Rumen-bypass choline chloride granules and preparation method thereof

Abstract

The present invention relates to rumen bypass choline chloride granules and a preparation method thereof. The rumen bypass choline chloride granules provided by the present invention include: a core, an inner coating film wrapped around the outside of the core, and an outer coating film wrapped around the inner coating film; and the core includes choline chloride and a carrier of the choline chloride, the carrier including a first oily component; the inner coating film includes a second oily component; and the outer coating film includes a pH-sensitive material; wherein the melting point of the first oily component is 37-46°C, and the melting point of the second oily component is above 60°C. By adding oil to the core, the moisture absorption of choline is slowed down, the amount of other carriers used is reduced, and the choline content in the product is increased, which is conducive to large-scale continuous production. By adopting specific inner and outer coating materials, the rumen bypass rate and small intestinal digestibility of the rumen bypass choline chloride granules are significantly improved, and the bioavailability of the product is significantly improved.

Description

Technical Field

[0001] The invention belongs to the technical field of feed additives, and in particular relates to rumen bypass choline chloride granules and a preparation method thereof, and more particularly relates to rumen bypass choline chloride granules with high bioavailability and suitable for large-scale continuous production and a preparation method thereof. Background Art

[0002] The increase in non-esterified fatty acids during the peripartum period is part of the normal biology of dairy cows, contributing to a smooth delivery and postpartum lactation. Under normal circumstances, the liver esterifies non-esterified fatty acids into triglycerides, which are then packaged with proteins, cholesterol, cholesterol esters, phosphatidylcholine, and other components into very low-density lipoproteins for delivery to other tissues.

[0003] Phosphatidylcholine is the most common form of choline in biological systems. Very-low-density lipoproteins (VLDLs) can only form when the body has sufficient phosphatidylcholine. Therefore, choline is an essential nutrient for the liver to package fat and transport it to tissues such as the mammary gland. Unfortunately, current dairy cows are choline deficient, leading to the accumulation of triglycerides in the liver, resulting in fatty liver. Furthermore, some non-esterified fatty acids enter the bloodstream, and when their concentrations reach a certain level, they can cause subclinical ketosis and ketosis. This leads to reduced feed intake and milk production. Furthermore, liver dysfunction prevents cows from effectively detoxifying excess ammonia produced by rumen fermentation, resulting in ammonia poisoning. Furthermore, the liver is unable to convert propionate from rumen fermentation into glucose, a precursor to lactose in milk and a key component in milk production, resulting in reduced milk production. The prevalence of fatty liver disease in dairy cows varies worldwide, ranging from 30% to 70%. Fatty liver disease reduces cow health, productivity, and fertility, causing significant losses to the dairy industry.

[0004] Adding choline to feed is a practical and effective method for preventing and alleviating fatty liver disease and ketosis in dairy cows. However, the majority of choline added directly to the diet is degraded by microorganisms in the rumen, with only about 10% reaching the small intestine. Therefore, rumen-passing technology is required to encapsulate the choline to reduce rumen degradation, allowing the majority of the choline to pass smoothly through the rumen and reach the small intestine for utilization. Compared to choline, choline chloride is more stable, its aqueous solution is neutral, and it is less irritating to animal tissues. Therefore, choline chloride is often used as a choline replacement in the feed industry. To effectively supply choline chloride for ruminant utilization, existing technologies have provided several solutions.

[0005] For example:

[0006] Reference 1 discloses a rumen-bypass choline microcapsule and its preparation process. The microcapsules use choline chloride as the core material, acrylic resin IV as the inner coating material, chitosan as the outer coating material, and ethyl cellulose as an additional layer material located between the inner and outer coating layers or on top of the outer coating layer. The inner and outer coating materials and the additional coating material each account for 3-5% of the core material. However, these coating materials must be dissolved in an organic solvent before spraying. The organic solvent accounts for approximately 90% of the coating solution. Drying and volatilizing these organic solvents is time-consuming and energy-intensive, resulting in waste of organic solvents. Furthermore, the effective utilization rate of the rumen-bypass choline is low. The effective release rate of the best-performing product in the embodiment was only 50.39%.

[0007] Cited Document 2 discloses a choline chloride composition granule designed for rumen protection and effective post-rumen release. The granule is coated with a double layer of oil: a first continuous layer comprising a hydrophobic substance selected from fats, hydrogenated oils, fatty acid monoglycerides, fatty acid diglycerides, fatty acid esters, and fatty acid alcohols; and a second, outermost layer comprising a hydrophobic substance selected from microcrystalline wax, paraffin, vegetable wax, and edible synthetic wax. This ensures a high rumen passage rate for the composition. However, further improvements in the post-rumen digestibility of choline chloride in the composition and the overall bioavailability of these substances are desired.

[0008] Reference 3 discloses a rumen-bypass choline chloride microcapsule and its preparation method. The microcapsule comprises a core composed of choline chloride and a carrier, an inner coating, and an outer coating. The inner coating is made of one or more vegetable fats with a melting point above 60°C. The outer coating is made of rice bran wax, zinc oxide powder, and a film-forming material; the film-forming material is phthalate glucose, polyethylene glycol, or sodium alginate. This prior art states that zinc oxide powder is embedded in the rice bran wax to form a tight film. This zinc oxide powder remains stable in the alkaline environment of the rumen. Upon reaching the small intestine, the zinc oxide powder rapidly reacts with the acidic intestinal fluid, forming numerous pores on the surface of the rice bran wax film, promoting the rapid release of the active ingredient, choline chloride. However, in reality, zinc oxide reacts with acidic silage and, upon entering the rumen, with acidic substances such as acetic acid, affecting its coating effectiveness.

