CN111227117B - Rumen bypass protection L-carnitine and preparation method and application thereof - Google Patents
Rumen bypass protection L-carnitine and preparation method and application thereof Download PDFInfo
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- CN111227117B CN111227117B CN202010048156.2A CN202010048156A CN111227117B CN 111227117 B CN111227117 B CN 111227117B CN 202010048156 A CN202010048156 A CN 202010048156A CN 111227117 B CN111227117 B CN 111227117B
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/142—Amino acids; Derivatives thereof
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/111—Aromatic compounds
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/20—Inorganic substances, e.g. oligoelements
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K40/00—Shaping or working-up of animal feeding-stuffs
- A23K40/10—Shaping or working-up of animal feeding-stuffs by agglomeration; by granulation, e.g. making powders
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K40/00—Shaping or working-up of animal feeding-stuffs
- A23K40/30—Shaping or working-up of animal feeding-stuffs by encapsulating; by coating
- A23K40/35—Making capsules specially adapted for ruminants
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/80—Food processing, e.g. use of renewable energies or variable speed drives in handling, conveying or stacking
- Y02P60/87—Re-use of by-products of food processing for fodder production
Abstract
The invention belongs to the technical field of feed additives, and particularly relates to rumen-protected L-carnitine and a preparation method and application thereof. The components of the material comprise a core material and a wall material, wherein the active ingredient of the core material is L-carnitine; the wall material comprises a polymer, tributyl citrate and talcum powder, wherein the polymer is any one or the combination of two of ethyl cellulose or polyacrylic resin IV. The preparation method comprises the steps of preparing water as an adhesive, preparing the L-carnitine into 20-40-mesh pellets by adopting a side spraying function of a fluidized bed, preparing a wall material into a solution, coating the pellets by adopting a bottom spraying function of the fluidized bed, and drying to obtain a finished product. The invention effectively reduces the damage of ruminant rumen microorganism to the bioactivity of the L-carnitine and improves the utilization value thereof; the rumen-protected L-carnitine is added into the diet, so that the amino acid balance can be effectively regulated, the protein synthesis of the body is promoted, and the reproductive performance of the ewe is improved.
Description
Technical Field
The invention belongs to the technical field of feed additives, and particularly relates to rumen-protected L-carnitine and a preparation method and application thereof.
Background
L-Carnitine (L-Carnitine) was found in 1905 to be widely present in animals, plants and microorganisms, and has various biological functions, and can not only participate in beta-oxidation of fatty acid, regulate the normal proportion of acetyl-CoA in mitochondria, promote protein synthesis, but also prevent diseases, resist fatigue and enhance immunity. In the 80 s of the 20 th century, L-carnitine was marketed abroad as a commodity and was widely used in medicine, infant food and livestock and poultry production. In recent years, the L-carnitine is taken as a safe and green nutritional feed additive in China, and has wide application in animal production because of various nutritional physiological effects of promoting animal growth, inhibiting oxidative damage, improving reproductive performance of livestock and poultry and the like. However, the use of l-carnitine in animal production has been focused on monogastric animals such as pigs and poultry, and has been relatively rarely used in ruminants such as cattle and sheep. The degradation of L-carnitine by ruminant rumen microorganisms damages the biological activity of L-carnitine to a certain extent, so that the application of the L-carnitine in ruminants is limited. The rumen bypass protection of the L-carnitine can reduce the release rate of the L-carnitine in the rumen, so that more active ingredients smoothly pass through the rumen to reach the small intestine, and the utilization rate of the L-carnitine in the small intestine is improved. The common rumen bypass protection method comprises a chemical method, a physical method and a coating method, wherein the coating method is widely applied at present, but the method has strict requirements on the selection of coating core materials and wall materials, and the corresponding preparation processes of different wall materials are different.
