CN112321484B - Preparation method of tryptophan zinc complex - Google Patents

Preparation method of tryptophan zinc complex Download PDF

Info

Publication number
CN112321484B
CN112321484B CN202011367567.4A CN202011367567A CN112321484B CN 112321484 B CN112321484 B CN 112321484B CN 202011367567 A CN202011367567 A CN 202011367567A CN 112321484 B CN112321484 B CN 112321484B
Authority
CN
China
Prior art keywords
tryptophan
zinc
reaction
preparation
carbonate
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
Application number
CN202011367567.4A
Other languages
Chinese (zh)
Other versions
CN112321484A (en
Inventor
向阳葵
邓敏
张亚伟
周孝治
倪国超
夏飞辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changsha Xingjia Biological Engineering Co Ltd
Original Assignee
Changsha Xingjia Biological Engineering Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Changsha Xingjia Biological Engineering Co Ltd filed Critical Changsha Xingjia Biological Engineering Co Ltd
Priority to CN202011367567.4A priority Critical patent/CN112321484B/en
Publication of CN112321484A publication Critical patent/CN112321484A/en
Application granted granted Critical
Publication of CN112321484B publication Critical patent/CN112321484B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/18—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D209/20—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals substituted additionally by nitrogen atoms, e.g. tryptophane
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Animal Husbandry (AREA)
  • Zoology (AREA)
  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Indole Compounds (AREA)

Abstract

The invention discloses a preparation method of a tryptophan zinc complex, which comprises the following steps: and (2) starting stirring, adding carbonate or bicarbonate into the organic solvent-water solution, stirring and dissolving, adding tryptophan, pressurizing and stirring until no bubbles emerge, heating, adding a zinc source for reaction, relieving pressure after the reaction is finished, cooling the reaction system, crystallizing, filtering, washing and drying to obtain the zinc tryptophan. The preparation method has the advantages of high reaction rate, high conversion rate, high yield, simple and convenient method, low cost, industrial large-scale production, no introduction of new impurities and no generation of byproducts. The prepared zinc tryptophan can be used as a novel nutrition enhancer, has the effect of supplementing tryptophan and trace elements compared with other zinc products, and has a good application prospect.