[0009] References:

[0010] Reference 1: CN101269051B

[0011] Reference 2: US11395803B2

[0012] Reference 3: CN109362950B Summary of the Invention

[0013] Problems to be solved by the invention

[0014] In order to conduct further research, the applicant of this application purchased the top four products in terms of sales volume on the market, and the bioavailability of the four samples was measured by a third-party institution, Northeast Agricultural University. Product A and Product B are rumen-passed choline chloride products imported from two different manufacturers in the United States, Product C is a rumen-passed choline chloride product imported from Italy, and Product D is a rumen-passed choline chloride product with high sales volume produced in China. As shown in Table 1 (wherein, lowercase letters are identifiers of significant differences (P < 0.05) between groups, and the identifiers of two groups of values that do not contain the same letter indicate a significant difference between the two groups, otherwise it indicates no significant difference), the measured values of the bioavailability (rumen-passing rate × small intestinal digestibility) of the four products are all less than 50%. This shows that although there are many types of rumen-passed choline products on the market, the problem that still exists is that products with high rumen-passing rates have low small intestinal digestibility (such as Product A), while products with high small intestinal digestibility often cannot pass through the rumen smoothly (such as Product B and Product D), resulting in low bioavailability of the products.

[0015] Table 1: Content, rumen bypass rate, small intestine digestibility and utilization of four rumen bypass choline products

[0016] project Product A Product B Product C Product D Choline content / % <![CDATA[38.4±0.42 b ]]> <![CDATA[30.9±1.22 c ]]> <![CDATA[66.7±1.89 a ]]> <![CDATA[31.5±2.58 c ]]> Rumen bypass rate / % <![CDATA[77.1±0.65 a ]]> <![CDATA[20.6±0.75 d ]]> <![CDATA[55.9±1.09 b ]]> <![CDATA[44.2±0.81 c ]]> Small intestinal digestibility / % <![CDATA[58.9±2.80 c ]]> <![CDATA[96.5±0.64 a ]]> <![CDATA[71.0±2.69 b ]]> <![CDATA[98.1±0.60 a ]]> Bioavailability / % <![CDATA[45.5±2.53 a ]]> <![CDATA[19.8±0.66 c ]]> <![CDATA[39.7±1.31 b ]]> <![CDATA[43.4±1.31 a ]]>

[0017] It can be seen that the current research in the prior art on choline chloride products that can smoothly pass through the rumen and have high utilization rates in the small intestine is still not sufficient. The purpose of the present invention is to use hot melt extrusion technology to granulate, and select different types of coating materials according to the characteristics of the ruminant digestive tract to coat the prepared choline chloride granules, thereby protecting the choline chloride from microbial degradation in the rumen as much as possible, while effectively releasing it in the post-rumen digestive tract for absorption and utilization by the body, in order to improve the bioavailability of rumen-bypass choline products by combining hot melt extrusion granulation with hot melt coating and pH-sensitive material coating.

[0018] Solutions for solving problems

[0019] Through extensive research, the inventors found that the above technical problems can be solved by the following technical solutions:

[0020] [1] A rumen-bypass choline chloride granule, characterized in that the rumen-bypass choline chloride granule comprises:

[0021] A core, an inner coating film wrapped around the core, and an outer coating film wrapped around the inner coating film;

[0022] Furthermore, the core comprises choline chloride and a carrier of the choline chloride, and the carrier comprises a first oily component;

[0023] The inner coating film includes a second oily component; and

[0024] The outer coating film comprises a pH sensitive material;

[0025] The melting point of the first oily component is 37-46°C, and the melting point of the second oily component is above 60°C.

[0026] [2] The rumen bypass choline chloride granules according to [1] are characterized in that the first oily component is selected from one or more of vegetable oils and waxes.

[0027] [3] The rumen bypass choline chloride granules according to [1] or [2], characterized in that the second oily component is selected from one or more plant oils or waxes.

[0028] [4] The rumen bypass choline chloride granules according to any one of [1] to [3], characterized in that the pH sensitive material is an acrylic resin, a polysaccharide component or a mixture thereof.

[0029] [5] The rumen bypass choline chloride granules according to any one of [1] to [4], characterized in that, based on the total mass of the rumen bypass choline chloride granules, they contain 25% to 65% by mass of choline chloride, 5% to 20% by mass of the first oily component, 10% to 20% by mass of the second oily component, and 2% to 5% by mass of the pH-sensitive material.

[0030] [6] The rumen bypass choline chloride granules according to any one of [1] to [5], characterized in that the carrier further comprises a filler, a binder and a lubricant;

[0031] The filler comprises at least one selected from the group consisting of silicate, zeolite powder, silicon dioxide and perlite;

[0032] The binder comprises at least one selected from the group consisting of potato starch, corn starch and hydroxypropyl methylcellulose;

[0033] The lubricant includes at least one selected from the group consisting of zinc stearate, magnesium stearate, and calcium stearate.

