CN111116394B - Preparation method and application of ferrous valine - Google Patents
Preparation method and application of ferrous valine Download PDFInfo
- Publication number
- CN111116394B CN111116394B CN201911365936.3A CN201911365936A CN111116394B CN 111116394 B CN111116394 B CN 111116394B CN 201911365936 A CN201911365936 A CN 201911365936A CN 111116394 B CN111116394 B CN 111116394B
- Authority
- CN
- China
- Prior art keywords
- valine
- ferrous
- salt
- reaction
- inorganic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
-
- 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
-
- 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
- A23K20/30—Oligoelements
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K50/00—Feeding-stuffs specially adapted for particular animals
- A23K50/30—Feeding-stuffs specially adapted for particular animals for swines
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K50/00—Feeding-stuffs specially adapted for particular animals
- A23K50/60—Feeding-stuffs specially adapted for particular animals for weanlings
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K50/00—Feeding-stuffs specially adapted for particular animals
- A23K50/70—Feeding-stuffs specially adapted for particular animals for birds
- A23K50/75—Feeding-stuffs specially adapted for particular animals for birds for poultry
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Animal Husbandry (AREA)
- Food Science & Technology (AREA)
- Birds (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of ferrous valine, which comprises the following steps: (1) Adding valine into water, adding sodium carbonate/potassium carbonate, stirring for reaction until no air bubbles emerge, and obtaining a valine salt solution; (2) Heating a valine salt solution, adding inorganic ferrous salt for reaction, and after the reaction is finished, carrying out solid-liquid separation and drying to obtain the ferrous valine. The invention also provides application of the ferrous valine as an animal feed additive in animals. In the invention, the reaction is divided into two steps, sodium carbonate salt/potassium carbonate salt is added into a valine solution to react to generate valine salt, and the product is obtained by utilizing the reaction of the valine salt and inorganic ferrous salt, so that the side reaction is less, and the product purity is high.
Description
Technical Field
The invention belongs to the field of animal feed additives, and particularly relates to a preparation method and application of an amino acid chelate.
Background
The trace element iron is one of the essential trace elements of animals. Iron is an important part of hemoglobin, and is present in red blood cells that supply oxygen to muscles, and is a component of many enzymes and immune system compounds. Iron can participate in oxygen transportation and storage, promote development, increase resistance to diseases, regulate tissue respiration, prevent fatigue, form heme, prevent and treat anemia caused by iron deficiency, and make animal skin bright with red hair. Animals take the majority of the iron needed from food and it is generally accepted in the art or related art that animals take little to no ferric iron for absorption. The iron element currently known and reported to be assimilated by animals is generally present in the form of divalent iron.
Valine, as a branched chain amino acid essential to livestock and poultry, can significantly improve the growth performance of animals and provide energy for organisms to synthesize nutrients. In addition, valine is also useful for synthesizing proteins, providing oxidative energy in a specific physiological period, mobilizing protein turnover in skeletal muscle, improving lactation performance, regulating nerves and endocrine, enhancing immune function, and the like.
The preparation method and application of ferrous valine are not reported in the prior art.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and defects mentioned in the background technology, and provide a preparation method and application of ferrous valine with the advantages of less side reaction and the like. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of ferrous valine comprises the following steps:
(1) Adding valine into water, adding sodium carbonate/potassium carbonate, stirring for reaction until no air bubbles emerge, and obtaining a valine salt solution;
(2) Heating a valine salt solution, adding inorganic ferrous salt for reaction, and after the reaction is finished, carrying out solid-liquid separation and drying to obtain the ferrous valine. The molecular formula of the ferrous valine is Fe (C) 5 H 10 NO 2 ) 2 ·H 2 And (O). In the above steps, even if the solution contains a trace amount of ferrous carbonate, the ferrous carbonate can react with the valine salt to generate the ferrous valine.
