CN107337625A - The preparation method of feed grade hydroxy methionine manganic chelates - Google Patents
The preparation method of feed grade hydroxy methionine manganic chelates Download PDFInfo
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- CN107337625A CN107337625A CN201710465655.XA CN201710465655A CN107337625A CN 107337625 A CN107337625 A CN 107337625A CN 201710465655 A CN201710465655 A CN 201710465655A CN 107337625 A CN107337625 A CN 107337625A
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- Prior art keywords
- reaction
- manganese
- hydroxy methionine
- methionine
- preparation
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- KFSJYZYQSZKRRQ-BYPYZUCNSA-N (2s)-2-(hydroxyamino)-4-methylsulfanylbutanoic acid Chemical compound CSCC[C@H](NO)C(O)=O KFSJYZYQSZKRRQ-BYPYZUCNSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000011572 manganese Substances 0.000 claims abstract description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 29
- 239000000047 product Substances 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000002893 slag Substances 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 5
- 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 claims abstract description 5
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 230000036632 reaction speed Effects 0.000 abstract description 2
- 238000012805 post-processing Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 12
- 229930182817 methionine Natural products 0.000 description 8
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 7
- SFBJBHRQDZBZAF-UHFFFAOYSA-M [Mn]O Chemical compound [Mn]O SFBJBHRQDZBZAF-UHFFFAOYSA-M 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000001556 precipitation Methods 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- DWNBOPVKNPVNQG-LURJTMIESA-N (2s)-4-hydroxy-2-(propylamino)butanoic acid Chemical compound CCCN[C@H](C(O)=O)CCO DWNBOPVKNPVNQG-LURJTMIESA-N 0.000 description 2
- ONFOSYPQQXJWGS-UHFFFAOYSA-N 2-hydroxy-4-(methylthio)butanoic acid Chemical compound CSCCC(O)C(O)=O ONFOSYPQQXJWGS-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 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
- 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 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008859 change 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
- 239000000470 constituent Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 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
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 2
- BZDIAFGKSAYYFC-UHFFFAOYSA-N manganese;hydrate Chemical compound O.[Mn] BZDIAFGKSAYYFC-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 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
- 150000003839 salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BZVFZBYIWNIHHL-WCCKRBBISA-N (2s)-2-amino-4-methylsulfanylbutanoic acid;manganese Chemical compound [Mn].CSCC[C@H](N)C(O)=O BZVFZBYIWNIHHL-WCCKRBBISA-N 0.000 description 1
- 206010003591 Ataxia Diseases 0.000 description 1
- 241000040710 Chela Species 0.000 description 1
- 206010010947 Coordination abnormal Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 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
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-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
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 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
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 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
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 235000019621 digestibility Nutrition 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 208000016290 incoordination Diseases 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000015097 nutrients 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
- 239000002244 precipitate Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 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
- 239000007790 solid phase Substances 0.000 description 1
- 210000001685 thyroid gland Anatomy 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
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
Landscapes
- 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 present invention relates to a kind of production method of feed addictive, specifically discloses a kind of preparation method of feed grade hydroxy methionine manganic chelates, comprises the following steps：A, metering sodium hydroxide reagent is added into the inorganic salt solution of manganese, obtains solid formation；B, solid formation is washed to remove wherein soluble component；C, water homogenate is added into washing slag；D, add hydroxy methionine according to the ratio of manganese content in slurry and molar ratio≤0.5 of hydroxy methionine and carry out chelatropic reaction；E, reaction product obtains product by post processing.It is an advantage of the invention that：1) the higher hydroxy methionine manganic chelates product of purity can be prepared, it is preferably to be used as feed addictive；2) chelatropic reaction speed is fast, and energy consumption is low, at normal temperatures can faster rate carry out, production method is easy, beneficial to industrially promoting.
Description
Technical field
The present invention relates to animal-breeding field, especially a kind of preparation method of feed addictive.
Background technology
The Major Nutrient physiological action of trace element manganese is in carbohydrate, lipid, protein and cholesterol metabolic
As the enzyme activation factor or part.Manganese can participate in the transmission of nervus centralis media and the energy supply of axoneure,
The essential material of brain eubolism function is maintained, if animal manganese deficiency can cause food ration decline, decreased growth, bone different
Often, incoordination, phenomena such as slow in reacting and breeding function is abnormal.In addition, the enzyme that thyroid synthesis must have activation manganese is urged
Change could be completed.Manganese ion also has much relations with chroma of hair, and chroma of hair light may then contain manganese abundance, hair dimness nothing
Gloss then may manganese deficiency.