[0034] [7] The rumen bypass choline chloride granules according to [6], characterized in that, based on the total mass of the rumen bypass choline chloride granules, they contain 10% to 23% by mass of a filler, 1% to 5% by mass of a binder, and 1% to 3% by mass of a lubricant.

[0035] [8] A method for preparing rumen bypass choline chloride granules according to any one of [1] to [7], characterized in that the preparation method comprises the following steps:

[0036] Granulation step: mixing choline chloride, a carrier and a first oily component and then performing hot-melt granulation to obtain a core;

[0037] The coating step comprises heating and melting the second oily component and then spraying the core with the first coating, dissolving the pH sensitive material in an organic solvent and then spraying the core with the first coating for the second coating.

[0038] [9] The preparation method according to [8] is characterized in that the granulation step is completed by a hot melt extruder and the coating step is completed by a fluidized bed.

[0039]

[10] An animal feed, characterized in that the feed contains the rumen bypass choline chloride granules according to any one of [1] to [7].

[0040] Effects of the Invention

[0041] By implementing the above technical solution, compared with the prior art, the present invention can achieve the following excellent technical effects:

[0042] (1) The present invention adopts hot melt extrusion technology and adds oil to the core, which slows down the moisture absorption of choline. It can not only reduce the amount of other carriers such as choline adsorption carriers added and increase the choline content in the product, but also help choline adapt to production in any weather, especially rainy days, and is more conducive to large-scale continuous production.

[0043] (2) The present invention utilizes specific inner and outer coating materials based on the differences in different parts of the ruminant digestive tract, significantly improving the rumen clearance rate and small intestinal digestibility of the rumen-bypass choline chloride granules, thereby significantly improving the product's bioavailability. In some embodiments, the rumen clearance rate of the rumen-bypass choline chloride granules provided by the present invention is greater than 93%, and the small intestinal digestibility is greater than 97%, both of which are higher than mainstream products on the market, significantly improving the utilization rate of choline chloride by ruminants.

[0044] (3) The granulation, coating materials and coating process used in the present invention make its properties more stable, can better resist mechanical damage during transportation, and have a longer shelf life. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 : Schematic cross-sectional view of the rumen bypass choline chloride granules provided by the present invention; wherein, the left figure is a schematic cross-sectional view, and the right figure is a schematic longitudinal cross-sectional view. DETAILED DESCRIPTION

[0046] The following describes the embodiments of the present invention, but the present invention is not limited thereto. The present invention is not limited to the various structures described below, and various modifications can be made within the scope of the invention. Embodiments and examples obtained by appropriately combining the technical means disclosed in different embodiments and examples are also included in the technical scope of the present invention.

[0047] In the present invention, a numerical range expressed using "numerical value A to numerical value B" or "numerical value A - numerical value B" means a range including the endpoints numerical values A and B.

[0048] In the present invention, a numerical range expressed using "above" or "below" means a numerical range including the number.

[0049] In the present invention, the use of "may" includes both the meanings of performing a certain process and not performing a certain process.

[0050] In the present invention, "optional" or "optionally" means that certain substances, components, execution steps, application conditions and other factors are used or not used.

[0051] In the present invention, the terms "comprising," "having," "including," or "containing" may be inclusive or open-ended, and do not exclude additional, unrecited elements or method steps. At the same time, "comprising," "having," "including," or "containing" may also be closed-ended, excluding additional, unrecited elements or method steps.

[0052] In the present invention, the term "about" is used to define the numerical ranges and parameters of the present invention. All numerical values in the specific embodiments have been presented as accurately as possible. Unless otherwise expressly stated, it should be understood that all ranges, quantities, values and percentages used in the present invention are modified by "about". Here, "about" generally means that the actual value is within ±10%, ±5%, ±1% or ±0.5% of a particular value or range.

[0053] In the present invention, the unit names used are all international standard unit names, and unless otherwise stated, the "%" used represents weight or mass percentage.

[0054] In the present invention, unless otherwise stated, "a plurality of" means two or more.

[0055] In the present invention, references to "some specific / preferred embodiments," "other specific / preferred embodiments," "embodiments," etc., mean that the specific elements (e.g., features, structures, properties, and / or characteristics) described in connection with the embodiments are included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it should be understood that the elements may be combined in various embodiments in any suitable manner.

[0056] Unless otherwise defined, other technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

[0057] Rumen-bypass choline chloride granules

[0058] The present invention provides a rumen-bypass choline chloride granule, characterized in that the rumen-bypass choline chloride granule comprises:

[0059] a core comprising choline chloride and a carrier comprising a first oily component;

[0060] an inner coating film comprising a second oily component; and

[0061] an outer coating film comprising a pH-sensitive material;

[0062] The melting point of the first oily component is 37-46°C, and the melting point of the second oily component is above 60°C.

[0063] The composition diagram of the rumen bypass choline chloride granules provided by the present invention is as follows: Figure 1 shown.

[0064] The present invention slows down the moisture absorption of choline chloride by adding a first oily component to the core, making the rumen-pass choline granules suitable for large-scale continuous production. In addition, by adopting a specific double-layer coating material, the rumen-pass rate (>93%) and small intestinal digestibility (>97%) of the product are higher than those of mainstream products on the market, thereby significantly improving the utilization rate of choline chloride by ruminants.

[0065] (Core)

[0066] Choline chloride is the main active ingredient, and the present invention does not particularly limit its source and properties. For example, it can be obtained commercially. In some typical embodiments, the choline chloride used in the present invention is a choline chloride crystalline powder with a purity of ≥99.5% and a particle size of 100-300 μm, which is beneficial for improving the purity of choline in the product.