Disclosure of Invention
The invention aims to provide rumen protected bioactive L-carnitine, and a preparation method and application thereof.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides rumen-protected L-carnitine, which comprises a core material and a wall material, wherein the active ingredient of the core material is L-carnitine; the wall material comprises a polymer, tributyl citrate and talcum powder, wherein the polymer is any one or the combination of two of ethyl cellulose or polyacrylic resin IV.
In the technical scheme, the wall material comprises 60-80% of core material and 20-40% of wall material according to mass fraction.
In the technical scheme, further, the core material consists of 60-90% of L-carnitine and 10-40% of water according to mass fraction; the wall material consists of 75% of polymer, 12.5% of tributyl citrate and 12.5% of talcum powder.
In the above technical scheme, further, the content of the carnitine in the L-carnitine is 50.4%.
In the above technical solution, further, the wall material is one or more layers of coating.
The invention also provides a preparation method of the rumen protected L-carnitine, which comprises the following steps:
(1) Preparing L-carnitine pellets: taking L-carnitine powder as a raw material, taking 60% -90% of L-carnitine, taking 10% -40% of water as an adhesive, making pills, drying after the pills are finished, and sieving the dried L-carnitine micropills for later use;
(2) Coating: fully dissolving the wall material in 95% ethanol solution to prepare coating liquid with the concentration of 10%, coating by taking the L-carnitine pellets as core materials, and drying after coating is finished to prepare the finished product.
In the above technical solution, further, the preparation process is completed in a fluidized bed; the technological parameters of the preparation of the L-carnitine pellet fluidized bed in the step (1) are as follows: the rotating speed of the rotating disc is 600 r/min-800 r/min, and the liquid supply rotating speed is 7 r/min-10 r/min; the coating process parameters in the step (2) are as follows: the liquid supply speed is 10 rpm-20 rpm, the air inlet temperature is 50-55 ℃, and the atomization pressure is 1 bar-2 bar.
In the above technical scheme, further, the l-carnitine pellets in the step (1) are 20-40 mesh pellets, and the yield is more than 70%.
In a third aspect, the invention provides the use of rumen protected l-carnitine as a feed additive in ruminants.
The invention has the beneficial effects that: the rumen bypass protection method effectively reduces the release rate of the L-carnitine in the rumen of ruminants, ensures that more effective components smoothly pass through the rumen, and avoids the damage of rumen microorganisms to the L-carnitine active components. The adopted coating material has higher slow release performance, wherein the polyacrylic resin IV is sensitive to pH, and swells and disintegrates in low pH solution, so that the L-carnitine can be effectively digested and absorbed in the small intestine, and the occurrence of over-protection phenomenon is avoided.
The rumen protected L-carnitine can effectively regulate the amino acid balance and promote the protein synthesis of organisms when being added into diet; improving the reproductive performance of the average birth weight, weaning weight and the like of the ewes.
The fluidized bed adopted in the preparation can realize multiple functions of drying, granulating, coating, pelleting and the like, has simpler and more convenient and practical operation and control of the coating process, and avoids the limitation of the coating process on the selection of wall materials and the preparation process.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way.
Example 1
Rumen protected L-carnitine comprises the following components: core material and wall material. Wherein, the wall material comprises 80% of core material and 20% of wall material by mass fraction. The core material consists of 90% of L-carnitine and 10% of water; the wall material consisted of 67.5% ethylcellulose, 7.5% polyacrylic resin IV, 12.5% tributyl citrate, and 12.5% talc.
Specifically, the preparation method of the rumen protected L-carnitine comprises the following steps:
(1) Preparing L-carnitine pellets: the levocarnitine powder is taken as a raw material, and is subjected to pelleting by adopting a fluidized bed. Weighing L-carnitine in a side-spraying type moving bed, lifting the moving bed, setting the air inlet temperature to be 35 ℃, the atomization pressure to be 1.2bar, adjusting the gap of a rotary table, starting the rotary table, taking water as an adhesive, starting spraying to make pills when the air inlet temperature is close to the set value, adjusting the liquid supply rotating speed to be 8r/min and the rotary table rotating speed to be 800r/min according to observation and sampling, closing the spraying after the pill making is finished, drying the materials for 10min under the set temperature condition, and sieving the dried L-carnitine pellets to obtain the finished product. Wherein, the L-carnitine micropills are micropills with 20 meshes to 40 meshes, and the yield is 77.11 percent.