Description

Preparation method of tryptophan zinc complex
Technical Field
The invention belongs to the field of feed additives, and particularly relates to a preparation method of a tryptophan zinc complex.
Background
With the improvement of living standard of people and the continuous development of breeding industry, tryptophan is used as amino acid for feed and is widely used for adding piglet feed, boar feed, broiler feed, prawn feed, eel feed and the like. Tryptophan used as an animal feed additive has the following characteristics: can adjust the balance of amino acid in the feed and promote the growth of animals; can improve meat quality; can improve the nutritional value of animal feed raw materials with low amino acid digestibility; can be used for producing low-protein feed, and is beneficial to saving protein resources; the cost of raw materials of the animal feed can be reduced; can reduce the nitrogen content in the livestock and poultry manure and urine, the ammonia concentration in the livestock and poultry house and the release speed. The tryptophan is used as a common restrictive amino acid for animals, the content and the proportion of the tryptophan directly influence the nutritive value of daily ration and the production performance of livestock and poultry, and the utilization rate of feed can be improved to the maximum extent by adding the restrictive amino acid into the daily ration of the animals.
Since the first confirmation of zinc as one of the essential trace elements for animal nutrition by rat test in 1934 by Todd et al, zinc is a component of more than 200 kinds of metalloenzymes, hormones and insulin in animal organism, and has been gradually found to promote growth and tissue regeneration of organism, maintain normal metabolism of organism, promote appetite, maintain normal sexual organs and functions, accelerate wound healing, protect skin health, enhance immune mechanism and improve resistance.
The complex is the main existing form of metal elements in organisms. Many basic life processes of animals, such as respiration, nerve pulse, storage and transportation of trace elements, and the like, relate to life activities of metal ions, and are directly connected with the complex. Amino acid complexes are widely used in the field of animal technology, since their effectiveness derives from the biological action of the metals involved, acting as activators in many enzymatic reactions and as regulators in various metabolic functions of all biological organisms. Chelation of metal ions with amino acids facilitates the absorption and utilization of metal ions, since metal ions can be smoothly transported to all regions of the body by means of amino acids. Particularly in the field of animal technology, amino acid complexes are used in various breeding and breeding fields to enhance the normal metabolism of organs while improving the productivity and growth performance of animals.
The current reports on tryptophan complexes are mentioned in the section of fluorescence spectrum research on the action of different metal ions and tryptophan from Doulimei, Hu-shou Han and Zhangyi Xin (New literature): zn (II), Cr (II), Co (II), Cu (II), Fe (II) and Mo (VI) can be mixed with-COOH and-NH in amino acids in tris buffer solution with pH 6.42Coordination occurs. The synthesis method comprises the following steps: different concentrations of metal ions were added to tryptophan solutions of a given concentration and diluted with tris buffer at pH 6.4. The reaction process is not fully described, and the reproducibility of the experiment is not strong. The following are mentioned in "voltammetric studies of zinc-copper tryptophan complex" by Liu's Pinus, Ma Pei pine: adding a certain amount of 4 multiplied by 10 into 0.01mol/L borax base solution-4The standard solutions of mol/LZn (II) and Cu (II) and 0.01mol/L tryptophan were deoxygenated with nitrogen for 10min, and then stirred for 60 mins, standing for 30min to obtain copper-tryptophan complex Cu (Trp)2And zinc-tryptophan complex Zn (Trp)2. However, this method produces a mixture of copper-tryptophan complex and zinc-tryptophan complex, which is not separately purified and affected by the reaction concentration, and cannot be applied to mass production. The synthesis, characterization and flow potential method of tryptophan coordination polymer for amino acid crystallization are mentioned in doctor of Wang Jian, the article: based on L-tryptophan coordination, the coordination polymer of series Fe (II), Co (II), Ni (II), Zn (II), Cd (II) and Zn (II) is synthesized. However, in the synthesis process of the tryptophan coordination polymer, the reaction system needs to be transferred into a Teflon liner, sealed by a stainless steel pressure kettle and reacted for 72 hours at 150 ℃. The reaction process takes longer time, has high requirements on a reaction kettle and is expensive in production cost; and the generated products are all polymers, have large molecular weight and are not beneficial to the absorption and utilization of animals.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings in the background art and provide a preparation method of the tryptophan zinc complex, which has the advantages of simple process, high product purity, low production cost and high reaction efficiency.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of a tryptophan zinc complex comprises the following steps: and (2) starting stirring, adding carbonate or bicarbonate into the organic solvent-water solution, stirring and dissolving, adding tryptophan, pressurizing and stirring until no bubbles emerge, heating, adding a zinc source for reaction, relieving pressure after the reaction is finished, cooling the reaction system, crystallizing, filtering, washing and drying to obtain the zinc tryptophan.
Carbonate or bicarbonate is added into an organic solvent-aqueous solution to form an alkaline environment, and tryptophan is added, so that the reaction system is always in an alkaline condition, a large amount of carbonate ions react with the tryptophan which is continuously added, the reaction rate can be accelerated, the stability of the reaction environment is maintained, and the reaction environment is not gradually transited from the acid environment to the alkaline environment. In addition, due to the influence of the structure of tryptophan and the weak alkalinity of carbonate/bicarbonate, the method cannot react under normal pressure and can only react under the condition of pressurization.