Methionine hydroxy manganese has low small toxicity, rumen digestibility, the synthesis of promotion rumen microorganism, saved in daily ration
Protein, the production performance for improving cow, the production performance for improving animal and immunocompetence, the discharge for reducing nitrogen, pollution environment
The features such as less, simple production process, relatively low price, it is a kind of most economical effective amino acid source of animal and manganese source.Therefore hydroxyl
Base manganese methionine commercially some more expensive amino acid of just gradual fictitious hosts.
The preparation method of methionine hydroxy manganese is typically：It is molten in alkalescence after hydroxy methionine is mixed with the inorganic salts of manganese
Higher reaction temperature is maintained in the presence of liquid and is made.
For example, in Publication No. CN1338254A patent document, embodiment part discloses a kind of hydroxy methionine
The preparation method of manganese feed addictive, it is to be existed using hydroxy methionine, manganese sulfate monohydrate, 98% industrial sodium hydroxide
Keep reacting 1 hour under 80 DEG C of reaction temperature, so as to which methionine hydroxy manganese be made.
And for example Publication No. is that embodiment part discloses a kind of methionine hydroxyl in CN103254104A patent document
The preparation method of base analog manganese, it is to be made into egg ammonia using addition lactic acid-aqueous solution in methionine hydroxy analog, stirring
The malonic acid aqueous solution of sour hydroxy analogs.Add 12% solution of potassium carbonate prepared in advance, stirring reaction 0.5h, control
PH value is 5.4.Four water manganese acetate solids are added, stirring reaction 1.5h, it is 7 to control endpoint pH.Reaction in course of reaction
Temperature control is in the range of 30~45 DEG C.After the completion of reaction, press filtration, after washed several times with water, vacuum drying, cross 40 mesh sieves and obtain product
Methionine hydroxy analog manganese.
Methionine hydroxy manganese is divided into complex compound, chelate：
Hydroxy methionine manganese complex is that one mole of manganese and a hydroxy methionine are complexed by coordinate bond to generate, shape
Into complex cation, complex compound positive charged ions.Hydroxy methionine complex molecules formula：MnC5H8O3S。
Hydroxy methionine manganic chelates be one mole of manganese and two hydroxy methionine by coordinate bond, covalent bond chelating and
Generation, forms inner complex salt, and chelate is into electroneutral.Hydroxy methionine manganic chelates molecular formula：Mn(C5H10O3S)2。
In above-mentioned two pieces patent document, the method in first can only occur complex reaction and produce methionine hydroxy manganese network
Compound.And the method for second patent document can produce hydroxy methionine manganic chelates.This method is to first pass through hydroxyl egg
Propylhomoserin and carbonic acid nak response generation hydroxy methionine potassium, then displacement reaction occurs by hydroxy methionine potassium and four water manganese acetates,
Methionine hydroxy manganese is separated by precipitation solution system, therefore this method is time-consuming very long, energy consumption is higher, and easily causes
Manganese hydrolysis production manganese oxide, causes product to be mixed into impurity, and this method does not clean method accordingly, can not ensure product matter
Amount, it is difficult to industrially promote.
The content of the invention
It is less in order to obtain product impurity content, the higher feed grade hydroxy methionine manganic chelates product of purity, and it is excellent
Change the production method of product, the invention provides a kind of preparation method of feed grade hydroxy methionine manganic chelates.
The technical solution adopted in the present invention is：The preparation method of feed grade hydroxy methionine manganic chelates, including it is following
Step：
A, metering sodium hydroxide reagent is added into the inorganic salt solution of manganese, fully separation of solid and liquid obtains solid phase after reaction
Thing；
B, solid formation is washed to remove wherein soluble component, obtains washing slag；
C, add water homogenate into washing slag, obtain slurry；
D, hydroxy methionine is added according to the ratio of manganese content in slurry and molar ratio≤0.5 of hydroxy methionine to carry out
Chelatropic reaction, reaction obtain reaction product after terminating；
E, reaction product by separation of solid and liquid, wash, be dried to obtain feed grade hydroxy methionine manganic chelates product.