Because ferrous sulfate or ferrous chloride can not be directly mixed with valine for reaction, alkali needs to be added, if the ferrous chloride, the ferrous sulfate and the alkali are directly mixed, ferrous hydroxide is firstly generated, then the ferrous hydroxide is quickly oxidized by oxygen in water to generate ferric hydroxide, and finally the ferric oxide with black color is generated by dehydration. Ferric iron is much less available for absorption in animals than ferrous iron. In addition, when heating is performed at a high alkali concentration, other side reactions such as dehydration condensation reaction of valine and the like may occur. In the invention, the reaction is divided into two steps, sodium carbonate salt/potassium carbonate salt is added into a valine solution to react to generate valine salt, and the product is obtained by utilizing the reaction of the valine salt and inorganic ferrous salt, so that the side reaction is less, and the product purity is high.
In the preparation method, preferably, the reduced iron powder is added after the inorganic ferrous salt is added, the addition amount of the reduced iron powder is 0.1-0.15% of the mass of the inorganic ferrous salt, and the particle size of the reduced iron powder is 10-200 meshes.
Because ferrous ions can react with weak oxygen in the solution to generate ferric ions, the reaction solution turns yellow, and the content of the ferric ions in the finally obtained product exceeds the standard. After the reduced iron powder is added into the reaction system, the reaction system is changed from light yellow to light green or blue green without the protection of inert gas. The particles of the reduced iron powder are too coarse, the specific surface area of the reaction is small, and the phenomenon that the reduced iron powder is wrapped by a product or the reaction is incomplete after a part of the reaction possibly exists; the fine particles of the fine reduced iron powder and the reaction rate are too fast and may not have the effect of protecting the oxidation of the ferrous ions into the ferric ions during the entire reaction, so the particle size of the fine reduced iron powder needs to be controlled to 10-200 mesh. In addition, the addition amount of the reduced iron powder is too small, the reaction system is still light yellow, part of ferric ions exist, the addition amount of the reduced iron powder is too large, too much reduced iron powder is remained after the reaction is finished, the filtration is needed, otherwise, a large amount of reduced iron powder is brought into the product to influence the purity of the product, and therefore, the addition amount of the reduced iron powder is 0.1-0.15% of the mass of the inorganic ferrous salt, which is the optimal choice.
The reduced iron powder has the parameters reaching the standard, namely Fe is more than or equal to 98 percent, carbon is less than or equal to 0.01 percent, phosphorus and sulfur are less than 0.03 percent, and the hydrogen loss is 0.1 to 0.2 percent.
In the above preparation method, preferably, the carbonate includes normal salt and acid salt; the normal salt comprises sodium carbonate and/or potassium carbonate; the acid salt comprises sodium bicarbonate and/or potassium bicarbonate; the inorganic ferrous salt comprises at least one of ferrous chloride and ferrous sulfate, and the ferrous sulfate also comprises a hydrated ferrous sulfate and other forms containing crystal water.
In the above production process, it is preferable to control the molar ratio of normal salt to valine to be (1.01 to 1.02): controlling the molar ratio of the acid salt to the valine to be (1.01-1.02): 1.
in the above preparation method, preferably, the molar ratio of the inorganic ferrous salt to valine is controlled to be (0.97-1.03): 2.
in the preparation method, preferably, in the step (2), when the inorganic ferrous salt is added for reaction, the reaction temperature is controlled not to exceed 48 ℃, and the reaction time is 1.1-2h after the inorganic ferrous salt is added. The reaction temperature and the reaction time are not preferably too long. Because of the high temperature and prolonged reaction time, ferrous ions will form ferrous hydroxide with the ionized trace amount of hydroxyl ions in the solution and will be quickly oxidized by the oxygen in the solution to ferric hydroxide, resulting in a reduction in product purity. In addition, valine may cause side reactions such as condensation, so the reaction temperature cannot be too high. The reaction time is too short, incomplete reaction is easily caused, and the product conversion rate is low; the reaction conversion rate is not obviously increased after the reaction time is too long, and part of water is evaporated, so that the materials are too viscous and conglomerated, the crystallization granularity is influenced, and the discharging and centrifuging are not good. The proper reaction time can ensure complete reaction and higher yield, and reduce the raw material waste caused by insufficient reaction time and the energy consumption caused by long-time reaction.