The reason why the carbonate/bicarbonate is adopted to replace sodium hydroxide and potassium hydroxide is as follows: compared with strong bases such as sodium hydroxide, potassium hydroxide and the like, the carbonate/bicarbonate is weak in alkalinity, the solution has a buffering effect, the pH value is slowly changed in the reaction, the reaction can be carried out at a constant speed, and the situation that the raw materials cannot be completely reacted due to the fact that the reaction rate is too fast and the product wraps the raw materials is avoided.
The reason why the zinc carbonate is not directly selected in the present invention is that: zinc carbonate is insoluble in water, whereas the acidity of tryptophan hardly dissolves zinc carbonate completely at a high rate. Most of the zinc carbonate can only be dissolved with tryptophan solution in a solid form at a water-solid two-phase interface, the reaction rate is slow, and the reaction is difficult to complete.
In the above preparation method, preferably, the zinc source includes zinc chloride and/or zinc sulfate.
Preferably, the molar ratio of tryptophan to zinc source is 2: 0.95-1.05.
Preferably, the carbonate is sodium carbonate and/or potassium carbonate; the bicarbonate is sodium bicarbonate and/or potassium bicarbonate; the molar ratio of the carbonate to the tryptophan is (1.01-1.02) to 2; the molar ratio of the bicarbonate to the tryptophan is (1.01-1.02) to 1.
The carbonate or bicarbonate reacts with tryptophan more mildly than other strong bases, and carbon dioxide bubbles released in the reaction process can temporarily change the viscosity of a reaction system, so that the material distribution in the reaction system is looser, the reaction rate is more uniform, and the particle size of the generated product tends to be consistent. At this point, tryptophan cannot be added too quickly, otherwise the solution would be prone to bumping.
The invention firstly makes tryptophan react with carbonate or bicarbonate with weak alkalinity at normal temperature, and does not need heating because the reaction of the tryptophan and strong base and weak acid salt is mild and can release heat. As the reaction proceeds, the carbonate or bicarbonate is continuously consumed, the generated carbon dioxide is continuously escaped, and the pH value is gradually changed from alkalinity to alkalescence. At pH < 7.5, intermolecular and intramolecular dehydration condensation reactions may occur with tryptophan, so in the present invention, although pH adjustment is not emphasized, a slight excess of base is required to reduce the occurrence of side reactions. However, if the carbonate or bicarbonate is too excessive, the alkaline concentration in the solution is too high, and the carbonic acid formed after the escaped carbon dioxide is dissolved in water can generate carbonate ions in the solution with higher pH, and the carbonate ions react with the subsequent zinc ions to generate zinc carbonate, so that the subsequent reaction is not facilitated. Thus, the amount of carbonate and bicarbonate needs to be strictly controlled. Preferably, the pressure for pressurization is 100-1000 KPa; more preferably, the pressurization pressure is 200kPa to 500 kPa.
The pressure is too low, the reaction is not carried out or the reaction rate is slow, and the conversion rate is low; the pressurization is too high, the requirement on equipment is high, the by-products generated in the product are increased, and the improvement on the reaction rate and the conversion rate is not obvious. Therefore, the pressurization pressure is preferably controlled to be 100-1000 KPa. Preferably, the temperature of the reaction system is controlled to be 50-75 ℃, and the reaction time is 2-5 h. The reaction is incomplete easily caused by too short time, 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 material is excessively viscous and agglomerated, the crystallization granularity is influenced, and the discharging and centrifuging are not facilitated. It is also considered that zinc tryptophan can be produced by the reaction with a tryptophan salt even if the solution contains a trace amount of zinc carbonate. 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 addition, under the influence of the indole group of tryptophan, the steric hindrance is large, the reaction is difficult, and higher temperature and longer reaction time are required. However, the temperature is not suitable to be too high, and the temperature is too high and the alkalinity is too strong, so that side reactions can occur, such as racemization, decarboxylation and deamination of acetyl on tryptophan.
Preferably, in the organic solvent-aqueous solution, the organic solvent is one or more of ethanol, propanol and isopropanol, and the volume ratio of the organic solvent to the aqueous solution is 0.1-0.2: 1. The dissolving speed of tryptophan in an alcohol solvent is higher, and the reaction rate can be improved by adding an alcohol organic solvent. Considering that the solubility of carbonate and inorganic zinc salt in water is much higher, the water-alcohol organic solvent can better improve the reaction rate. Meanwhile, the uniformity of the particle size of the product obtained by crystallization after the reaction is finished is better.
Preferably, the organic solvent is also added with allyl alcohol, and the volume of the allyl alcohol is 0.1-0.3% of that of the organic solvent. The allyl alcohol is non-toxic, is a good dispersant and cosolvent, and can reduce the amount of the added organic solvent by adding the allyl alcohol under the same reaction effect.
Preferably, a catalyst is also added after the zinc source is added.
More preferably, the catalyst is benzene sulfonic acid or a molecular sieve.
More preferably, the benzenesulfonic acid is benzenesulfonic acid or p-toluenesulfonic acid; the molecular sieve is solid-supported hetungstate.
More preferably, the supported hetungstate is a solid hetungstic acid containing XW9O34 n-、XW11O39 n-Or XW9Mo2O39 n-Wherein X is Si, P or Ge, and n is the number of charges carried by the group.
More preferably, the amount of the catalyst added is 0.2% to 5% by weight of the zinc tryptophan.
