 6.0 / 0.6

Note: any of the calcium salt solution compositions listed in the table is suitable for the formation of microgranules of the compositions shown in examples 1-7.

Table 3 shows the compositions obtained using various water-soluble iron salts at different mass ratios between coniferous green extract and the polymer matrix binder, as well as at various mass ratios between sodium alginate and gelatin in the binder composition, formulations of several feed additives, reflecting variations as according to the content of components in microgranules, and by the nature and content of iron salts used for spatial crosslinking of the polymer matrix, which are included in the precipitation Anna.

Table 3 Components The content of components, wt.% Example 8 Example 9 Example 10 Example 11 Coniferous green extract (in terms of dry matter) 85 85 80 80 Sodium Alginate (dry matter) 8.97 8.97 15.96 15.94 Gelatin (dry matter) 5.98 5.98 3.98 3.96 Crosslinking agent (in terms of Fe ³⁺ ion content) 0.05 0.05 0.06 0.1 The composition of the bath with iron salts Name of salts The content of iron salt, wt.% / Ion content Fe ³⁺ , wt.% Example 8 Example 9 Example 10 Example 11 Iron-potassium sulfate (alum) Fe ₂ (SO ₄ ) ₃ · KSO ₄ · 24H ₂ O 4,55 / 0,5 Iron sulfate, hydrate Fe ₂ (SO ₄ ) ₃ · 9Н ₂ O 2.67 / 0.5 Iron chloride FeCl ₃ 1.71 / 0.6 Iron chloride, hydrate FeCl ₃ · 6H ₂ O 4.76 / 1.0

Note: any of the compositions of solutions of iron salts listed in the table is suitable for the formation of microgranules of the compositions shown in examples 8-11.

FINDINGS

- Microgranules obtained by the claimed method, in an in vitro experiment showed a protective effect - the preservation of biologically active components in the gastric juice at the level of microencapsulated products, while in the intestinal juice microgranules disintegrate faster, which contributes to their physiological effectiveness.

- Reduced the duration of the production cycle compared with the known method (prototype) from a period of at least 1 day at any volume of the reactor to the short-term formation of microspheres, the number of which is limited only by the number of dies of the granulator apparatus.

- In contrast to the known method, the claimed method (options) can be hardware-designed as a continuous process.

- The practical absence of wastewater due to the repeated use of solutions of crosslinking agents - calcium salts.

The proposed invention will find application in the fields of poultry, livestock, animal husbandry, fish farming in diets as an effective feed additive.

Claims (9)

1. A method of obtaining a feed additive, including processing extracts of coniferous herbs, characterized in that microgranulation of the neutralized extract of coniferous herbs is carried out using a water-soluble polymer matrix - a binder in the form of an aqueous solution, which is combined with the above extract, and then the resulting mixture is introduced dropwise into an aqueous solution a crosslinking agent, while sodium alginate or a protein-anionic polysaccharide-type complex consisting of yellow atin and sodium alginate, and as a crosslinking agent, water-soluble calcium salts are used to provide an insoluble matrix of microgranules, and the obtained dried granules contain the following components, wt.% (in terms of dry matter): Coniferous extracts 70-90 Polymer matrix binder 9-25 Crosslinking agent (in terms of calcium ion Ca ²⁺ ) 0.04-0.10 2. A method of obtaining a feed additive, including processing extracts of coniferous herbs, characterized in that microgranulation of the neutralized extract of coniferous herbs is carried out using a water-soluble polymer matrix binder in the form of an aqueous solution, which is combined with the above extract, and then the resulting mixture is introduced dropwise into an aqueous solution a crosslinking agent, while a protein-anionic polysaccharide complex consisting of gelatin and sodium alginate is used as a polymer matrix binder Riya, and as a cross-linking agent, water-soluble salts of iron are used to provide an insoluble matrix of microgranules, and the obtained dried granules contain the following components, wt.% (in terms of dry matter): Coniferous extracts 70-90 Polymer matrix binder 9-25 Crosslinking agent (in terms of iron ion Fe ³⁺ ) 0.05-0.50 3. The feed additive obtained by the method according to claim 1, containing a biologically active substance - extracts of coniferous herbs, characterized in that it contains the following components, wt.% (In terms of dry matter): Coniferous extracts 70-90 Polymer matrix binder 9-25 Crosslinking agent (in terms of calcium ion Ca ⁺ ) 0.04-0.10 4. The feed additive according to claim 3, characterized in that the polymer matrix binder contains sodium alginate or sodium alginate with gelatin, in the following ratio, wt.%: Sodium Alginate 9-25 Gelatin 0-10 and as a crosslinking agent, water-soluble or partially water soluble calcium salts. 5. Feed additive according to claims 3 and 4, characterized in that the polymer matrix binder contains sodium alginate or sodium alginate with gelatin, taken in a mass ratio of 4: 1 to 3: 2. 6. The feed additive according to claim 3, characterized in that water-soluble or partially water-soluble salts of calcium and various inorganic acids — calcium dichloride, calcium glycerophosphate, and organic acids, such as aliphatic, are used as a source of calcium ions of Ca ²⁺ . for example, calcium acetate, hydroxy acids, for example, lactic, gluconic, aromatic, for example, benzoic, salicylic, acetyl-o-salicylic, in the concentrations necessary to ensure the concentration of calcium ions in a bath with a solution of a crosslinking agent ²⁺ in the range 0.4-1.0 wt.%. 7. The feed additive obtained by the method according to claim 2, containing a biologically active substance - extracts of coniferous herbs, characterized in that it contains the following components, wt.% (In terms of dry matter): Coniferous extracts 70-90 Polymer matrix binder 9-25 Crosslinking agent (in terms of iron ion Fe ³⁺ ) 0.05-0.50 8. The feed additive according to claim 7, characterized in that the polymer matrix binder contains sodium alginate with gelatin, taken in a mass ratio of 4: 1 to 3: 2, in the following ratio of components, wt.%: Sodium Alginate 6-18 Gelatin 2-12, and as a crosslinking agent, water-soluble or partially water soluble iron salts. 9. The feed additive according to claim 7, characterized in that the source of iron ions Fe ³⁺ use water-soluble or partially water soluble salts of iron and inorganic acids, for example hydrochloric, sulfuric, including mixed salts of the type of alum, in concentrations necessary to ensure in the bath with a solution of a crosslinking agent the concentration of iron ions Fe ³⁺ in the range of 0.5-5.0 wt.%.