In the above production method, preferably, in the step (2), the solid content of the reaction system is 18 to 28%. The solids content is related to the volume of solution added, i.e. to the amount of water added. If the water adding amount is too small, most raw materials cannot be uniformly diffused, and the raw materials are wrapped by the product, so that the collision reaction probability is reduced, and the reaction rate is very low; the reaction system becomes more viscous due to the concentration problem, and the reaction product wraps the raw materials, so that the reaction rate is finally influenced. Meanwhile, too much water can affect the subsequent crystallization yield and increase the filtering workload.
In the above preparation method, preferably, after the reaction is finished, an organic solvent is added for crystallization, and then solid-liquid separation and drying are performed, wherein the organic solvent is one or more of ethanol, propanol and isopropanol, and the volume ratio of the organic solvent to the reaction solution after the reaction is finished is (0.05-0.2): 1. because the solubility of the valine in water at 25 ℃ is 88.5g/L, the valine is slightly soluble in ethanol, propanol and isopropanol, the ferrous valine is similar to the valine in property, and the solubility of the ferrous valine in water is higher than that of the ferrous valine in an organic solvent, the addition of the organic solvent is beneficial to crystallization, and the yield is improved. Because the solubility of the sodium salt and the potassium salt of the by-product in water is high, when the ferrous valine is crystallized, the by-product still remains in a liquid phase, and the solid-liquid separation is directly carried out.
As a general technical concept, the invention also provides an application of the ferrous valine as an animal feed additive in animals, wherein the animals are pigs, poultry, ruminants and aquatic animals, and the molecular formula of the ferrous valine is Fe (C) 5 H 10 NO 2 ) 2 ·H 2 O, ferrous valine are prepared by the preparation method.
In the application, preferably, the addition amount of the ferrous valine in each ton of pig feed is 30-120ppm calculated by iron element; the addition amount of the iron element in each ton of poultry feed is 30-100ppm.
The amino acid complex as the 3 rd generation microelement additive has excellent biological functions which are proved by a large number of tests, compared with inorganic microelement additives, the amino acid complex has better chemical stability, can obviously improve the bioavailability of microelements, improves the growth performance of animals, enhances the immunity and the anti-stress capability, improves the quality of animal products, can reduce the addition of the microelements by using the amino acid complex, and reduces the pressure to the environment while keeping the microelements in the animals at a high level. The invention utilizes the combination of valine and inorganic ferrous salt to exert the advantages of the valine and the inorganic ferrous salt.
The invention is based on the following principle:
firstly, reacting carbonate/bicarbonate with valine at normal temperature to generate valine salt and carbon dioxide; taking carbonate as an example, the reaction equation is as follows:
Na 2 CO 3 +2C 5 H 11 NO 2 +H 2 O＝2C 5 H 10 NO 2 Na·H 2 O+CO 2 ↑；
K 2 CO 3 +2C 5 H 11 NO 2 +H 2 O＝2C 5 H 10 NO 2 K·H 2 O+CO 2 ↑。
secondly, reacting valine salt with ferrous salt under heating to generate ferrous valine and sodium salt/potassium salt; taking ferrous sulfate and ferrous chloride as examples, the reaction equation is as follows:
2C 5 H 10 NO 2 Na·H 2 O+FeSO 4 ＝(C 5 H 10 NO 2 ) 2 Fe·H 2 O+Na 2 SO 4 ；
2C 5 H 10 NO 2 Na·H 2 O+FeCl 2 ＝(C 5 H 10 NO 2 ) 2 Fe·H 2 O+2NaCl；
2C 5 H 10 NO 2 K·H 2 O+FeSO 4 ＝(C 5 H 10 NO 2 ) 2 Fe·H 2 O+K 2 SO 4 ；
2C 5 H 10 NO 2 K·H 2 O+FeCl 2 ＝(C 5 H 10 NO 2 ) 2 Fe·H 2 O+2KCl。
in the invention, the pH value of the valine is 5.5-6.5, and the valine is weakly acidic. The carbonate is strong base and weak acid salt, is not strong base, and has mild reaction with valine. Valine reacts with carbonate/bicarbonate to form valine salts and carbon dioxide.