In the invention, the catalyst and the reactant react to change the reaction path, thereby reducing the activation energy of the reaction and accelerating the reaction efficiency. When no catalyst is added, the reaction conversion rate in unit time is very low, and the reaction is difficult; the catalyst is added, so that the reaction time can be shortened, and the reaction temperature can be reduced.
In the invention, zinc sulfate or zinc chloride reacts with tryptophan under the heating condition to generate zinc tryptophan, and the chemical reaction equation is as follows:
Na2CO3+2C11H12N2O2＝2C11H11N2O2Na+H2O+CO2↑；
NaHCO3+C11H12N2O2＝C11H11N2O2Na+H2O+CO2↑；
K2CO3+2C11H12N2O2＝2C11H11N2O2K+H2O+CO2↑；
KHCO3+C11H12N2O2＝C11H11N2O2K+H2O+CO2↑；
ZnSO4+2C11H11N2O2Na+H2O＝(C11H11N2O2)2Zn·H2O+Na2SO4；
ZnCl2+2C11H11N2O2Na+H2O＝(C11H11N2O2)2Zn·H2O+2NaCl；
ZnSO4+2C11H11N2O2K+H2O＝(C11H11N2O2)2Zn·H2O+K2SO4；
ZnCl2+2C11H11N2O2K+H2O＝(C11H11N2O2)2Zn·H2O+2KCl。
the above reaction raw materials include two forms of crystal water-containing and crystal water-free.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method has the advantages of high reaction rate, high conversion rate, high yield, simple and convenient method, low cost, industrial large-scale production, no introduction of new impurities and no generation of byproducts.
2. The zinc tryptophan prepared by the invention can be used as a novel nutrition enhancer, has the function of supplementing tryptophan and trace elements compared with other zinc products, and has good application prospect.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the invention is not limited to the specific embodiments described 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 zinc content of the products of the following examples was determined by EDTA titration and the tryptophan content by azotometry, losing crystalline water at 180 ℃ and free water at 104 ℃.
Example 1:
the preparation method of the zinc tryptophan comprises the following steps:
the stirring was started and 218.5Kg of sodium carbonate of 98% purity were added to 7m3Ethanol-water solution (V)Ethanol:VWater (W)1:9), adding 833.6Kg of tryptophan with the purity of 98 percent after stirring and dissolving, pressurizing and maintaining the pressure at 100KPa, stirring until no more bubbles emerge, heating to 50 ℃, adding 347.9Kg of zinc sulfate monohydrate with the purity of 98 percent for reaction, releasing the pressure after the reaction is carried out for 5 hours, cooling the reaction system, crystallizing, filtering, washing and drying to obtain 636.3Kg of zinc tryptophan.
The content of tryptophan in the zinc tryptophan product is 81.9 percent by measurement, and Zn is obtained2+13.2%, a water loss of 3.6% at 180 ℃ and a water loss of 1.2% at 104 ℃, i.e. a purity of 98.7%, a yield of 64.1% in terms of zinc, i.e. a molar ratio of tryptophan to zinc of about 2:1, and a molecular formula of (C)11H11N2O2)2Zn·H2O。
Example 2:
the preparation method of the zinc tryptophan comprises the following steps: starting stirring at 5m3Ethanol-water solution (V)Ethanol:VWater (W)1.8L of allyl alcohol is added into 1:7), 287.7Kg of potassium carbonate with the purity of 98 percent is added, 833.6Kg of tryptophan with the purity of 98 percent is added after stirring and dissolving, the pressure is increased and maintained at 200KPa, the temperature is raised to 60 ℃ after stirring until no bubbles are emitted, 616.1Kg of zinc sulfate heptahydrate with the purity of 98 percent and 15Kg of p-toluenesulfonic acid are added for reaction, the pressure is released after 4 hours of reaction, and the reaction system is cooled, crystallized, filtered, washed and dried, thus 857.1Kg of zinc tryptophan is obtained.
The content of tryptophan in the zinc tryptophan product is 80.9 percent by measurement, and Zn is obtained2+13.0%, a water loss of 3.6% at 180 ℃ and a water loss of 2.3% at 104 ℃, i.e. a purity of 97.5%, a yield of 85.3% in terms of zinc, i.e. a molar ratio of tryptophan to zinc of about 2:1, and a molecular formula of (C)11H11N2O2)2Zn·H2O。
Example 3:
the preparation method of the zinc tryptophan comprises the following steps: starting the stirring, at 4m3Propanol-water solution (V)Propanol(s):VWater (W)1.8L of allyl alcohol is added into 1:5), 346.3Kg of sodium bicarbonate with the purity of 98 percent is added, 833.6Kg of tryptophan with the purity of 98 percent is added after stirring and dissolving, the pressure is increased and maintained at 500KPa, the temperature is raised to 70 ℃ after stirring until no air bubbles emerge, 369.9Kg of zinc sulfate monohydrate with the purity of 98 percent and 41.6Kg of benzenesulfonic acid are added for reaction, the pressure is released after the reaction is carried out for 3 hours, and the reaction system is cooled, crystallized, filtered, washed and dried, thus obtaining 890.8Kg of zinc tryptophan.
The content of tryptophan in the zinc tryptophan product is 81.4 percent and Zn is measured2+13.1%, a water loss of 3.6% at 180 ℃ and a water loss of 1.8% at 104 ℃, i.e. a purity of 98.1%, a yield of 89.2% in terms of zinc, i.e. a molar ratio of tryptophan to zinc of about 2:1, and a molecular formula of (C)11H11N2O2)2Zn·H2O。
Example 4:
the preparation method of the zinc tryptophan comprises the following steps: starting the stirring, at 4m3Isopropanol-water solution (V)Isopropanol (I-propanol):VWater (W)Adding 0.8L of allyl alcohol into 1:10), adding 416.8Kg of potassium bicarbonate with the purity of 98%, stirring and dissolving, adding 833.6Kg of tryptophan with the purity of 98%, pressurizing and maintaining the pressure at 1000KPa, stirring until no bubbles are emitted, heating to 75 ℃, adding 283.7Kg of zinc chloride with the purity of 98% and 2.0Kg of molecular sieve solid hetungstic acid for reaction, relieving the pressure after 2 hours of reaction, cooling, crystallizing, filtering, washing and drying the reaction system, thus obtaining 922.9Kg of zinc tryptophan.
The content of tryptophan in the zinc tryptophan product is 81.7 percent by measurement, and Zn is obtained2+13.1%, a water loss of 3.6% at 180 ℃ and a water loss of 1.5% at 104 ℃, i.e. a purity of 98.4%, a yield of 92.7% in terms of zinc, i.e. a molar ratio of tryptophan to zinc of about 2:1, and a molecular formula of (C)11H11N2O2)2Zn·H2O。