(2) Rumen protected l-carnitine was prepared: the L-carnitine pellets are used as core materials, and are coated by a fluidized bed. Placing the core material into a bottom-spraying type moving bed, and lifting the moving bed; the wall material is fully dissolved in 95% ethanol solution to prepare coating liquid. Setting the air inlet temperature at 55 ℃, the atomization pressure at 1.2bar and the liquid supply rotating speed at 10r/min, opening spraying to coat when the air inlet temperature is close to the set value, closing spraying after coating is finished, and drying for 10min in a heating state to obtain a finished product. Wherein the concentration of the coating liquid is 10%.
Example 2
Rumen protected L-carnitine comprises the following components: core material and wall material. Wherein, the wall material comprises 60% of core material and 40% of wall material by mass fraction. The core material consists of 90% of L-carnitine and 10% of water; the wall material consists of 71.25% of ethyl cellulose, 3.75% of polyacrylic resin IV, 12.5% of tributyl citrate and 12.5% of talcum powder.
Specifically, the preparation method of the rumen protected L-carnitine comprises the following steps:
(1) Preparing L-carnitine pellets: the levocarnitine powder is taken as a raw material, and is subjected to pelleting by adopting a fluidized bed. Weighing L-carnitine in a side-spraying type moving bed, lifting the moving bed, setting the air inlet temperature to 35 ℃, atomizing the air at 1.2bar, adjusting the gap of a rotary table, starting the rotary table, taking water as an adhesive, starting spraying to make pills when the temperature of the material is close to a set value, adjusting the liquid supply rotating speed to 8r/min and the rotary table rotating speed to 800r/min according to observation and sampling, closing the spraying after the pill making is finished, drying the material for 10min under the set temperature condition, and sieving the dried L-carnitine pellets to obtain the finished product. Wherein, the L-carnitine micropills are micropills with 20 meshes to 40 meshes, and the yield is 77.11 percent.
(2) Rumen protected l-carnitine (one layer coating) was prepared: the L-carnitine pellets are used as core materials, and are coated by a fluidized bed. Placing the core material into a bottom-spraying type moving bed, and lifting the moving bed; the wall material with the mass fraction of 20 percent is fully dissolved in 95 percent ethanol solution to prepare coating liquid. Setting the air inlet temperature at 55 ℃, the atomization pressure at 1.2bar and the liquid supply rotating speed at 10r/min, opening spraying to coat when the air inlet temperature is close to the set value, closing spraying after coating is finished, and drying for 10min in a heating state to obtain a finished product. Wherein the concentration of the coating liquid is 10%; the wall material comprises 67.5% of ethyl cellulose, 7.5% of polyacrylic resin IV, 12.5% of tributyl citrate and 12.5% of talcum powder by mass fraction.
(3) Rumen protected l-carnitine (two-layer coating) was prepared: and (3) coating the finished product in the preparation step (2) serving as a core material by adopting a fluidized bed. Placing the core material into a bottom-spraying type moving bed, and lifting the moving bed; the wall material with the mass fraction of 20 percent is fully dissolved in 95 percent ethanol solution to prepare coating liquid. Setting the air inlet temperature at 55 ℃, the atomization pressure at 1.2bar and the liquid supply rotating speed at 8r/min, opening spraying to coat when the air inlet temperature is close to the set value, closing spraying after coating is finished, and drying for 10min in a heating state to obtain a finished product. Wherein the concentration of the coating liquid is 10%; the wall material comprises 75% of ethyl cellulose, 12.5% of tributyl citrate and 12.5% of talcum powder by mass fraction.