[0067] Since the present application adds the first oily component to the core, it has a certain plasticity, effectively reducing the amount of other carriers in the rumen bypass choline chloride granules, and correspondingly increasing the choline chloride content in the finished product.

[0068] In some specific embodiments, based on the total mass of the rumen-bypass choline chloride granules, the rumen-bypass choline chloride granules contain 25% to 65% by mass of choline chloride, and the stability of the rumen-bypass choline chloride granules is optimal at this effective content. In some typical embodiments, the rumen-bypass choline chloride granules contain 25%, 28%, 30%, 35%, 38%, 40%, 45%, 48%, 50%, 55%, 58%, 60%, or 65% by mass of choline chloride.

[0069] In order to facilitate the preparation of the core by hot melt extrusion granulation, in some specific embodiments, the melting point of the first oily component of the present invention is 37-46°C, preferably 38-44°C.

[0070] In some preferred embodiments, the first oily component of the present invention can be one or more of a vegetable oil and a wax. In principle, there is no particular limitation on the type of these oily components, as long as their melting points fall within the above-mentioned range. In some typical embodiments, the vegetable oil includes one or more selected from the group consisting of lauric acid, cocoa butter substitutes, and petroleum wax, all with a melting point of approximately 40°C, and palm oil, all with a melting point of approximately 44°C. In some preferred embodiments, the first oily component is palm oil, which has a melting point of approximately 44°C and is more readily available in large quantities.

[0071] The invention adds the first oily component, especially the vegetable oil, to the core, thereby slowing down the moisture absorption of choline, and can continuously produce rumen-passed choline chloride particles in large quantities even on wet and rainy days.

[0072] The present invention does not particularly limit the amount of the first oily component added to the core. To reduce the digestive burden on animals, in some specific embodiments, the rumen-bypass choline chloride granules contain 5% to 20% by mass of the first oily component, preferably 10% to 20% by mass, based on the total mass of the rumen-bypass choline chloride granules. In some typical embodiments, the rumen-bypass choline chloride granules contain 5%, 10%, 15%, or 20% by mass of the first oily component, especially the above-mentioned vegetable oil.

[0073] In some specific embodiments, the carrier further comprises a filler, a binder, and a lubricant.

[0074] In some specific embodiments, the filler comprises at least one selected from the group consisting of silicate, zeolite powder, silicon dioxide, and perlite. In some typical embodiments, the filler is silicon dioxide. Silicon dioxide has good fluidity and adsorption properties and can fully adsorb active substances.

[0075] In some specific embodiments, the binder comprises at least one selected from the group consisting of potato starch, corn starch, and hydroxypropyl methylcellulose. In some typical embodiments, the binder is corn starch. Corn starch is an abundant natural resource and can increase the solid content of the granules and improve the granule stability after gelatinization.

[0076] In some specific embodiments, the lubricant comprises at least one selected from the group consisting of zinc stearate, magnesium stearate, and calcium stearate. In some typical embodiments, the lubricant is magnesium stearate. Magnesium stearate has a greasy feel and is absorbent, and is a commonly used lubricant in tablets and capsules.

[0077] Since the present invention adds a first oily component such as vegetable oil to the core, it has a certain plasticity, thereby reducing the amount of other carriers. In some specific embodiments, based on the total mass of the rumen bypass choline chloride granules, the rumen bypass choline chloride granules contain 10% to 23% by mass of fillers, 1% to 5% by mass of binders, and 1% to 3% by mass of lubricants. In some typical embodiments, the rumen bypass choline chloride granules contain 10%, 16% or 23% by mass of fillers. In some typical embodiments, the rumen bypass choline chloride granules contain 1%, 2%, 3%, 4% or 5% by mass of binders. In some typical embodiments, the rumen bypass choline chloride granules contain 1%, 2% or 3% by mass of lubricants.

[0078] (Coating film)

[0079] The rumen-bypass choline chloride granules provided by the present invention, after being ingested by ruminants such as dairy cows, successively pass through the rumen, reticulum, omasum and abomasum before reaching the small intestine. The pH of the rumen of cattle and sheep ranges from 5.5 to 7.5, the pH of the small intestine is about 7.6, but the pH of the abomasum is about 2.0. Post-rumen intestinal digestion mainly includes abomasum digestion, small intestine digestion, etc., and fat digestion mainly occurs in the small intestine. To ensure that the rumen-bypass choline has a high bioavailability, a second oily component with a melting point of greater than or equal to 60°C and a pH-sensitive material are selected to coat the choline chloride granules respectively.

[0080] To prevent the coating from melting in the rumen, in some specific embodiments, the present invention uses a second oily component with a melting point higher than the rumen fermentation temperature as the inner coating material. In some typical embodiments, the melting point of the second oily component is greater than or equal to 60°C and less than 90°C, preferably less than or equal to 85°C.

[0081] The specific second oily component of the present invention can generally be selected from components derived from plant oils or waxes, etc., preferably plant fat components. In principle, there is no particular limitation on its specific type, as long as its melting point meets the above range. In some typical embodiments, the second oily component includes one or more selected from the group consisting of hydrogenated palm oil, hydrogenated soybean oil, beeswax, rice bran wax and carnauba wax. Under the premise of ensuring that the rumen-passing choline chloride granules can pass through the rumen smoothly, in order to obtain a higher small intestinal digestibility, in some preferred embodiments, the second oily component is hydrogenated palm oil. It has been found that it has a higher small intestinal digestibility than carnauba wax and the like, and is relatively low in price.