Claims (9)

1. A preparation method of a tryptophan zinc complex is characterized by comprising the following steps: starting stirring, adding carbonate or bicarbonate into an organic solvent-water solution, stirring and dissolving, adding tryptophan, pressurizing and stirring until no bubbles emerge, heating, adding a zinc source for reaction, relieving pressure after the reaction is finished, cooling, crystallizing, filtering, washing and drying a reaction system to obtain the zinc tryptophan;
the carbonate is sodium carbonate and/or potassium carbonate; the bicarbonate is sodium bicarbonate and/or potassium bicarbonate; the zinc source is zinc chloride and/or zinc sulfate.
2. The method of claim 1, wherein the molar ratio of tryptophan to the zinc source is 2: 0.95 to 1.05.
3. The preparation method according to claim 1, wherein the molar ratio of the carbonate to the tryptophan is (1.01-1.02) to 2; the molar ratio of the bicarbonate to the tryptophan is (1.01-1.02) to 1.
4. The method as claimed in claim 1, wherein the pressurization pressure is 100kPa 1000 kPa.
5. The preparation method according to claim 1, wherein the temperature of the reaction system is controlled to be 50-75 ℃, and the reaction time is 2-5 h.
6. The preparation method according to claim 1, wherein in the organic solvent-aqueous solution, the organic solvent is one or more of ethanol, propanol and isopropanol, and the volume ratio of the organic solvent to the aqueous solution is 0.1-0.2: 1.
7. The preparation method of claim 6, wherein the organic solvent is further added with allyl alcohol, and the volume of the allyl alcohol is 0.1-0.3% of the volume of the organic solvent.
8. The production method according to any one of claims 1 to 7, wherein a catalyst is further added after the zinc source is added; the catalyst is benzene sulfonic acid or a molecular sieve; the benzenesulfonic acid is benzenesulfonic acid or p-toluenesulfonic acid; the molecular sieve is solid-supported hetungstate.
9. The method of claim 8, wherein the catalyst is added in an amount of 0.2% to 5% by weight of the zinc tryptophan.
CN202011367567.4A 2020-11-27 2020-11-27 Preparation method of tryptophan zinc complex Active CN112321484B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011367567.4A CN112321484B (en) 2020-11-27 2020-11-27 Preparation method of tryptophan zinc complex