In the present invention, inventor, which uses, is first prepared intermediate slip, then carries out chela with slurry and hydroxy methionine
Close reaction and prepare hydroxy methionine manganic chelates.This method can effectively avoid anion in the inorganic salt solution of manganese and miscellaneous
The non-targeted impurity in products such as cation or anion in matter cation and alkaline solution is mixed into product, also can effectively be prevented
The hydrolysis of manganese, it is preferably to be used as feed addictive so as to prepare the higher hydroxy methionine manganese product of purity.
On the other hand, with hydroxy methionine chelatropic reaction can occur for the intermediate slip in the present invention, realize hydroxyl egg
Propylhomoserin chelate Mn (C5H10O3S)2Preparation.Because hydroxy methionine manganic chelates are microsolubility materials, thus will not the moisture absorption,
Be advantageous to feed manufacturing；In addition, methionine hydroxy manganese is more stable under acid environment, manganese will not be by phytic acid, oxalic acid etc. in enteron aisle
Material, which combines, causes absorptivity to decline.
The third aspect, by forming intermediate slurry, more conducively chelatropic reaction is carried out so that reaction rate faster, more saves
Can, it is demonstrated experimentally that in the present invention chelatropic reaction at room temperature can faster speed carry out, completely without heat necessity,
Technique is also simplified while production cost reduces.
As a further improvement on the present invention, step D chelatropic reaction condition is：20~30 DEG C of reaction temperature, during reaction
Between 20~40 minutes, 40~80 revs/min of the mixing speed in course of reaction, reaction system pH=6~7.The program is invention
The preferable chelatropic reaction condition that people is summed up by many experiments, under the reaction conditions, it both can guarantee that chelatropic reaction with very fast
Speed carry out, also energy consumption can be maintained reduced levels so that this programme is more conducively industrially promoted.
It will be appreciated by those skilled in the art that the nothing of the manganese of generation hydroxide precipitation can be reacted with sodium hydroxide reagent
Machine saline solution generally can serve as the raw material of the present invention, but consider from the cost of raw material and the security standpoint of production, best
Make raw materials for production from manganese sulfate solution, manganese chloride solution.
As a further improvement on the present invention, in step C slurry the mass percent concentration of manganese (being counted using Mn) as 22~
26%, suitable pulp density can ensure that chelatropic reaction is carried out with faster rate.
As a further improvement on the present invention, the reaction in step A terminates rear liquid phase pH=9~10, can be used as with this
The Con trolling index of sodium hydroxide reagent addition, it is ensured that the manganese in solution fully precipitates, while is added without the hydrogen of undue excess again
Sodium reagent is aoxidized, the load for increasing follow-up washing step is also avoided that while reducing wastage of material.
The beneficial effects of the invention are as follows：1) the higher hydroxy methionine manganic chelates product of purity can be prepared, it is more suitable
Preferably it is used as feed addictive to use；2) chelatropic reaction speed is fast, and energy consumption is low, at normal temperatures can faster rate carry out, production
Simple process, beneficial to industrially promoting.
Brief description of the drawings
Fig. 1 is the process chart of embodiment one.
Embodiment
The present invention is further described with reference to the accompanying drawings and examples.
Embodiment one：
Feed grade hydroxy methionine manganic chelates product A is prepared in accordance with the following methods：
(1) solid manganese sulfate monohydrate is dissolved, insoluble matter is removed by way of press filtration, obtain manganese sulfate solution.
(2) sodium hydroxide solution is added into manganese sulfate solution, solid formation is fully collected by way of press filtration after reaction,
The solable matters such as the sodium sulphate that will be contained again by way of washing in solid formation, sodium hydroxide are rinsed well, utilize chlorination
Whether barium detection sulfate radical is rinsed well, obtains washing slag.
(3) washing slag is transferred to retort, adds clear water homogenate.Extraction homogenate detection manganese content is 23.3% (quality hundred
Divide ratio).
(4) it is 1 according to manganese and hydroxy methionine mol ratio by determining manganese content:2.05 carry out chelatropic reaction, reaction temperature
23 DEG C of degree, 30 minutes reaction time, 60 revs/min of mixing speed, the pH=6 of reaction system.
(5) hydroxy methionine manganic chelates precipitation passes through press filtration, washes, removes excessive hydroxy methionine.
(6) hydroxy methionine manganic chelates crude product is obtained by expansion drying, is removed unnecessary moisture, is finally produced
Product A.
Constituent analysis is carried out to product A, the results are shown in Table 1.
Embodiment two：
Feed grade hydroxy methionine manganic chelates product B is prepared in accordance with the following methods：
(1) solid tetrahydrate manganese chloride is dissolved, insoluble matter is removed by way of press filtration, obtain manganese chloride solution.
(2) sodium hydroxide solution is added into manganese chloride solution, solid formation is fully collected by way of press filtration after reaction,
The solable matters such as the sodium chloride that will be contained again by way of washing in solid formation, sodium hydroxide are rinsed well, are washed
Slag.
(3) washing slag is transferred to retort, adds clear water homogenate.Extraction homogenate detection manganese content is 25.1% (quality hundred
Divide ratio).
(4) it is 1 according to manganese and hydroxy methionine mol ratio by determining manganese content:2.1 carry out chelatropic reaction, reaction temperature
25 DEG C of degree, 20 minutes reaction time, 80 revs/min of mixing speed, the pH=6.8 of reaction system.
(5) hydroxy methionine manganic chelates precipitation passes through press filtration, washes, removes excessive hydroxy methionine.
(6) hydroxy methionine manganic chelates crude product is obtained by expansion drying, is removed unnecessary moisture, is finally produced
Product B.
Constituent analysis is carried out to product B, the results are shown in Table 1.
Table 1：Feed grade hydroxy methionine manganic chelates product composition analytical table
| Mn(C5H10O3S)2 | Moisture | Lead (mg/kg) | Arsenic (mg/kg) | Cadmium (mg/kg) | Yield | |
| 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 (5)
1. the preparation method of feed grade hydroxy methionine manganic chelates, comprises the following steps：
A, metering sodium hydroxide reagent is added into the inorganic salt solution of manganese, fully separation of solid and liquid obtains solid formation after reaction；
B, solid formation is washed to remove wherein soluble component, obtains washing slag；
C, add water homogenate into washing slag, obtain slurry；
D, hydroxy methionine is added according to the ratio of manganese content in slurry and molar ratio≤0.5 of hydroxy methionine to be chelated
Reaction, reaction obtain reaction product after terminating；
E, reaction product by separation of solid and liquid, wash, be dried to obtain feed grade hydroxy methionine manganic chelates product.
2. the preparation method of feed grade hydroxy methionine manganic chelates according to claim 1, it is characterised in that：Step D
Chelatropic reaction condition be：20~30 DEG C of reaction temperature, 20~40 minutes reaction time, mixing speed 40 in course of reaction~
80 revs/min, reaction system pH=6~7.
3. the preparation method of feed grade hydroxy methionine manganic chelates according to claim 1, it is characterised in that：The manganese
One kind for manganese sulfate solution, in manganese chloride solution of inorganic salt solution.
4. the preparation method of the feed grade hydroxy methionine manganic chelates according to any claim in claims 1 to 3,
It is characterized in that：The mass percent concentration of manganese (being counted using Mn) is 22~26% in step C slurry.
5. the preparation method of the feed grade hydroxy methionine manganic chelates according to any claim in claims 1 to 3,
It is characterized in that：Reaction in step A terminates rear liquid phase pH=9~10.
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| CN113582893A (en) * | 2021-08-25 | 2021-11-02 | 湖南德邦生物科技有限公司 | Method for synthesizing manganese hydroxymethionine |
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| CN101735122A (en) * | 2009-12-18 | 2010-06-16 | 李宁 | Preparation method of hydroxy methionine salt and compound |
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| CN101735122A (en) * | 2009-12-18 | 2010-06-16 | 李宁 | Preparation method of hydroxy methionine salt and compound |
Non-Patent Citations (1)
| Title |
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| 范雪荣: "《纺织浆料检测技术》", 28 February 2007, 中国纺织出版社 * |
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| CN113582893A (en) * | 2021-08-25 | 2021-11-02 | 湖南德邦生物科技有限公司 | Method for synthesizing manganese hydroxymethionine |
| WO2023024222A1 (en) * | 2021-08-25 | 2023-03-02 | 湖南德邦生物科技有限公司 | Synthesis method for manganese hydroxymethionine |
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