CN107337625B - Preparation method of feed-grade hydroxyl manganese methionine chelate - Google Patents
Preparation method of feed-grade hydroxyl manganese methionine chelate Download PDFInfo
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- CN107337625B CN107337625B CN201710465655.XA CN201710465655A CN107337625B CN 107337625 B CN107337625 B CN 107337625B CN 201710465655 A CN201710465655 A CN 201710465655A CN 107337625 B CN107337625 B CN 107337625B
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- 239000013522 chelant Substances 0.000 title claims abstract description 33
- YIHIRFSMXSYUQJ-FHNDMYTFSA-M N[C@@H](CCSC)C(=O)O.O[Mn] Chemical compound N[C@@H](CCSC)C(=O)O.O[Mn] YIHIRFSMXSYUQJ-FHNDMYTFSA-M 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- 239000011572 manganese Substances 0.000 claims abstract description 33
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 30
- JFQYZKYIEOVMQJ-WCCKRBBISA-N [Mn].ON[C@@H](CCSC)C(=O)O Chemical compound [Mn].ON[C@@H](CCSC)C(=O)O JFQYZKYIEOVMQJ-WCCKRBBISA-N 0.000 claims abstract description 30
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 30
- 238000005406 washing Methods 0.000 claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- KFSJYZYQSZKRRQ-BYPYZUCNSA-N (2s)-2-(hydroxyamino)-4-methylsulfanylbutanoic acid Chemical compound CSCC[C@H](NO)C(O)=O KFSJYZYQSZKRRQ-BYPYZUCNSA-N 0.000 claims abstract description 20
- 230000009920 chelation Effects 0.000 claims abstract description 13
- 239000007790 solid phase Substances 0.000 claims abstract description 12
- 239000002893 slag Substances 0.000 claims abstract description 10
- 238000003825 pressing Methods 0.000 claims description 12
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 5
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000011565 manganese chloride Substances 0.000 claims description 5
- 235000002867 manganese chloride Nutrition 0.000 claims description 5
- 229940099607 manganese chloride Drugs 0.000 claims description 5
- 229940099596 manganese sulfate Drugs 0.000 claims description 5
- 239000011702 manganese sulphate Substances 0.000 claims description 5
- 235000007079 manganese sulphate Nutrition 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 4
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 20
- 239000002002 slurry Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000003674 animal food additive Substances 0.000 abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 5
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 4
- 239000007795 chemical reaction product Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 229930182817 methionine Natural products 0.000 description 4
- 241001465754 Metazoa Species 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- ADJVQIUTYQSXKP-WCCKRBBISA-N [K].ON[C@@H](CCSC)C(=O)O Chemical compound [K].ON[C@@H](CCSC)C(=O)O ADJVQIUTYQSXKP-WCCKRBBISA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 2
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 210000004767 rumen Anatomy 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WAYHNLGKMVZKIA-BYPYZUCNSA-N (2S)-2-amino-4-(hydroxymethylsulfanyl)butanoic acid Chemical compound OCSCC[C@H](N)C(=O)O WAYHNLGKMVZKIA-BYPYZUCNSA-N 0.000 description 1
- BSYNFGPFPYSTTM-UHFFFAOYSA-N 2-hydroxypropanoic acid;hydrate Chemical compound O.CC(O)C(O)=O BSYNFGPFPYSTTM-UHFFFAOYSA-N 0.000 description 1
- 206010003591 Ataxia Diseases 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003975 animal breeding Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003248 enzyme activator Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 235000012631 food intake Nutrition 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 230000037308 hair color Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 230000007102 metabolic function Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 210000002569 neuron Anatomy 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- SGPVHWVNCXAMID-UHFFFAOYSA-N propanedioic acid;hydrate Chemical compound O.OC(=O)CC(O)=O SGPVHWVNCXAMID-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001850 reproductive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 210000001685 thyroid gland Anatomy 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Animal Husbandry (AREA)
- Zoology (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a production method of a feed additive, and particularly discloses a preparation method of a feed-grade hydroxy manganese methionine chelate, which comprises the following steps: A. adding a sodium hydroxide reagent into the inorganic salt aqueous solution of manganese to obtain a solid phase substance; B. washing the solid phase with water to remove soluble components; C. adding water into the washing slag for homogenate; D. adding hydroxymethionine according to the proportion that the molar ratio of the manganese content in the slurry to the hydroxymethionine is less than or equal to 0.5 to carry out chelation reaction; E. and carrying out post-treatment on the reaction product to obtain the product. The invention has the advantages that: 1) the hydroxyl methionine manganese chelate product with higher purity can be prepared and is more suitable to be used as a feed additive; 2) the chelation reaction has high speed and low energy consumption, can be carried out at a high speed at normal temperature, has simple and convenient production method, and is beneficial to industrial popularization.