[0082] In order to reduce the digestive burden on animals, in some specific embodiments, the rumen-bypass choline chloride granules contain 10% to 20% by mass of the second oily component, based on the total mass of the rumen-bypass choline chloride granules. In some typical embodiments, the rumen-bypass choline chloride granules contain 10%, 12%, 15%, 17%, or 20% by mass of the second oily component.

[0083] To ensure smooth passage of rumen-bypass choline chloride granules through the rumen and their disintegration in the abomasum for subsequent digestion in the small intestine, in some specific embodiments, the present invention utilizes acrylic resins and / or polysaccharide components as outer coating materials. Preferably, polyacrylic resin IV, chitosan, or a mixture thereof in any proportion can be used. Polyacrylic resin IV and chitosan are virtually insoluble in the rumen environment at a pH of approximately 5.5 to 7.5, but dissolve in the acidic abomasum at a pH of approximately 2 (<5). Using them as outer coatings can resist invasion by rumen microorganisms. In some preferred embodiments, the pH-sensitive material is polyacrylic resin IV, and its solvent is an ethanol solution. Spraying the granules on the surface allows for easier evaporation and drying, making them more easily recyclable.

[0084] In some specific embodiments, the rumen-bypass choline chloride granules contain 2% to 4% by mass of pH-sensitive materials, based on the total mass of the rumen-bypass choline chloride granules. In some typical embodiments, the rumen-bypass choline chloride granules contain 2%, 3%, or 4% by mass of pH-sensitive materials.

[0085] Since choline is highly hygroscopic, it is necessary to wrap the hydrophobic plant fat in the inner layer under the pH-sensitive material. The double-layer coating not only prevents the rumen-passing choline product from absorbing moisture during storage and resisting mechanical damage during transportation, but also better protects choline chloride from passing through the rumen smoothly. After reaching the abomasum, due to the relatively low pH, the outermost pH-sensitive material disintegrates in the abomasum. After reaching the small intestine, the fat is decomposed under the action of lipase in the small intestine, thereby improving the bioavailability of the choline chloride product.

[0086] When only one layer of coating film is used, it is too thin to achieve the ideal rumen-passing effect. To achieve the ideal rumen-passing effect, a large amount of plant fat or pH-sensitive material is required. Too much fat will cause the posterior digestive tract to not be digested in time, affecting the bioavailability of the rumen-passing choline product; and the large amount of pH-sensitive material used will result in a long time and high energy consumption, which is not conducive to production.

[0087] Preparation method of rumen bypass choline chloride granules

[0088] The present invention provides a method for preparing rumen-bypass choline chloride granules, which comprises the following steps:

[0089] Granulation step: mixing choline chloride, a carrier and a first oily component and then performing hot-melt granulation to obtain a core;

[0090] The coating step comprises heating and melting the second oily component and then spraying the core with the first coating, dissolving the pH sensitive material in an organic solvent and then spraying the core with the first coating for the second coating.

[0091] In some specific embodiments, in the granulation step, choline chloride is first mixed with the carrier, and then the first oily component is added and mixed evenly.

[0092] In some specific embodiments, the granulation step is performed by a hot melt extruder.

[0093] In some specific embodiments, during the coating step, the pH sensitive material can be optionally used by dissolving it in an (organic) solvent, for example, dissolving polyacrylic acid resin IV in an ethanol solution, dissolving chitosan in a glacial acetic acid solution, etc.

[0094] In order to facilitate the volatilization of the (organic) solvent and the drying of the product, in some specific embodiments, during the coating step, the content of the pH sensitive material in the organic solvent is 1% (W / V) to 5% (W / V).

[0095] In some specific embodiments, the coating step is performed by a fluidized bed.

[0096] Animal feed

[0097] The present invention provides an animal feed comprising the rumen bypass choline chloride granules. In addition, in order to meet the different feeding requirements of animals, the feed may further contain any other nutritional components.

[0098] Example

[0099] The embodiments of the present invention will be described in detail below with reference to the examples. However, it will be understood by those skilled in the art that the following examples are only intended to illustrate the present invention and should not be construed as limiting the scope of the invention. Where specific conditions are not specified in the examples, the methods were performed according to conventional conditions or the conditions recommended by the manufacturer. Unless otherwise specified, the materials or instruments used were commercially available conventional products.

[0100] Example 1

[0101] The invention discloses rumen bypass choline chloride microparticles, which are composed of the following raw materials in percentage by mass: 28% choline chloride; 23% silicon dioxide; 5% corn starch; 3% magnesium stearate; 20% palm oil; 17% hydrogenated palm oil; 2% polyacrylic acid resin IV; and 2% chitosan.