According to the invention, valine is firstly reacted with carbonate with weak alkalinity at normal temperature. Heating is not required because valine reacts mildly with carbonate and is exothermic. As the reaction proceeds, carbonate is continuously consumed, the generated carbon dioxide can continuously escape, and the pH value is gradually changed from alkalinity to alkalescence. but-NH at valine at pH < 7.5 2 and-COO - Intermolecular dehydration condensation reaction may occur. Therefore, in the present invention, the adjustment of pH is not emphasized, butA slight excess of base is required to reduce the occurrence of side reactions. However, if the carbonate is excessive, the alkaline concentration in the solution is too high, and carbonate ions can be generated in the carbonic acid formed after the escaped carbon dioxide is dissolved in water in the solution with higher pH value, and the carbonate ions react with subsequent ferrous ions to generate ferrous carbonate, which is not beneficial to the subsequent reaction. And the alkaline solubility is too high, after the ferrous salt is added, ferrous ions can generate ferrous hydroxide and can be quickly oxidized into ferric hydroxide by the solution, so that the product purity is reduced.
In the invention, the carbonate does not generate decomposition reaction in a lower-temperature aqueous solution to generate carbon dioxide to escape, so the default is that the bubble is generated as a byproduct generated by the reaction of the carbonate and valine. And (3) stirring until no bubbles emerge, defaulting to the fact that the valine and the carbonate have basically completely reacted, and even if the valine and the carbonate are not completely reacted, a small amount of residual valine and carbonate can be continuously reacted without influencing the subsequent reaction.
Compared with the prior art, the invention has the advantages that:
1. compared with other ferrous products, the valine ferrous is a restricted ferrous amino acid product, and can be preferentially absorbed by animals, so that the yield utilization rate is higher, and the application prospect is good.
2. In the invention, the reaction is divided into two steps, sodium carbonate salt/potassium carbonate salt is added into a valine solution to react to generate valine salt, and the product is obtained by utilizing the reaction of the valine salt and inorganic ferrous salt, so that the side reaction is less, and the product purity is high.
3. The invention only needs to calculate the weight of the added insoluble ferrous iron source and the added carbonate, does not need to adjust the pH value in the reaction, and can reduce the workload.
4. The preparation method has the advantages of high chemical reaction rate, high product yield, high product purity, no by-product and the like. In addition, the method of the invention can also reduce energy consumption, simplify the process and avoid waste liquid discharge and environmental pollution.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is an XRD pattern of ferrous valine prepared in example 1.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
The ferrous content of the product in the following examples is determined by ammonium ferrous sulfate titration, the valine content is determined by nitrogen determination, and water loss at 180 ℃ is lost as crystal water, and water loss at 104 ℃ is lost as free water.
Example 1:
a preparation method of ferrous valine comprises the following steps: starting stirring, adding 239.1Kg of valine with the purity of 98% into 2.2t of water, starting stirring, adding 109.2Kg of sodium carbonate with the purity of 98%, stirring until no bubbles emerge, adding 171.7Kg of ferrous sulfate monohydrate with the purity of 96%, heating to 30 ℃, reacting for 2h, after the reaction is finished, performing pressure filtration, and performing flash evaporation and drying to obtain 301.8Kg of a product.
In this example, the valine content of the ferrous valine product was determined to be 73.7%, fe 2+ 16.0% of Fe 3+ 1.7 percent, the water loss rate at 180 ℃ is 5.7 percent, the water loss rate at 104 ℃ is 2.4 percent, namely the purity is 97.1 percent, and the yield is reducedThe rate was 98.7% calculated as total iron, i.e. the molar ratio of valine to ferrous was about 2:1, molecular formula of Fe (C) 5 H 10 NO 2 ) 2 ·H 2 And O. The powder diffraction pattern of the ferrous valine obtained in this example is shown in FIG. 1.