The comparative test of the embodiment 1 and the embodiment 2 and the common L-carnitine is carried out, so that the practical application effect of the rumen protected L-carnitine on the L-carnitine is further embodied.
1. Evaluation of sustained-release effect of rumen protected L-carnitine
1.1 in vitro Release Rate assay
25.00g (accurate to 0.001 g) of the samples of the example 1, the example 2 and the common L-carnitine are accurately weighed, 500mL of buffer solution with pH of 6.6 is added, the temperature is set at 39 ℃, the rotating basket rotating speed is 80r/min, the rumen environment of ruminants is simulated, samples are respectively taken after 2 hours, 4 hours, 8 hours, 12 hours and 24 hours, the samples are dried in an oven at 65 ℃ to constant weight, the L-carnitine content in the samples is measured, the release rate of the L-carnitine is calculated, and 3 samples are parallel.
The calculation formula of the release rate of each sample at different time points:
A(％)＝(B-C)/B×100％
wherein: a-the release rate (%) of L-carnitine at different time points of the sample to be tested;
b-rumen protected content of L-carnitine (g) in bioactive L-carnitine;
C-L-carnitine content (g) in samples to be tested at different time points.
1.2 rumen bypass protection measurement
The test adopts a nylon bag method, and the degradation time is divided into 6 treatments, namely 0, 2, 4, 8, 12 and 24 hours, each treatment is repeated for 3 times, each time point of each repetition is repeated for 3 parallel sample bags, each bag sample is 7g, and 0 hour which is not subjected to rumen treatment is used as a control group. The sample obtained in example 2 was placed in a nylon bag, dried in an oven at 65 ℃ for 48 hours, and weighed for use.
And respectively digesting nylon bags in rumen for 2, 4, 8, 12 and 24 hours, taking out, slowly washing in clear water for 5-10 minutes until water flow is clear, drying in a drying oven at 65 ℃ for 48 hours, weighing, and calculating the protection rate of the sample in the rumen.
The formula:
rumen bypass protection rate (%) = sample rumen bypass post-l-carnitine content/sample corrected rumen bypass pre-l-carnitine content x 100%
1.3 measurement of small intestine degradation Rate
The degradation rate of the sample in the small intestine was determined by an in vitro method.
1.3.1 reagent preparation
(1) Acid pepsin: 1.0g of pepsin (1:10000) is accurately weighed and dissolved in 1000mL of 0.1mol/L hydrochloric acid.
(2) Pancreatic enzyme solution: weighing 6.8g KH 2 PO 4 Dissolving in 750mL distilled water, adjusting pH to 7-8 with NaOH solution, and fixing volume with distilled water in 1L volumetric flask to obtain 0.5mol/L KH 2 PO 4 3g of trypsin and 50mg of thymol are dissolved in more than 1L of solution and fully dissolved for 1h.
(3) 1.0mol/L NaOH solution.
(4) Preparing sample residues: a proper amount of the sample obtained in the example 2 is weighed into a nylon bag, placed into the rumen for 8 hours, taken out, washed until the sample is clear, dried at 65 ℃ for 48 hours, and weighed for standby.
1.3.2 test methods
(1) 60mL of acid pepsin solution is added into a culture flask containing 2g of sample, and the mixture is placed into a water bath shaking table for culture (39 ℃) for 1h;
(2) 1.5mL of 1mol/L sodium hydroxide is added into each bottle, 80mL of pancreatin solution is added for culture, the bottles are taken out respectively at 2, 4, 8, 12 and 24 hours, the bottles are slowly washed in clean water for 5 to 10 minutes until the bottles are clear, then the bottles are dried at 65 ℃ for 48 hours and then weighed, the degradation rate of rumen protected bioactive L-carnitine in the small intestine is measured, and 3 times of each time point are parallel.
1.3.3 results calculation
Small intestine degradation rate (%) = (1-sample small intestine degradation post-l-carnitine content/sample small intestine degradation pre-l-carnitine content) ×100%
1.4 results and analysis
1.4.1 in vitro sustained Release Rate determination
The sustained release rates at different time points of examples 1 and 2 from common L-carnitine are shown in Table 1.
TABLE 1 comparison of in vitro Release Rate of different products
As can be seen from table 1, the release rates of examples 1 and 2 and ordinary l-carnitine in buffer solutions with pH 6.6 increased with time. The release rate of the common L-carnitine reaches more than 90% after 2 hours, and the common L-carnitine is almost completely released after 24 hours, and compared with the common L-carnitine, the common L-carnitine has different slow release effects in examples 1 and 2. Wherein, the slow release effect of the examples 1 and 2 is enhanced along with the increase of the coating layers, the release rate of the example 1 reaches more than 70% in 8 hours, and the release rate of the example 1 is close to complete release in 24 hours, compared with the example 1, the slow release effect of the example 2 is better because the coating layers are two layers, and the slow release rate of the example 1 in 24 hours is 65.09%.
1.4.2 determination of rumen bypass protection Rate and Small intestine degradation Rate
The rumen bypass protection rate and small intestine degradation rate of example 2 are shown in table 2.
TABLE 2 rumen bypass protection and small intestine degradation at different time points
As can be seen from table 2, with the extension of time, the rumen bypass protection rate of the product obtained in example 2 gradually decreases, the small intestine degradation rate gradually increases, the rumen bypass protection rate for 8 hours is 56.04%, and the rumen bypass protection rate for 24 hours is still close to 30% of the L-carnitine, so that the L-carnitine can smoothly pass through the rumen, which indicates that the invention can effectively improve the pass rate of the L-carnitine in the rumen; the small intestine degradation rate of the product gradually increases, and the small intestine degradation rate of 24 hours exceeds 80 percent, which indicates that the invention does not have over-protection phenomenon in the small intestine.
2. Evaluation of feeding effect of rumen protected bioactive L-carnitine
2.1 materials and methods
2.1.1 test design and feeding management
30 small-tailed han sheep ewes with similar weight [ (51.78+/-7.15) kg ], good body condition and same fetus number are selected and bred by adopting an artificial insemination mode. The test adopts a single-factor completely random design, and is divided into 3 groups, each group is divided into 10 repeats, each repeat is fed by 1 sheep, each single-column is fed for 2 times per day, the free drinking water is fed at 7:00 and 16:00, the pre-feeding period is 7d, and the test is finished by the 60 th day (weaning) after delivery and is 210 days in total.
2.1.2 test diet
The control group is fed with basic ration, the test group diet is respectively added with common L-carnitine and rumen-protected bioactive L-carnitine in example 2 (the adding amount of the L-carnitine is 200 mg/kg) on the basis of the control group diet, and the basic ration is prepared by referring to NRC (2007) standard.
2.1.3 measurement index
Reproductive performance: the average lambing number of the ewes was recorded, and the lambs birth weight and weaning weight were weighed and recorded.
Biochemical indexes of blood: at the 1d of lactation period, 5mL of blood is collected from the jugular vein of each ewe by a heparin vacuum anticoagulation tube before feeding in the morning, the collected blood sample is kept stand for 30min at room temperature, and then centrifuged for 10min at 3000r/min, and the separated serum is stored at-20 ℃. And measuring the total protein and urea nitrogen content by adopting a full-automatic biochemical analyzer.
2.1.4 data processing and analysis
The data is initially arranged by Excel 2007, then single-factor analysis of variance (one-way ANOVA) and significance test are carried out by SPSS 19.0 statistical software, multiple comparison is carried out on the data by Duncan's method, the test result is represented by mean value + -standard error, and the difference is significant and is judged to be P <0.05.
2.2 results and analysis
2.2.1 Effect of rumen protected bioactive L-Carnitine on the reproductive performance of Cold-tailed sheep ewes
TABLE 3 influence of rumen protected bioactive L-carnitine on the reproductive performance of ewes of Han sheep
The different lower case letters of the same line represent significant differences (P < 0.05). Table 4 is the same.
The effect of adding L-carnitine into the diet on the average lambing number is not obvious (P is more than 0.05); the addition of L-carnitine can significantly improve the birth weight and weaning weight of the lambs (P < 0.05), and the average weaning weight of the rumen protected L-carnitine group is significantly higher than that of the common L-carnitine group (P < 0.05). (Table 3)
2.2.2 effects of rumen protected bioactive L-Carnitine on blood Biochemical index of Small tailed han sheep
TABLE 4 influence of rumen protected bioactive L-carnitine on blood Biochemical index of small tailed han sheep
The effect of adding L-carnitine into the diet on the TP content in blood is not obvious (P is more than 0.05); the addition of l-carnitine significantly reduced the BUN content in the blood (P < 0.05), and the rumen protected l-carnitine group added had significantly lower BUN content in the blood than the normal l-carnitine group (P < 0.05). (Table 4)
Many possible variations and modifications of the disclosed technology can be made by anyone skilled in the art without departing from the scope of the technology, or the technology can be modified to be equivalent. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention shall still fall within the scope of the technical solution of the present invention.
Claims (4)
1. Rumen protected L-carnitine for ewes comprises a core material and a wall material, and is characterized in that: the wall material consists of 60-80% of core material and 20-40% of wall material in mass fraction; the core material consists of 60% -90% of L-carnitine and 10% -40% of water; the wall material is coated by two layers, and the inner wall material consists of 67.5% of ethyl cellulose, 7.5% of polyacrylic resin IV, 12.5% of tributyl citrate and 12.5% of talcum powder according to mass fraction; the outer wall material consists of ethyl cellulose, tributyl citrate and talcum powder;
the preparation method of the rumen protected L-carnitine comprises the following steps:
(1) Preparing L-carnitine pellets: taking L-carnitine powder as a raw material, taking 60% -90% of L-carnitine, taking 10% -40% of water as an adhesive, making pills, drying after the pills are finished, and sieving the dried L-carnitine micropills for later use; the L-carnitine micropills are micropills with the size of 20 meshes to 40 meshes; the pellets are completed in a fluidized bed, and the technological parameters of the fluidized bed are as follows: the rotating speed of the rotating disc is 600 r/min-800 r/min, and the liquid supply rotating speed is 7 r/min-10 r/min;
(2) Coating: fully dissolving the wall material in 95% ethanol solution to prepare coating liquid with the concentration of 10%, coating by taking the L-carnitine pellets as core materials, and drying after coating is finished to prepare a finished product; the coating is done in a fluidized bed; the coating process parameters are as follows: the liquid supply speed is 10 rpm-20 rpm, the air inlet temperature is 50-55 ℃, and the atomization pressure is 1 bar-2 bar.
2. The rumen protected l-carnitine according to claim 1, wherein: the carnitine content of the L-carnitine is 50.4%.
3. The rumen protected l-carnitine according to claim 1, wherein: the yield in the step (1) is more than 70 percent.
4. Use of rumen protected l-carnitine according to claim 1 as a feed additive for improving the reproductive performance of ewes, said reproductive performance being the improvement of birth weight and weaning weight of lambs.
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| CN102326714B (en) * | 2011-09-28 | 2012-09-26 | 山东农业大学 | Ruminant rumen by-pass coating material and application thereof in choline coating |
| CA3032906A1 (en) * | 2016-08-13 | 2018-02-22 | Vivek Anand PARACHUR | Rumen bypass composition of biologically active ingredients |
| CN107712319A (en) * | 2017-09-25 | 2018-02-23 | 张自力 | A kind of ruminant animal nutrition functional feedstuff additive and its production technology |
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