Description
Technical Field
The invention relates to the field of animal breeding, in particular to a preparation method of a feed additive.
Background
The main nutritional and physiological role of the trace element manganese is as an enzyme activator or component in carbohydrate, lipid, protein and cholesterol metabolism. Manganese can participate in the transmission of central nerve mediators and the energy supply of central nerve cells, and maintain substances essential for the normal metabolic function of the brain, and if the animals lack manganese, the phenomena of food intake reduction, growth slowing, bone abnormality, ataxia, reaction retardation, abnormal reproductive function and the like can be caused. Furthermore, thyroid synthesis must be catalyzed by enzymes that activate manganese. Manganese ions also have a large relationship with hair color, which may be rich in manganese if the hair is bright, and manganese may be deficient if the hair is dull or lusterless.
The hydroxyl manganese methionine has the characteristics of low toxicity, low rumen degradation rate, promotion of rumen microorganism synthesis, protein saving in daily ration, improvement of production performance of dairy cows, improvement of animal production performance and immunity, reduction of nitrogen emission, less environmental pollution, simple production process, lower price and the like, and is the most economical and effective amino acid source and manganese source for animals. Therefore, manganese hydroxymethionine is gradually replacing some amino acids with higher price in the market.
The preparation method of the hydroxyl methionine manganese generally comprises the following steps: mixing hydroxymethionine with inorganic manganese salt, and maintaining high reaction temperature in the presence of alkaline solution.
For example, in the patent document with publication number CN1338254A, the example section thereof discloses a method for preparing manganese hydroxymethionine feed additive, which comprises reacting hydroxymethionine, manganese sulfate monohydrate, 98% industrial grade sodium hydroxide at a reaction temperature of 80 ℃ for 1 hour to obtain manganese hydroxymethionine.
Also, for example, in patent document CN103254104A, its example discloses a method for preparing manganese, a methionine hydroxy analogue, which comprises adding lactic acid-water solution to methionine hydroxy analogue, and stirring to obtain malonic acid water solution of methionine hydroxy analogue. Then adding a prepared 12 percent potassium carbonate solution, stirring and reacting for 0.5h, and controlling the pH value to be 5.4. Then adding manganese acetate tetrahydrate solid, stirring and reacting for 1.5h, and controlling the end point pH value to be 7. The reaction temperature in the reaction process is controlled within the range of 30-45 ℃. And after the reaction is finished, performing pressure filtration, washing with water for a plurality of times, performing vacuum drying, and sieving by a 40-mesh sieve to obtain the product of the methionine hydroxy analogue manganese.
Manganese hydroxy methionine is classified into complex and chelate:
the hydroxyl methionine manganese complex is generated by complexing one mole of manganese and one mole of hydroxyl methionine through a coordination bond to form a complex cation, and the complex is positively charged. Hydroxymethionine complex formula: MnC5H8O3S。
The hydroxyl methionine manganese chelate is formed by chelating one mole of manganese and two moles of hydroxyl methionine through coordination bonds and covalent bonds to form an inner complex salt, and the chelate is electrically neutral. The molecular formula of the hydroxyl methionine manganese chelate is as follows: mn (C)5H10O3S)2。
In the two patent documents, the method in the first patent document can only produce hydroxyl methionine manganese complex through complexation reaction. While the method of the second patent document can produce manganese hydroxy methionine chelate. According to the method, hydroxy methionine reacts with potassium carbonate to generate hydroxy methionine potassium, and then the hydroxy methionine potassium and manganese acetate tetrahydrate are subjected to a displacement reaction to separate hydroxy methionine manganese through a precipitation solution system, so that the method is long in time consumption and high in energy consumption, manganese is hydrolyzed to produce manganese oxide, and the product is mixed with impurities.
Disclosure of Invention
The invention provides a preparation method of feed-grade manganese hydroxymethionine chelate, aiming at obtaining the feed-grade manganese hydroxymethionine chelate product with less impurity content and higher purity and optimizing the production method of the product.