Example 2:
a preparation method of ferrous valine comprises the following steps: starting stirring, adding 239.1Kg of valine with the purity of 98% into 2.3t of water, starting stirring, adding 143.9Kg of potassium carbonate with the purity of 98%, stirring until no bubbles emerge, adding 249.4Kg of ferrous sulfate pentahydrate with the purity of 98%, heating to 40 ℃, adding 0.37Kg of 10-mesh reduced iron powder, reacting for 1.5h, cooling to below 40 ℃ after the reaction is finished, adding 190L of ethanol, crystallizing, centrifuging, drying in a drying room, and obtaining 299.6Kg of product.
The valine content in the ferrous valine product is 74.6 percent and the Fe content is measured 2+ 17.8% of Fe 3+ 0.1%, a water loss of 5.8% at 180 ℃ and a water loss of 1.0% at 104 ℃, i.e. a purity of 98.3%, the yield is 96.2% calculated on valine, i.e. the molar ratio of valine to ferrous is about 2:1, molecular formula of Fe (C) 5 H 10 NO 2 ) 2 ·H 2 O。
Example 3:
a preparation method of ferrous valine comprises the following steps: starting stirring, adding 239.1Kg of valine with the purity of 98% into 2.0t of water, starting stirring, adding 173.1Kg of sodium bicarbonate with the purity of 98%, stirring until no bubbles emerge, adding 280.9Kg of ferrous sulfate heptahydrate with the purity of 99%, heating to 45 ℃, adding 0.28Kg of 40-mesh reduced iron powder, reacting for 1.8h, cooling to below 40 ℃ after the reaction is finished, adding 420L of isopropanol, crystallizing, centrifuging, and flash-evaporating for drying to obtain 305.1Kg of product.
The valine content in the ferrous valine product is 74.1 percent and the Fe content is measured 2+ 17.7% of Fe 3+ 0.1 percent, the water loss rate at 180 ℃ is 5.7 percent, the water loss rate at 104 ℃ is 2.0 percent, namely the purity is 97.7 percent, the yield is 97.4 percent calculated by valine, namely the molar ratio of the valine to the ferrousThe ratio is about 2:1, molecular formula of Fe (C) 5 H 10 NO 2 ) 2 ·H 2 O。
Example 4:
a preparation method of ferrous valine comprises the following steps: starting stirring, adding 239.1Kg of valine with the purity of 98% into 1.5t of water, starting stirring, adding 208.5Kg of potassium bicarbonate with the purity of 98%, stirring until no bubbles emerge, adding 206.9Kg of ferrous chloride tetrahydrate with the purity of 99%, heating to 48 ℃, adding 0.23Kg of 200-mesh reduced iron powder, reacting for 1.1h, cooling to below 40 ℃ after the reaction is finished, adding 340L of propanol, crystallizing, centrifuging, and flash evaporating for drying to obtain 300.2Kg of product.
The valine content in the ferrous valine product is 74.7 percent and the content of Fe is measured 2+ 17.9% of Fe 3+ 0.03%, a water loss of 5.8% at 180 ℃ and a water loss of 1.3% at 104 ℃, i.e. a purity of 98.4%, a yield of 96.5% calculated on valine, i.e. a molar ratio of valine to ferrous of about 2:1, molecular formula of Fe (C) 5 H 10 NO 2 ) 2 ·H 2 O。
Application example 1:
the ferrous valine prepared in example 1 was used in feeding test of weaned piglets.