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011367567.4A CN112321484B (en) 2020-11-27 2020-11-27 Preparation method of tryptophan zinc complex

Publications (2)

Publication Number Publication Date
CN112321484A CN112321484A (en) 2021-02-05
CN112321484B true CN112321484B (en) 2022-02-11

Family

ID=74309100

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011367567.4A Active CN112321484B (en) 2020-11-27 2020-11-27 Preparation method of tryptophan zinc complex

Country Status (1)

Country Link
CN (1) CN112321484B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112979504B (en) * 2021-03-09 2023-02-28 长沙兴嘉生物工程股份有限公司 Preparation method and application of argininyl manganese

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130123397A1 (en) * 2010-07-23 2013-05-16 Nissan Chemical Industries, Ltd. Crystalline resin composition
CN101941938A (en) * 2010-08-27 2011-01-12 长沙兴嘉生物工程股份有限公司 Tryptophan chelate and preparation method and application thereof
CN102835610B (en) * 2012-09-27 2013-08-28 淮阴工学院 Feed additive for broiler chickens and preparation method thereof
CN102977002A (en) * 2012-12-04 2013-03-20 山东省化工研究院 Preparation method of tryptophan and zinc complex as feed additive

Also Published As

Publication number Publication date
CN112321484A (en) 2021-02-05

Similar Documents

Publication Publication Date Title
CN103224461B (en) Preparation method of large granule crystal form methionine metal chelate and application thereof
CN112321484B (en) Preparation method of tryptophan zinc complex
CN103694107A (en) Preparation method of feed additive calcium beta-hydroxy-beta-methylbutyrate
CN105601542A (en) Method for crystallizing N-carbamylglutamic acid with mixed acid
CN113068769A (en) Solid methionine hydroxy analogue calcium salt compound with antibacterial and acidifying properties and preparation method thereof
NZ511152A (en) Chelated feed additive and method of preparation
CN107879959A (en) The preparation method of the methylthio calcium butyrate of 2 hydroxyl of D, L 4
CN109053516A (en) A kind of selenomethionine zinc and preparation method thereof
CN102948620B (en) Preparation method of modified methionine hydroxy analog-calcium feed additive
CN106631283A (en) Fertilizer and water essence special for aquaculture
CN113185456A (en) Method for refining nicotinic acid
CN111484426A (en) Method for synthesizing aminoacetonitrile hydrochloride from hydrocyanic acid
CN112941116A (en) Method for preparing alpha-ketoglutarate calcium by enzyme method
CN109123101B (en) Preparation method of manganese nicotinate
CN112457998A (en) Yeast culture method and yeast cell wall breaking method
CN112430193B (en) Preparation method and application of copper tyrosine
CN112409200B (en) Preparation method and application of isoleucine chelate metal
CN111116438B (en) Preparation method and application of manganese cystine
CN112979504B (en) Preparation method and application of argininyl manganese
CN110897039B (en) Preparation method and application of manganese valine
CN112006172A (en) Novel rumen-bypass pantothenic acid coating process
CN116120196A (en) Preparation method of 5-aminolevulinic acid chelated zinc
CN111116390B (en) Preparation method of calcium glutamate
CN114451497B (en) Composition containing ethylenediamine dihydroiodine, and preparation method and application thereof
CN117645559A (en) Methionine composition and preparation method and application thereof

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
GR01 Patent grant
GR01 Patent grant