[0102] The specific preparation process is as follows:

[0103] (1) 280 kg of choline chloride was mixed with 230 kg of silicon dioxide, 50 kg of corn starch, and 30 kg of magnesium stearate, and then pulverized to obtain a mixture I;

[0104] (2) Melting 200 kg of palm oil and thoroughly stirring it with mixture I, and then extruding and granulating it using a hot melt extruder to obtain primary core particles;

[0105] (3) 170 kg of hydrogenated palm oil was melted, the primary core particles were placed in a fluidized bed, and the melted hydrogenated palm oil was sprayed into the fluidized bed to obtain secondary core particles;

[0106] (4) 20 kg of polyacrylic acid resin IV was added to 95% (V / V) ethanol solution to prepare a 3% (W / V) polyacrylic acid resin IV solution, and 20 kg of chitosan was added to 4% (V / V) glacial acetic acid solution to prepare a 3% (W / V) chitosan solution. The solution was sprayed on the surface of the secondary core particles in a fluidized bed to obtain rumen-bypass choline chloride with an effective choline chloride content of not less than 25% (mass fraction).

[0107] Example 2

[0108] The invention discloses rumen bypass choline chloride microparticles, which are composed of the following raw materials in percentage by mass: 28% choline chloride; 23% silicon dioxide; 5% corn starch; 3% magnesium stearate; 20% palm oil; 17% hydrogenated palm oil; and 4% polyacrylic acid resin IV.

[0109] The specific preparation process is as follows:

[0110] (1) 280 kg of choline chloride was mixed with 230 kg of silicon dioxide, 50 kg of corn starch, and 30 kg of magnesium stearate, and then pulverized to obtain a mixture I;

[0111] (2) Melting 200 kg of palm oil and thoroughly stirring it with mixture I, and then extruding and granulating it using a hot melt extruder to obtain primary core particles;

[0112] (3) 170 kg of hydrogenated palm oil was melted, the primary core particles were placed in a fluidized bed, and the melted hydrogenated palm oil was sprayed into the fluidized bed to obtain secondary core particles;

[0113] (4) 40 kg of polyacrylic acid resin IV was added to a 95% (V / V) ethanol solution to prepare a 3% (W / V) polyacrylic acid resin IV solution, which was sprayed on the surface of the secondary core particles in a fluidized bed to obtain rumen-bypass choline chloride with an effective choline chloride content of not less than 25% (mass fraction).

[0114] Example 3

[0115] The invention discloses rumen bypass choline chloride microparticles, which are composed of the following raw materials in percentage by mass: 28% choline chloride; 23% silicon dioxide; 5% corn starch; 3% magnesium stearate; 20% palm oil; 17% hydrogenated palm oil; and 4% chitosan.

[0116] The specific preparation process is as follows:

[0117] (1) 280 kg of choline chloride was mixed with 230 kg of silicon dioxide, 50 kg of corn starch, and 30 kg of magnesium stearate, and then pulverized to obtain a mixture I;

[0118] (2) Melting 200 kg of palm oil and thoroughly stirring it with mixture I, and then extruding and granulating it using a hot melt extruder to obtain primary core particles;

[0119] (3) 170 kg of hydrogenated palm oil was melted, the primary core particles were placed in a fluidized bed, and the melted hydrogenated palm oil was sprayed into the fluidized bed to obtain secondary core particles;

[0120] (4) 40 kg of chitosan was added to a 4% (V / V) glacial acetic acid solution to prepare a 3% (W / V) chitosan solution, which was sprayed on the surface of the secondary core particles in a fluidized bed to obtain rumen-bypass choline chloride with an effective choline chloride content of not less than 25% (mass fraction).

[0121] Comparative Example 1

[0122] The raw material composition is as follows, in percentage by mass: 28% choline chloride; 23% silicon dioxide; 5% corn starch; 3% magnesium stearate; 20% water; 20% palm oil; 17% hydrogenated palm oil; 2% polyacrylic acid resin IV; and 2% chitosan.

[0123] The specific preparation process is as follows:

[0124] (1) 280 kg of choline chloride was mixed with 230 kg of silicon dioxide, 50 kg of corn starch, and 30 kg of magnesium stearate, and then pulverized to obtain a mixture I;

[0125] (2) 100 kg of water was slowly added to the mixture I and stirred thoroughly, and the mixture was extruded into granules using an extruder and then dried to obtain primary core particles;

[0126] (3) 200 kg of palm oil was melted, the primary core particles were placed in a fluidized bed and dried, and then the melted palm oil was sprayed into the fluidized bed to obtain secondary core particles;

[0127] (4) 170 kg of hydrogenated palm oil was melted, the secondary core particles were placed in a fluidized bed, and the melted hydrogenated palm oil was sprayed into the fluidized bed to obtain tertiary core particles;

[0128] (5) 20 kg of polyacrylic acid resin IV was added to 95% (V / V) ethanol solution to prepare a 3% (W / V) polyacrylic acid resin IV solution, and 20 kg of chitosan was added to 4% (V / V) glacial acetic acid solution to prepare a 3% (W / V) chitosan solution, which was sprayed on the surface of the tertiary core particles in a fluidized bed in sequence to obtain rumen-bypass choline chloride with an effective choline chloride content of not less than 25% (mass fraction).

[0129] Comparative Example 2

[0130] The raw material composition is as follows, calculated by mass percentage: 28% of choline chloride; 23% of silicon dioxide; 5% of corn starch; 3% of magnesium stearate; 20% of palm oil; and 21% of hydrogenated palm oil.