And (3) experimental design: 144 weaned piglets with 25 days of age and similar weight are selected and randomly divided into 4 groups, each group has 6 repetitions, 6 pigs are repeated, 1 group is a control group and is fed with ferrous sulfate monohydrate, the dosage is 150mg/kg calculated by iron, 2-4 groups are respectively fed with ferrous valine accounting for 60, 80 and 120mg/kg calculated by iron, the formula of the experimental daily ration is designed according to NRC2012 nutritional standards, and the other nutritional water is kept consistent on average except that the iron source and the additive amount of each treatment group are inconsistent. The test period was 28 days, during which the initial temperature was 26 ℃ and then decreased by 1 ℃ every 7 days, the relative humidity was maintained at 65-75%. The experimental piglets are raised at 1.2 multiplied by 2m in different columns 2 In the ring, a plastic-sprayed floor with a leak, a stainless steel adjustable trough and a nipple-shaped water fountain. The powder is used for feeding, and the food is taken and drunk freely.
Detection indexes are as follows: the feed intake of each repetition is recorded in the test process, the weight of each repetition is weighed at the beginning and the end of the test, the red wetness degree of the center of the hip of each repeated piglet is detected in the last day of the test, and the number of dead and washed piglets of each repetition in the test process is recorded.
The test results are shown in table 1 below:
table 1: influence of different iron sources and gradients on growth performance and fur appearance of weaned piglets
In the above table, L is an expression of skin brightness, and the higher the L value, the whiter the skin, and the lower the L value, the blacker the skin. A is the expression of redness, the higher the A value, the more red the skin, the lower the A value, the greener the skin. The higher the B value, the more yellow the skin, and the lower the B value, the more blue the skin. The smaller the P value, the more significant the result. In the same row, the different superscript letters a and b represent significant differences.
From the above table, the treatment group with the addition of 120mg/kg of ferrous valine calculated as iron showed the best effect, compared with ferrous sulfate monohydrate, the daily gain increased by 10.8%, and the material weight ratio decreased by 5.2%, and from the viewpoint of skin redness, the addition of 120mg/kg of ferrous valine calculated as iron showed the best skin brightness and redness. The addition of 60mg/kg ferrous valine calculated by iron can replace 150mg/kg ferrous sulfate monohydrate calculated by iron, but the addition of 120mg/kg ferrous valine calculated by iron has the best effect, so that the addition of 60-120mg/kg ferrous valine calculated by iron in the weaned piglet feed is recommended to replace the currently commonly used ferrous sulfate to improve the growth performance of animals and the appearance of fur.
Application example 2:
the ferrous valine prepared in example 2 was used for broiler feeding test
And (3) experimental design: 480 feathers are selected to hatch 1-day-old healthy Yijia broilers from the same hatchery. The broiler chicken is placed in a broiler chicken cage for feeding, freely takes food and water during the whole process, and is immunized according to a conventional immunization program. Randomly divided into 4 groups of 6 replicates each, each replicate 20 feathers. Wherein 1 group of control groups are fed with 100mg/kg ferrous sulfate monohydrate calculated by iron, the 1-3 groups of treatment groups are respectively fed with 30, 60 and 100mg/kg ferrous valine calculated by iron to replace the ferrous sulfate, except for the iron source and the dosage, other factors of each treatment group in the daily ration are kept consistent, the test period is 42 days, and the feeding management is carried out according to the AA broiler feeding management manual.
Detection indexes are as follows: the broilers are weighed on the 1 st day and the 42 th day of the test, the feed intake and the death number of the broilers are recorded, and the average daily gain, the average daily feed intake, the feed-weight ratio and the death rate in different stages are calculated.
The test results are shown in table 2 below:
table 2: influence of different iron sources and dosages on growth performance and death rate of Aliguajia broiler chickens
From the above table, it can be seen that the growth performance of ferrous valine of 30mg/kg in terms of iron can achieve the effect of ferrous sulfate monohydrate of 100mg/kg in terms of iron, and the influence of ferrous valine of 60mg/kg in terms of iron and ferrous valine of 100mg/kg in terms of iron on the growth performance and the mortality of animals is not significant, but is better than the effect of ferrous sulfate of 100mg/kg in terms of iron, so that the dosage of the ferrous valine in broiler chickens is 30-100mg/kg in terms of iron, and the broiler chickens have better growth performance and better survival rate performance.