The technical scheme adopted by the invention is as follows: the preparation method of the feed-grade hydroxyl manganese methionine chelate comprises the following steps:
A. adding a metered sodium hydroxide reagent into an inorganic salt aqueous solution of manganese, and carrying out solid-liquid separation after full reaction to obtain a solid-phase substance;
B. washing the solid phase substance with water to remove soluble components therein to obtain washing slag;
C. adding water into the washing slag for homogenate to obtain slurry;
D. adding hydroxymethionine according to the proportion that the molar ratio of the manganese content in the slurry to the hydroxymethionine is less than or equal to 0.5 to carry out chelation reaction, and obtaining a reaction product after the reaction is finished;
E. and carrying out solid-liquid separation, washing and drying on the reaction product to obtain a feed-grade hydroxyl methionine manganese chelate product.
In the invention, the inventor prepares the intermediate slurry first and then carries out chelation reaction on the intermediate slurry and the hydroxymethionine to prepare the manganese hydroxymethionine chelate. The method can effectively prevent anions and impurity cations in the inorganic salt aqueous solution of manganese and impurities of non-target products such as cations or anions in the alkaline solution from being mixed into the product, and can also effectively prevent manganese from being hydrolyzed, so that the hydroxyl methionine manganese product with higher purity can be prepared, and is more suitable for being used as a feed additive.
On the other hand, the intermediate slurry in the invention can generate chelation reaction with the hydroxymethionine, thereby realizing hydroxylMethionine chelate Mn (C)5H10O3S)2And (4) preparing. Because the hydroxyl methionine manganese chelate is a slightly soluble substance, the hydroxyl methionine manganese chelate cannot absorb moisture and is beneficial to feed processing; in addition, the hydroxyl manganese methionine is more stable in acid environment, and the absorption rate of manganese in intestinal tracts cannot be reduced due to the fact that the manganese is combined by substances such as phytic acid and oxalic acid.
In the third aspect, the intermediate slurry is formed, so that the chelating reaction is more favorably carried out, the reaction rate is higher, and the energy is saved.
As a further improvement of the invention, the chelating reaction conditions of the step D are as follows: the reaction temperature is 20-30 ℃, the reaction time is 20-40 minutes, the stirring speed in the reaction process is 40-80 r/min, and the pH value of a reaction system is 6-7. The scheme is a better chelation reaction condition summarized by a large number of experiments, under the reaction condition, the chelation reaction can be carried out at a higher speed, and the energy consumption can be maintained at a lower level, so that the scheme is more favorable for industrial popularization.
It will be understood by those skilled in the art that an aqueous solution of an inorganic salt of manganese capable of reacting with a sodium hydroxide reagent to form a hydroxide precipitate is generally used as the starting material in the present invention, but a manganese sulfate solution or a manganese chloride solution is preferably used as the starting material in view of the cost of the starting material and the safety of production.
As a further improvement of the method, the mass percent concentration of manganese (calculated by Mn) in the slurry in the step C is 22-26%, and the appropriate slurry concentration can ensure that the chelation reaction is performed at a faster rate.
As a further improvement of the method, after the reaction in the step A is finished, the pH value of the liquid phase is 9-10, and the pH value can be used as a control index of the addition amount of the sodium hydroxide reagent to ensure that manganese in the solution is fully precipitated, and excessive sodium hydroxide reagent is not added, so that the waste of raw materials is reduced, and the load of a subsequent washing process is avoided.
The invention has the beneficial effects that: 1) the hydroxyl methionine manganese chelate product with higher purity can be prepared and is more suitable to be used as a feed additive; 2) the chelation reaction has high speed and low energy consumption, can be carried out at a high speed at normal temperature, has simple and convenient production process, and is beneficial to industrial popularization.
Drawings
FIG. 1 is a process flow diagram of the first embodiment.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
The first embodiment is as follows:
preparing a feed-grade hydroxyl manganese methionine chelate product A according to the following method:
(1) and (3) dissolving the solid manganese sulfate monohydrate, and removing insoluble substances in a filter pressing mode to obtain a manganese sulfate solution.
(2) Adding a sodium hydroxide solution into a manganese sulfate solution, fully reacting, collecting a solid-phase substance in a filter pressing mode, washing soluble substances such as sodium sulfate and sodium hydroxide contained in the solid-phase substance in a washing mode, and detecting whether sulfate radicals are washed out or not by using barium chloride to obtain washing residues.
(3) Transferring the water washing slag into a reaction tank, and adding clear water for homogenate. Extracting homogenate to detect the manganese content to be 23.3% (mass percentage).
(4) By measuring the content of manganese, a chelation reaction is carried out according to the molar ratio of manganese to hydroxymethionine of 1:2.05, the reaction temperature is 23 ℃, the reaction time is 30 minutes, the stirring speed is 60 revolutions per minute, and the pH value of the reaction system is 6.
(5) And removing excessive hydroxymethionine by filter pressing and washing the precipitate of the manganese hydroxymethionine chelate.
(6) And (3) carrying out flash evaporation drying on the obtained hydroxyl methionine manganese chelate crude product to remove redundant water, and finally obtaining a product A.
The composition of product A was analyzed and the results are shown in Table 1.
Example two:
preparing a feed-grade hydroxyl manganese methionine chelate product B according to the following method:
(1) dissolving solid manganese chloride tetrahydrate, and removing insoluble substances in a filter pressing mode to obtain a manganese chloride solution.
(2) Adding a sodium hydroxide solution into a manganese chloride solution, fully reacting, collecting a solid-phase substance in a filter pressing mode, and washing soluble substances such as sodium chloride, sodium hydroxide and the like contained in the solid-phase substance in a water washing mode to obtain water washing slag.
(3) Transferring the water washing slag into a reaction tank, and adding clear water for homogenate. Extracting homogenate to detect the manganese content to be 25.1% (mass percentage).
(4) By measuring the content of manganese, carrying out chelation reaction according to the molar ratio of manganese to hydroxymethionine of 1:2.1, wherein the reaction temperature is 25 ℃, the reaction time is 20 minutes, the stirring speed is 80 r/min, and the pH value of a reaction system is 6.8.
(5) And removing excessive hydroxymethionine by filter pressing and washing the precipitate of the manganese hydroxymethionine chelate.
(6) And (3) carrying out flash evaporation drying on the obtained hydroxyl methionine manganese chelate crude product to remove redundant water, and finally obtaining a product B.
The composition of product B was analyzed and the results are shown in Table 1.
Table 1: feed-grade hydroxyl manganese methionine chelate product ingredient analysis table
| Mn(C5H10O3S)2 | Moisture content | Lead (mg/kg) | Arsenic (mg/kg) | Cadmium (mg/kg) | Yield of | |
| Product A | 86.2％ | 7.8％ | 5.3 | 2.1 | 6.7 | 97.4％ |
| Product B | 86.0％ | 8.0％ | 4.6 | 1.7 | 5.3 | 97.1％ |
Claims (2)
1. The preparation method of the feed-grade hydroxyl manganese methionine chelate comprises the following steps:
A. dissolving solid manganese sulfate monohydrate, and removing insoluble substances in a filter pressing mode to obtain a manganese sulfate solution;
B. adding a sodium hydroxide solution into a manganese sulfate solution, fully reacting, collecting a solid-phase substance in a filter pressing mode, and washing soluble substances in the solid-phase substance completely in a water washing mode to obtain washing slag;
C. transferring the water washing slag into a reaction tank, adding clear water for homogenate, and extracting the homogenate to detect that the mass percentage content of manganese is 23.3%;
D. according to the measured manganese content, carrying out chelation reaction according to the molar ratio of manganese to hydroxymethionine of 1:2.05, wherein the reaction temperature is 23 ℃, the reaction time is 30 minutes, the stirring speed is 60 revolutions per minute, and the pH of the reaction system is = 6;
E. removing excessive hydroxymethionine from the precipitate of the manganese hydroxymethionine chelate through filter pressing and water washing;
F. and (3) flash-drying the obtained hydroxyl methionine manganese chelate crude product to remove redundant moisture to obtain the hydroxyl methionine manganese chelate.
2. The preparation method of the feed-grade hydroxyl manganese methionine chelate comprises the following steps:
A. dissolving solid manganese chloride tetrahydrate, and removing insoluble substances in a filter pressing mode to obtain a manganese chloride solution;
B. adding a sodium hydroxide solution into a manganese chloride solution, fully reacting, collecting a solid-phase substance in a filter pressing mode, and washing soluble substances in the solid-phase substance completely in a water washing mode to obtain washing slag;
C. transferring the water washing slag into a reaction tank, adding clear water for homogenate, and extracting homogenate to detect that the mass percentage content of manganese is 25.1%;
D. according to the measured manganese content, carrying out chelation reaction according to the molar ratio of manganese to hydroxymethionine of 1:2.1, wherein the reaction temperature is 25 ℃, the reaction time is 20 minutes, the stirring speed is 80 r/min, and the pH of the reaction system is = 6.8;
E. removing excessive hydroxymethionine from the precipitate of the manganese hydroxymethionine chelate through filter pressing and water washing;
F. and (3) flash-drying the obtained hydroxyl methionine manganese chelate crude product to remove redundant moisture to obtain the hydroxyl methionine manganese chelate.
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