[0131] The specific preparation process is as follows:

[0132] (1) 280 kg of choline chloride was mixed with 230 kg of silicon dioxide, 50 kg of corn starch, and 30 kg of magnesium stearate, and then pulverized to obtain a mixture I;

[0133] (2) Melting 200 kg of palm oil and thoroughly stirring it with mixture I, and then extruding and granulating it using a hot melt extruder to obtain primary core particles;

[0134] (3) 210 kg of hydrogenated palm oil was melted, and the primary core particles were placed in a fluidized bed, and the melted hydrogenated palm oil was sprayed into the fluidized bed to obtain rumen-bypass choline chloride having an effective choline chloride content of not less than 25% (mass fraction).

[0135] Comparative Example 3

[0136] The raw material composition is as follows in percentage by mass: 28% of choline chloride; 23% of silicon dioxide; 5% of corn starch; 3% of magnesium stearate; 20% of palm oil; 10.5% of polyacrylic acid resin IV; and 10.5% of chitosan.

[0137] The specific preparation process is as follows:

[0138] (1) 280 kg of choline chloride was mixed with 230 kg of silicon dioxide, 50 kg of corn starch, and 30 kg of magnesium stearate, and then pulverized to obtain a mixture I;

[0139] (2) Melting 200 kg of palm oil and thoroughly stirring it with mixture I, and then extruding and granulating it using a hot melt extruder to obtain primary core particles;

[0140] (3) 105 kg of polyacrylic acid resin IV was added to 95% (V / V) ethanol solution to prepare a 3% (W / V) polyacrylic acid resin IV solution, and 105 kg of chitosan was added to 4% (V / V) glacial acetic acid solution to prepare a 3% (W / V) chitosan solution. The solution was sprayed onto the surface of the primary core particles in a fluidized bed to obtain rumen-bypass choline chloride with an effective choline chloride content of not less than 25% (mass fraction).

[0141] The anti-hygroscopic effect of the products was evaluated by weight measurement, and the rumen passage rate and small intestinal dissolution rate of the products of the above examples and comparative examples were determined by nylon bag degradation method.

[0142] Experimental content:

[0143] 10 g of each sample of the embodiment and the comparative example were placed in a constant temperature and humidity incubator at a temperature of 25° C. and a humidity of 45%. The samples were weighed after 24 hours. Six parallel experiments were performed.

[0144] S=(m2-m1) / m1×100%

[0145] S: moisture absorption;

[0146] m1: initial mass of the sample;

[0147] m2: The mass of the sample after absorbing moisture.

[0148] Table 2 Hygroscopicity test of rumen bypass choline (%)

[0149] time <![CDATA[S 实施例1 ]]> <![CDATA[S 实施例2 ]]> <![CDATA[S 实施例3 ]]> <![CDATA[S 对比例1 ]]> <![CDATA[S 对比例2 ]]> <![CDATA[S 对比例3 ]]> 24h 0.11 0.12 0.15 0.21 0.11 0.26

[0150] From the above results, it can be seen that Example 1 and Comparative Example 2 have the lowest moisture absorption. This is because compared with other examples and comparative examples, the cores of Example 1 and Comparative Example 2 contain oil. In addition to the hydrophobic oil coating, the product of Example 1 also has polyacrylic resin IV and chitosan coating. The hydrophobic oil content of the coating layer in Comparative Example 2 is the highest.

[0151] Fistula cattle were used to detect the rumen passage rate and small intestinal digestibility of the products of this embodiment and the comparative example. The experimental content is as follows: a nylon filter cloth with a pore size of 50 μm was selected to make a nylon bag of 10 cm × 20 cm (length × width). 7 g of feed sample was accurately weighed in the nylon bag, and the nylon bag mouth was tightened with a rubber band. Three repetitions were set for each cow at each time point. The feed was put in before morning feeding and put into the rumen in sequence according to the time points of 48, 36, 24, 16, 12, 8, 4, 2, and 0 h. Finally, all the nylon bags were taken out at 0 h and rinsed with cold water until the running water was clear. The rinsed nylon bags were placed in a 55°C oven and dried for 48 h to a constant weight, and the total weight of the drying was recorded. According to national standards, the choline content in the feed additive was determined by the Reinecke salt weight method.

[0152] Table 3 Rumen bypass rate of choline (%)

[0153] time Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 0h 98.50±0.19 98.36±0.30 97.59±0.34 85.84±0.20 98.74±0.25 90.08±0.23 2h 97.64±0.16 97.28±0.15 95.40±0.34 80.68±0.12 97.74±0.14 84.83±0.11 4h 94.71±0.13 94.42±0.24 93.94±0.37 79.68±0.23 94.73±0.23 84.21±0.18 8h 93.96±0.22 93.86±0.12 93.41±0.20 77.53±0.27 94.28±0.20 83.48±0.44 12h 93.56±0.06 93.43±0.13 93.09±0.12 75.82±0.21 93.87±0.22 82.52±0.76 16h 92.80±0.21 92.73±0.24 93.08±0.12 75.04±0.34 93.68±0.18 82.25±0.48 24h 91.78±0.14 91.68±0.14 92.83±0.17 74.89±0.09 92.35±0.12 79.20±0.66 36h 91.74±0.06 91.51±0.17 91.45±0.11 69.08±0.14 92.03±0.25 75.66±0.12 48h 91.42±0.36 91.33±0.20 90.48±0.21 67.33±0.25 91.88±0.16 70.04±0.89

[0154] As can be seen from Table 3, the rumen-passing effects of Comparative Example 1 (no oil added during granulation) and Comparative Example 3 (no oil added to the coating layer, polyacrylic acid resin IV and chitosan coating) are both poor.

[0155] The in vitro three-step method was used to determine the small intestinal digestibility of rumen-bypass choline samples. The rumen-bypass choline samples were placed in the rumen of dairy cows for 16 hours, then removed and pretreated according to the in vitro three-step method. The small intestinal digestibility was then determined under digestive enzyme treatment. The specific method is as follows:

[0156] 1. Approximately 7 g of the feed samples from Examples 1-3 and Comparative Examples 1-3 were placed in rumen nylon bags. The bags were tied tightly with rubber bands. Three replicates were set up for each cow at each time point. The feed was placed in the rumen of the cow in the morning, removed 16 hours later, rinsed, and then dried at 55°C for 48 hours to constant weight.

[0157] 2. Place 1g of the residual sample after rumen degradation into a nylon bag (5cm x 10cm). Incubate up to 12 bags per 2L Erlenmeyer flask. Place 2L of preheated hydrochloric acid solution (pH 1.9) containing 1g / L pepsin (P-7012, Sigma, USA, activity ≥2500U / mg prot, 100% titer) in the flask. Incubate at 39°C for 1 hour. After incubation, remove the nylon bag, drain, and rinse with tap water until clear.

[0158] 3. Place the cleaned nylon bag into a 2 L conical flask and add preheated 0.5 mol / L phosphate buffer containing 3 g / L trypsin (P-7545, Sigma, USA, activity, 8 USPU (United States Pharmacopoeia Units)) and 50 μg / L thymol, pH = 7.75, and incubate at 39°C with constant rotation. After 24 hours, remove the bag, wash, dry, weigh, and measure the degradation rate.

[0159] Small intestine digestibility = (choline content of original feed - choline content in residue after enzymatic hydrolysis) / choline content of original feed × 100%

[0160] Table 4 Small intestinal digestibility of choline chloride by rumen (%)

[0161] index Small intestinal digestibility Example 1 97.85±0.13 Example 2 98.82±0.11 Example 3 98.92±0.06 Comparative Example 1 99.08±0.04 Comparative Example 2 76.43±0.88 Comparative Example 3 99.70±0.25

[0162] As can be seen from Table 4, the small intestine digestibility of rumen-free choline in Comparative Example 2 (oil coating only) is the lowest.

[0163] In summary, the rumen passage rate and small intestinal release rate of Examples 1, 2 and 3 all reached a high level. However, considering that chitosan needs to be dissolved in an acetic acid aqueous solution and the drying time during coating is relatively long, we recommend selecting the formula of Example 2 in actual production.

[0164] Industrial applicability

[0165] The rumen bypass choline chloride granules provided by the present invention have high rumen bypass rate and small intestine digestibility. The preparation method of the rumen bypass choline chloride granules provided by the present invention is simple to operate and suitable for large-scale industrial production.

Claims

1. A rumen bypass choline chloride granule, characterized in that: The rumen bypass choline chloride granules include: A core, an inner coating film wrapped around the core, and an outer coating film wrapped around the inner coating film; Furthermore, the core comprises choline chloride and a carrier of the choline chloride, and the carrier comprises a first oily component; The inner coating film includes a second oily component; and The outer coating film comprises a pH sensitive material; The melting point of the first oily component is 37-46°C, and the melting point of the second oily component is above 60°C. Based on the total mass of the rumen bypass choline chloride granules, the granules contain 25% to 65% by mass of choline chloride, 5% to 20% by mass of a first oily component, 10% to 20% by mass of a second oily component, and 2% to 5% by mass of a pH-sensitive material; The pH sensitive material is polyacrylic acid resin IV and / or chitosan.

2. The rumen bypass choline chloride granules according to claim 1, characterized in that The first oily component is selected from one or more of vegetable oils and waxes.

3. The rumen bypass choline chloride granules according to claim 1, characterized in that The second oily component is selected from one or more of plant oils and waxes.

4. The rumen bypass choline chloride granules according to any one of claims 1 to 3, characterized in that The carrier also contains a filler, a binder, and a lubricant; The filler comprises at least one selected from the group consisting of silicate, zeolite powder, silicon dioxide and perlite; The binder comprises at least one selected from the group consisting of potato starch, corn starch and hydroxypropyl methylcellulose; The lubricant includes at least one selected from the group consisting of zinc stearate, magnesium stearate, and calcium stearate.

5. The rumen bypass choline chloride granules according to claim 4, characterized in that Based on the total mass of the rumen bypass choline chloride granules, the granules contain 10% to 23% by mass of a filler, 1% to 5% by mass of a binder, and 1% to 3% by mass of a lubricant.

6. A method for preparing rumen bypass choline chloride granules according to any one of claims 1 to 5, characterized in that: The preparation method comprises the following steps: Granulation step: mixing choline chloride, a carrier and a first oily component and then performing hot-melt granulation to obtain a core; The coating step comprises heating and melting the second oily component and then spraying the core with the first coating, dissolving the pH sensitive material in an organic solvent and then spraying the core with the first coating for the second coating.

7. The preparation method according to claim 6, characterized in that The granulation step is completed by a hot melt extruder, and the coating step is completed by a fluidized bed.

8. An animal feed, characterized in that The feed comprises the rumen bypass choline chloride granules according to any one of claims 1 to 5.

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