Application example 3:
the ferrous valine prepared in example 3 was used in the feeding test of laying hens
And (3) experimental design: 1200 feathers of 420-day-old Hailan-brown laying hens are selected and placed in a laying hen cage for feeding, and the feathers are randomly divided into 4 groups, each group has 6 repetitions, and each repetition has 50 feathers. Wherein 1 group of control groups is fed with 80mg/kg ferrous sulfate calculated by iron, the treatment groups 1-3 are respectively fed with 40, 60 and 80mg/kg ferrous valine calculated by iron to replace the ferrous sulfate, other factors of each treatment group in the experimental daily ration are kept consistent except the iron source and the dosage, the experimental period is 56 days, and the whole course is freely eaten and drunk, so that the illumination is ensured for 16 hours every day.
Detection indexes are as follows: calculating the laying rate, the egg breaking rate and the feed-egg ratio of each repeated egg on the 5 th day of the test; randomly extracting 20 eggs and calculating the proportion of the white-shell eggs.
The test results are shown in table 3 below:
table 3: effect of different iron sources and dosages on eggshell color and egg laying performance
From the above table, it is known that the effect of ferrous valine of 40mg/kg calculated by iron on egg laying performance and egg shell color improvement is equivalent to that of ferrous sulfate of 80mg/kg calculated by iron, the effect of ferrous valine of 60mg/kg and 80mg/kg calculated by iron on egg shell color, egg breaking rate and egg laying performance improvement is better than that of ferrous sulfate of 80mg/kg calculated by iron, and it is recommended to add ferrous valine of 60-80mg/kg calculated by iron to daily feed of laying hens to replace ferrous sulfate. If the economic cost is considered, 40-60mg/kg ferrous valine in terms of iron is added into daily ration of the laying hens.
Claims (3)
1. The preparation method of the ferrous valine is characterized by comprising the following steps of:
(1) Adding valine into water, adding sodium carbonate/potassium carbonate, stirring for reaction until no air bubbles emerge, and obtaining a valine salt solution;
(2) Heating a valine salt solution, adding inorganic ferrous salt for reaction, and after the reaction is finished, carrying out solid-liquid separation and drying to obtain the ferrous valine;
the sodium carbonate salt/potassium carbonate salt is normal salt and acid salt; the normal salt is sodium carbonate and/or potassium carbonate; the acid salt is sodium bicarbonate and/or potassium bicarbonate; the inorganic ferrous salt comprises at least one of ferrous chloride and ferrous sulfate;
controlling the molar ratio of the normal salt to the valine to be (1.01-1.02): controlling the molar ratio of the acid salt to the valine to be (1.01-1.02): 1;
adding reduced iron powder after adding the inorganic ferrous salt, wherein the adding amount of the reduced iron powder is 0.1-0.15% of the mass of the inorganic ferrous salt, and the granularity of the reduced iron powder is 10-200 meshes;
controlling the molar ratio of the inorganic ferrous salt to the valine to be (0.97-1.03): 2;
when inorganic ferrous salt is added for reaction, the reaction temperature is controlled not to exceed 48 ℃, and the reaction time is 1.1-2h after the inorganic ferrous salt is added.
2. The production method according to claim 1, wherein in the step (2), the solid content of the reaction system is 18 to 28%.
3. The preparation method according to claim 1, wherein an organic solvent is added after the reaction is finished, the mixture is crystallized and then subjected to solid-liquid separation and drying, the organic solvent is one or more of ethanol, propanol and isopropanol, and the volume ratio of the organic solvent to the reaction solution after the reaction is finished is (0.05-0.2): 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911365936.3A CN111116394B (en) | 2019-12-26 | 2019-12-26 | Preparation method and application of ferrous valine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911365936.3A CN111116394B (en) | 2019-12-26 | 2019-12-26 | Preparation method and application of ferrous valine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111116394A CN111116394A (en) | 2020-05-08 |
| CN111116394B true CN111116394B (en) | 2022-12-13 |
Family
ID=70503057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911365936.3A Active CN111116394B (en) | 2019-12-26 | 2019-12-26 | Preparation method and application of ferrous valine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111116394B (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070269495A1 (en) * | 2006-05-18 | 2007-11-22 | Ashmead H Dewayne | Compositions and methods for enhancing mineral levels in animals with reduced environmental impact |
| CN101941915A (en) * | 2010-09-07 | 2011-01-12 | 湖北神舟化工有限公司 | Method for preparing amino acid ferrous chelates |
| CN103086901A (en) * | 2011-11-03 | 2013-05-08 | 青岛康地恩药业股份有限公司 | Preparation method of amino acid ferrous sulfate chelate |
| CN109081786A (en) * | 2018-10-15 | 2018-12-25 | 禄丰天宝磷化工有限公司 | A kind of preparation method of amino acid ferrous chelate compound |
| CN110003036A (en) * | 2019-04-24 | 2019-07-12 | 河北力维素科技有限公司 | A kind of amino acid-ferrous preparation method |
-
2019
- 2019-12-26 CN CN201911365936.3A patent/CN111116394B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111116394A (en) | 2020-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102309008B (en) | Preparation method of collagen polypeptide chelated calcium | |
| CN102550836B (en) | Animal nutrition additive trace element is combined bag and its preparation method and application | |
| CN102524540B (en) | Saving trace element compound packet as well as preparation method and application thereof | |
| CN111072508B (en) | Preparation method and application of zinc valine | |
| CN108967806A (en) | Vitamin c effervescent tablet and preparation method thereof | |
| CN102948620B (en) | Preparation method of modified methionine hydroxy analog-calcium feed additive | |
| Pandav et al. | Trials on metal enriched Spirulina platensis supplementation on poultry growth | |
| CN111116394B (en) | Preparation method and application of ferrous valine | |
| CN106243176B (en) | The copper complex formazan preparation method of sucrose | |
| CN102626181B (en) | Calcium citrate organic feed additive and preparation method thereof | |
| CN102550830B (en) | Method for applying and preparing gamma-aminobutyric acid complex compound | |
| CN102603778A (en) | N-carbamyl-L-glutamic zinc complex and preparation method of N-carbamyl-L-glutamic zinc complex | |
| RU2716989C1 (en) | Carbohydrate-vitamin-mineral saltlick concentrate | |
| CN102578386B (en) | Compound many ore deposits of glycine and its preparation method and application | |
| CN111100039A (en) | Preparation method and application of argininyl zinc | |
| CN109123101B (en) | Preparation method of manganese nicotinate | |
| RU2465783C1 (en) | Preliminarily prepared fodder mixture containing multiple microelements and mixture production method | |
| CN112409200B (en) | Preparation method and application of isoleucine chelate metal | |
| CN104605161B (en) | The preparation method and applications of glycocyamine complex | |
| CN107032410B (en) | The preparation method and applications of alkali formula manganese sulfate | |
| CN102007884A (en) | Method for producing eggs rich in multiple trace elements | |
| CN112979504B (en) | Preparation method and application of argininyl manganese | |
| CN110897039B (en) | Preparation method and application of manganese valine | |
| CN111116438B (en) | Preparation method and application of manganese cystine | |
| CN108522414A (en) | A kind of production method of high yield Se-enriched egg |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220524 Address after: 410299 No. 320, Huanglong Road, Tongguan circular economy industrial base, Wangcheng economic and Technological Development Zone, Changsha City, Hunan Province Applicant after: Xinjia Biotechnology (Changsha) Co.,Ltd. Address before: No. 370, Kangning Road, Changsha National biological industry base, Liuyang, Changsha, Hunan 410300 Applicant before: CHANGSHA XINGJIA BIO-ENGINEERING Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |