CN114957023A - Preparation method of betaine metal chelate crystal, product and application thereof - Google Patents
Preparation method of betaine metal chelate crystal, product and application thereof Download PDFInfo
- Publication number
- CN114957023A CN114957023A CN202210518469.9A CN202210518469A CN114957023A CN 114957023 A CN114957023 A CN 114957023A CN 202210518469 A CN202210518469 A CN 202210518469A CN 114957023 A CN114957023 A CN 114957023A
- Authority
- CN
- China
- Prior art keywords
- betaine
- stirring
- crystal
- solution
- water
- 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.)
- Pending
Links
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 title claims abstract description 267
- 229960003237 betaine Drugs 0.000 title claims abstract description 133
- 239000013078 crystal Substances 0.000 title claims abstract description 98
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 56
- 239000002184 metal Substances 0.000 title claims abstract description 56
- 239000013522 chelant Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 title 1
- 238000003756 stirring Methods 0.000 claims abstract description 122
- 239000000243 solution Substances 0.000 claims abstract description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000011572 manganese Substances 0.000 claims abstract description 37
- 239000011701 zinc Substances 0.000 claims abstract description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 29
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000706 filtrate Substances 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 28
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 26
- 238000010992 reflux Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- 235000019730 animal feed additive Nutrition 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000003674 animal food additive Substances 0.000 claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 241001465754 Metazoa Species 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- KWRYODXJVFJUSG-UHFFFAOYSA-L manganese(2+);chloride;hydroxide Chemical compound [OH-].[Cl-].[Mn+2] KWRYODXJVFJUSG-UHFFFAOYSA-L 0.000 claims description 2
- 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
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- VOSQOLXQDQZVCL-UHFFFAOYSA-L zinc;chloride;hydroxide Chemical compound [OH-].[Cl-].[Zn+2] VOSQOLXQDQZVCL-UHFFFAOYSA-L 0.000 claims description 2
- 238000009360 aquaculture Methods 0.000 claims 2
- 244000144974 aquaculture Species 0.000 claims 2
- 239000006052 feed supplement Substances 0.000 claims 2
- 150000004697 chelate complex Chemical class 0.000 claims 1
- 238000011160 research Methods 0.000 abstract description 4
- 239000012452 mother liquor Substances 0.000 abstract description 2
- 238000001953 recrystallisation Methods 0.000 abstract description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 46
- 239000011592 zinc chloride Substances 0.000 description 23
- 235000005074 zinc chloride Nutrition 0.000 description 23
- 238000012360 testing method Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 15
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 15
- 239000011565 manganese chloride Substances 0.000 description 15
- 235000002867 manganese chloride Nutrition 0.000 description 15
- 229940099607 manganese chloride Drugs 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 241000238557 Decapoda Species 0.000 description 13
- 238000011282 treatment Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 125000004429 atom Chemical group 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- 241000238553 Litopenaeus vannamei Species 0.000 description 7
- 241000251468 Actinopterygii Species 0.000 description 5
- 210000004369 blood Anatomy 0.000 description 5
- 239000008280 blood Substances 0.000 description 5
- 230000034994 death Effects 0.000 description 5
- 231100000517 death Toxicity 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 230000002354 daily effect Effects 0.000 description 4
- -1 lysine halide Chemical class 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 150000001413 amino acids Chemical class 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 230000004584 weight gain Effects 0.000 description 3
- 235000019786 weight gain Nutrition 0.000 description 3
- GZCWLCBFPRFLKL-UHFFFAOYSA-N 1-prop-2-ynoxypropan-2-ol Chemical compound CC(O)COCC#C GZCWLCBFPRFLKL-UHFFFAOYSA-N 0.000 description 2
- 102000013563 Acid Phosphatase Human genes 0.000 description 2
- 108010051457 Acid Phosphatase Proteins 0.000 description 2
- 102000002260 Alkaline Phosphatase Human genes 0.000 description 2
- 108020004774 Alkaline Phosphatase Proteins 0.000 description 2
- 241000252211 Carassius Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 102000019197 Superoxide Dismutase Human genes 0.000 description 2
- 108010012715 Superoxide dismutase Proteins 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 235000014590 basal diet Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000037396 body weight Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000003203 everyday effect Effects 0.000 description 2
- 230000037406 food intake Effects 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000016709 nutrition Nutrition 0.000 description 2
- 230000035764 nutrition Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 210000002966 serum Anatomy 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 230000004083 survival effect Effects 0.000 description 2
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000252229 Carassius auratus Species 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000019733 Fish meal Nutrition 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000019742 Vitamins premix Nutrition 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000003797 alkaloid derivatives Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- VVYPIVJZLVJPGU-UHFFFAOYSA-L copper;2-aminoacetate Chemical compound [Cu+2].NCC([O-])=O.NCC([O-])=O VVYPIVJZLVJPGU-UHFFFAOYSA-L 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 102000038379 digestive enzymes Human genes 0.000 description 1
- 108091007734 digestive enzymes Proteins 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000004467 fishmeal Substances 0.000 description 1
- 235000012631 food intake Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036737 immune function Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000037356 lipid metabolism Effects 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002366 mineral element Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 230000001706 oxygenating effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 235000019629 palatability Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000022558 protein metabolic process Effects 0.000 description 1
- 238000001243 protein synthesis Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000019553 satiation Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 230000014616 translation Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- UJNPHNKJSKIVTE-SCGRZTRASA-L zinc;(2s)-2-amino-5-(diaminomethylideneamino)pentanoate Chemical compound [Zn+2].[O-]C(=O)[C@@H](N)CCCNC(N)=N.[O-]C(=O)[C@@H](N)CCCNC(N)=N UJNPHNKJSKIVTE-SCGRZTRASA-L 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/105—Aliphatic or alicyclic compounds
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/20—Inorganic substances, e.g. oligoelements
- A23K20/30—Oligoelements
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K50/00—Feeding-stuffs specially adapted for particular animals
- A23K50/80—Feeding-stuffs specially adapted for particular animals for aquatic animals, e.g. fish, crustaceans or molluscs
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
- C07C227/42—Crystallisation
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Food Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Animal Husbandry (AREA)
- Insects & Arthropods (AREA)
- Marine Sciences & Fisheries (AREA)
- Birds (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a betaine metal chelate crystal, which comprises the following steps: dissolving betaine powder in water, adding hydrochloric acid to adjust the pH value to be acidic, and stirring to form a betaine solution; dissolving divalent metal salt powder in water, and stirring to form a metal salt solution; adding a metal salt solution into the betaine solution, continuously adjusting the pH value to be acidic, heating, stirring and refluxing uniformly to form a reaction system, reacting to obtain a reaction solution, filtering to obtain a filtrate, standing and standing to obtain the betaine. According to the invention, through adjusting the pH, the temperature and the water addition amount in the solution, trimethylglycine and divalent metal salts (manganese and zinc) are combined by a one-step method for the first time, and the single crystal structure is obtained by utilizing the difference of solubility, so that the recrystallization times are reduced, the utilization rate of the mother liquor is improved, and a foundation is laid for the biological efficacy research of the betaine metal chelate. Also discloses a betaine metal chelate crystal and application thereof in preparing animal feed additives.
Description
Technical Field
The invention relates to the field of animal feed additives, and particularly relates to a preparation method of a betaine metal chelate crystal, and a product and application thereof.
Background
Betaine, also known as trimethylglycine inner salt, is a quaternary ammonium type alkaloid. Betaine is harmless to human bodies and the environment, most of betaine is metabolized in animal bodies and finally enters a protein synthesis series, and nitrogen generated during decomposition has extremely small load on the environment; it acts as a methyl donor and plays a central role in the protein and lipid metabolism of animals. In addition, the betaine also has the functions of relieving emergency, improving the activity of digestive enzyme, improving the palatability of feed, maintaining the stability of vitamin premix and the like.
The metal mineral elements related to human nutrition mainly comprise iron, zinc, calcium, copper, manganese and the like. Although the content of the compounds in the human body is not high, the compounds have extremely important physiological effects and participate in almost all metabolic processes of the human body. Conventional diets or feeds generally do not meet the requirements of the human and animal body for trace elements and must be additionally added or fortified. The metal element amino acid chelate is used as a new generation mineral nutrition enhancer and has wide application prospect.
Patent CN104853727A provides a method for synthesizing an oral care product comprising zinc oxide and trimethylglycine, but the method results in a mixture which, when diluted with water, produces a zinc oxide precipitate, indicating that it is simply complexed and does not actually sequester. Patent CN104853720A describes a method for the synthesis of a composition containing a zinc arginine/lysine halide precursor, mainly for personal care of the skin or hair, wherein a zinc salt is delivered to provide an antibacterial effect, but it does not provide a specific structure, but only supposes the possible structures.
Chelates of divalent metals such as zinc, copper have been studied extensively, and in general, divalent metals coordinate to oxygen and nitrogen on amino acids to form four-or six-coordinate bidentate chelates. However, little research has been done on chelates of betaines and are in the field of development. Therefore, how to prepare the betaine metal chelate with a definite structure has great significance.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings in the background technology and provide a preparation method of a betaine metal chelate crystal and a product and application thereof. On the basis of the current research situation of amino acid chelate at home and abroad, the reaction conditions are accurately controlled as follows: regulating the pH, temperature and water addition amount in the solution to obtain the betaine manganese chelate with a clear single crystal structure.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of betaine metal chelate crystal is provided, which comprises the following steps:
(1) dissolving betaine powder in water, adding hydrochloric acid to adjust pH to acidity, and stirring to form betaine solution;
(2) dissolving divalent metal salt powder in water, and stirring to form a metal salt solution;
(3) adding the metal salt solution into the betaine solution, continuously adjusting the pH value to be acidic, heating, stirring and refluxing uniformly to form a reaction system, and reacting to obtain a reaction solution;
(4) and filtering unreacted raw materials from the reaction solution to obtain filtrate, and standing to obtain the betaine metal chelate crystal.
In the above method, the concentration of the betaine solution in the step (1) is preferably 10 to 100 mM.
Preferably, in the step (1), the concentration of the betaine solution is 10-100 mM; the adding amount of the water is calculated by mixing 42-84 mL of water with 50-100 g of betaine; adjusting the pH value to 2-4; the stirring conditions are as follows: stirring at 50-120 rpm for 15-60 min (preferably at 90 rpm for 30 min).
Preferably, in step (2), the divalent metal salt comprises any one or more of zinc oxide, zinc chloride hydroxide, zinc sulfate, manganese oxide, manganese chloride tetrahydrate, manganese chloride hydroxide and manganese sulfate; the molar ratio of the divalent metal salt to the betaine is 1: 10-10: 1 (preferably 2:1), the concentration of the metal salt solution is 20-200 mM, and the stirring conditions are as follows: stirring at 90-120 rpm for 15-30 min (preferably at 100 rpm for 20 min).
Preferably, in the step (3), the pH is adjusted to 2-4; the stirring conditions are as follows: stirring for 4-12 h (preferably 100 r/min and stirring for 8h) at 90-120 r/min;
the volume of the reaction system is more than 50mL (preferably 50-1000 mL, more preferably 100-1000 mL, more preferably 200-500 mL, and most preferably 500 mL);
the reaction conditions are as follows: the pressure is 0.1-1 MPa, the reaction temperature is 40-100 ℃, and the reaction time is 4-12 h (preferably, the pressure is 0.1MPa, the reaction reflux temperature is 60 ℃, and the reaction time is 8 h).
Preferably, in the step (4), the reaction solution is filtered by suction through a buchner funnel, and is left standing for 0.5 to 7 days, preferably 2 days, to obtain crystals.
The invention controls the generation of crystals by adjusting the pH, the temperature and the water addition amount in the solution. If the pH is too high, the concentration of hydroxide ions in the solution is high, and the binding rate of divalent metal ions and betaine is influenced; too low a pH value may affect the reactivity of the carboxyl group and may be susceptible to some unwanted side reactions; the temperature not only influences the reaction speed, but also influences the crystallization speed, and when the temperature is too high, side reactions can occur; the temperature is too low, the reaction can not be carried out, and the betaine metal chelate of the invention can form betaine metal chelate crystals only at proper temperature; the amount of water added mainly affects the concentration of reactants and thus the reaction rate, and in addition, the amount of water added also affects the control of temperature and the growth of crystals.
The invention adopts hydrochloric acid to adjust the pH value because of the Cl of the hydrochloric acid - 、H + Is a component of the crystal itself, and does not introduce new impurities, under which the crystal characteristics of the present invention can be formed.
Based on a general inventive concept, the invention also provides a betaine metal chelate crystal which can be a betaine manganese crystal or a betaine zinc crystal.
The molecular structural formula of the betaine manganese crystal is shown in figure 3, and the molecular structural formula of the betaine zinc crystal is shown in figure 6.
Based on a general inventive concept, the present invention also provides an application of the betaine metal chelate crystal in preparing an animal feed additive.
In the above application, preferably, the animal feed additive is an aquatic feed additive.
Preferably, the betaine metal chelate crystal is added into the aquatic feed additive in an amount of 60-100ppm calculated by manganese and 30-70ppm calculated by zinc.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the preparation method, through adjusting the pH, the temperature and the water adding amount in the solution, trimethylglycine and divalent metal salts (manganese and zinc) are combined by a one-step method for the first time, and the single crystal structure is obtained by utilizing the difference of solubility, so that the recrystallization times are reduced, the utilization rate of the mother liquor is improved, and a foundation is laid for the biological efficacy research of the betaine metal chelate.
2. The preparation method disclosed by the invention is simple to operate, low in cost, high in preparation efficiency and environment-friendly.
3. The betaine metal chelate crystal can be a betaine manganese crystal or a betaine zinc crystal, is used for preparing a feed additive, particularly can be used for preparing an aquatic feed additive, has a remarkable improvement effect on the growth performance and the feed conversion rate of aquatic animals, can relieve the influence caused by osmotic pressure under the condition of a water area, can promote the shelling of shrimps, and has an antibacterial and insect-resistant effect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a crystal appearance of betaine manganese of the present invention.
FIG. 2 shows the crystal structure of betaine manganese according to the present invention.
FIG. 3 is the molecular structural formula of betaine manganese of the present invention.
FIG. 4 is the crystal appearance of betaine zinc chelate complexes of the present invention.
FIG. 5 is a crystal structure of betaine zinc chelate complex of the present invention.
FIG. 6 shows the molecular structure of the betaine zinc chelate complex of the present invention.
Detailed Description
In order to facilitate understanding of the invention, the invention will be described more fully and in detail with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
a preparation method of a betaine metal chelate crystal (betaine manganese crystal) comprises the following steps:
dissolving 50g of betaine powder in 42ml of water, adding dilute hydrochloric acid to adjust the pH to 2, stirring at 90 revolutions per minute for 30min to form betaine solution for later use; according to the mol ratio of betaine to manganese chloride of 10:1, dissolving manganese chloride of 5.4g in water of 40ml, stirring at 100 r/min for 20min, adding the betaine solution, continuously stirring and refluxing, adjusting the pH to 2, wherein the reaction temperature of the whole system is 60 ℃, the pressure is 0.1MPa, the stirring time is 8h, and the rotating speed is 100 r/min; and then, carrying out suction filtration on the reacted solution through a Buchner funnel, standing the obtained filtrate for 2 days, and obtaining light yellow crystals.
Example 2:
a preparation method of a betaine metal chelate crystal (betaine manganese crystal) comprises the following steps:
the difference between the embodiment and the embodiment 1 is that the temperature is different, 50g of betaine powder is dissolved in 42ml of water, dilute hydrochloric acid is added to adjust the pH value to be 2, the stirring speed is 90 revolutions per minute, and the stirring time is 30 minutes, so that betaine solution is formed for standby; then dissolving 28g of manganese chloride in 40ml of water, stirring at the speed of 100 r/min for 20min, adding the solution into the betaine solution, continuously stirring and refluxing, adjusting the pH to 2, wherein the reaction temperature of the whole system is 40 ℃, the pressure is 0.1MPa, the stirring time is 8h, and the rotating speed is 100 r/min; the reacted solution was then suction filtered through a buchner funnel, and the resulting filtrate was left to stand for 1 day to give pale yellow crystals.
Example 3:
a preparation method of a betaine metal chelate crystal (betaine manganese crystal) comprises the following steps:
the difference between the embodiment and the embodiment 1 lies in that the temperature is different, 50g of betaine powder is dissolved in 42ml of water, diluted hydrochloric acid is added to adjust the pH value to be 2, the stirring speed is 90 r/min, and the stirring time is 30min for standby; then 28g of manganese chloride is dissolved in 40ml of water, the stirring speed is 100 r/min, the betaine solution is added after the stirring time is 20min, the stirring and the reflux are continued, the pH value is adjusted to 2, the reaction temperature of the whole system is 80 ℃, the pressure is 0.1MPa, the stirring time is 8h, and the rotating speed is 100 r/min; the reacted solution was then filtered with suction through a buchner funnel, and the resulting filtrate was left to stand still for 0.5 days to give pale yellow crystals.
Example 4:
a preparation method of a betaine metal chelate crystal (betaine manganese crystal) comprises the following steps:
the difference between the embodiment and the embodiment 1 is that the pH is different, 50g of betaine powder is dissolved in 42ml of water, diluted hydrochloric acid is added to adjust the pH to be 2, the stirring speed is 90 r/min, and the stirring time is 30min, so that betaine solution is formed for standby; then dissolving 28g of manganese chloride in 40ml of water, stirring at the speed of 100 r/min for 20min, adding the solution into the betaine solution, continuously stirring and refluxing, adjusting the pH to 4, wherein the reaction temperature of the whole system is 100 ℃, the pressure is 0.1MPa, the stirring time is 8h, and the rotating speed is 100 r/min; the reacted solution was then filtered by suction through a buchner funnel, and the resulting filtrate was left to stand for 3 days to give pale yellow crystals.
Example 5:
a preparation method of a betaine metal chelate crystal (betaine manganese crystal) comprises the following steps:
dissolving 50g of betaine powder in 42ml of water, adding dilute hydrochloric acid to adjust the pH to 3, stirring at 90 revolutions per minute for 30min to form betaine solution for later use; dissolving 540g of manganese chloride in 40ml of water according to the molar ratio of the betaine to the manganese chloride of 1:10, stirring at 100 r/min for 20min, adding the betaine solution, continuously stirring and refluxing, adjusting the pH to 3, wherein the reaction temperature of the whole system is 60 ℃, the pressure is 0.1MPa, the stirring time is 4h, and the rotating speed is 100 r/min; the reacted solution was then suction filtered through a buchner funnel, and the resulting filtrate was left to stand for 7 days to give pale yellow crystals.
The results of the tests conducted on the crystals obtained in examples 1 to 5 of the present invention are shown in FIGS. 1 to 3 and tables 1 to 3.
FIG. 1 shows the resulting crystals, which have a tetragonal yellow appearance; FIG. 2 is a molecular structure diagram of chelate crystal, which is proved to be a one-dimensional chain structure, and a single crystal with the size of 0.30mm multiplied by 0.4mm is placed in a Bruker Smart 1000COn a CD type single crystal diffractometer, a Mo Ka (lambda is 0.071073nm) radiation light source monochromized by graphite collects 5875 independent diffraction points within the range of 2.26 degrees to 28.24 degrees under 293K, wherein 3523 can be observed points. The crystal structure is given by a direct method, all non-hydrogen atom coordinates and anisotropic parameters are corrected by a full matrix least square method, the table 1 shows the crystal parameters of the betaine manganese chelate, the crystal is a trigonal system, the space group is P-3(147),
Z＝2，
Dc＝1.51988g/cm 3 ，F(000)＝620，F(000)‘＝622.72，R1＝0.0347(1339)，wR2＝0.1023(1693)。
MnCl in FIG. 3 4 Is embedded in a crystal structure, the structural formula is obtained by analyzing the crystal structure, in the figure, a curve, a solid line and a dotted line are all bonds, and the curve and the dotted line represent single-double bond conjugation.
Table 2 lists all the atomic parameters of the chelate; table 3 lists the major bond lengths and angles of the molecules of the chelate, betaine providing 2 coordinating atoms, 2 oxygen atoms in the carboxyl group. As can be seen from fig. 3 in combination with the data in tables 2 and 3, the atoms coordinated with the central manganese ion are derived from two sites, one site is derived from oxygen in betaine molecules, and the other site is derived from chlorine atoms brought by manganese chloride, so that the coordination number of the central ion is in a saturated state of 6, and an octahedral complex is formed in the complex to form a one-dimensional chain structure; while manganese and chlorine are present in a tetra-coordinated form. The major bond length and bond angle of the molecule is: mn (1) -O1
Mn(2)—O2
Mn(3)—Cl2
Mn(3)—Cl1
O1W—H1WD
O1W—H1WB
O1W—H1WC
O1—Mn(1)—O193.18°，O1—Mn(1)—O1 180.00°，O1—Mn(1)—O1 86.82°；O2—Mn(2)—O2 88.26°，O2—Mn(2)—O2180.00°，O2—Mn(2)—O291.74°，Mn1—O(1)—C1136.2°，Mn2—O(2)—C1122.0°；Cl2—Mn(3)—Cl1105.86°，Cl1—Mn(3)—Cl1112.81°。
TABLE 1 structural data for betaine manganese
TABLE 2 relative coordinates of the atoms of betaine manganese
TABLE 3 bond length of betaine manganese chelate
| Atom 1 | Atom 2 | Length of key |
| MN1 | O1 | 2.1904 |
| MN2 | O2 | 2.1681 |
| MN3 | Cl2 | 2.373 |
| MN3 | Cl1 | 2.369 |
| C1 | C2 | 1.5329 |
| C1 | O1 | 1.2488 |
| C1 | O2 | 1.2558 |
| C2 | H2A | 0.9700 |
| C3 | H3A | 0.9600 |
| N1 | C2 | 1.5044 |
| N1 | C3 | 1.4988 |
| N1 | C4 | 1.5018 |
| N1 | C5 | 1.4911 |
Example 6:
a preparation method of betaine metal chelate crystals (betaine zinc crystals) comprises the following steps:
dissolving 50g of betaine powder in 42ml of water, adding dilute hydrochloric acid to adjust the pH to 2, and stirring at the speed of 90 revolutions per minute for 30 minutes for later use; then dissolving 30g of zinc chloride in 42ml of water, stirring at the speed of 100 revolutions per minute for 20 minutes, adding the zinc chloride into the solution, continuously stirring and refluxing, adjusting the pH to 2, wherein the reaction temperature of the whole system is 60 ℃, the pressure is 0.1MPa, the stirring time is 8 hours, and the rotating speed is 100 revolutions per minute; and then, carrying out suction filtration on the reacted solution through a Buchner funnel, standing the obtained filtrate for 2 days, and obtaining a white crystalline product.
Example 7:
a preparation method of betaine metal chelate crystals (betaine zinc crystals) comprises the following steps:
the difference between the embodiment and the embodiment 6 lies in that the temperature is different, 50g of betaine powder is dissolved in 42ml of water, diluted hydrochloric acid is added to adjust the pH value to be 2, the stirring speed is 90 revolutions per minute, and the stirring time is 30 minutes for standby; then dissolving 30g of zinc chloride in 42ml of water, stirring at the speed of 100 revolutions per minute for 20 minutes, adding the zinc chloride into the solution, continuously stirring and refluxing, adjusting the pH to 2, wherein the reaction temperature of the whole system is 40 ℃, the pressure is 0.1MPa, the stirring time is 8 hours, and the rotating speed is 100 revolutions per minute; the reacted solution was then filtered through a buchner funnel with suction, and the resulting filtrate was left to stand for 3 days. A crystalline product is obtained.
Example 8:
a preparation method of betaine metal chelate crystals (betaine zinc crystals) comprises the following steps:
the difference between the example and the example 6 is that the pH is different, 50g of betaine powder is dissolved in 42ml of water, diluted hydrochloric acid is added to adjust the pH to be 2, the stirring speed is 90 revolutions per minute, and the stirring time is 30 minutes for standby; then dissolving 30g of zinc chloride in 42ml of water, stirring at the speed of 100 revolutions per minute for 20 minutes, adding the zinc chloride into the solution, continuously stirring and refluxing, adjusting the pH to 4, wherein the reaction temperature of the whole system is 80 ℃, the pressure is 0.1MPa, the stirring time is 8 hours, and the rotating speed is 100 revolutions per minute; the reacted solution was then filtered through a buchner funnel with suction, and the resulting filtrate was left to stand for 0.5 days. A crystalline product is obtained.
Example 9:
a preparation method of a betaine metal chelate crystal (betaine zinc crystal) comprises the following steps:
the difference between the embodiment and the embodiment 6 lies in that the temperature and the pH are different, 50g of betaine powder is dissolved in 42ml of water, diluted hydrochloric acid is added to adjust the pH to be 4, the stirring speed is 90 revolutions per minute, and the stirring time is 30 minutes for standby; then dissolving 30g of zinc chloride in 42ml of water, stirring at the speed of 100 revolutions per minute for 20 minutes, adding the zinc chloride into the solution, continuously stirring and refluxing, adjusting the pH to 4, wherein the reaction temperature of the whole system is 40 ℃, the pressure is 0.1MPa, the stirring time is 8 hours, and the rotating speed is 100 revolutions per minute; and then, carrying out suction filtration on the reacted solution through a Buchner funnel, standing the obtained filtrate for 4 days, and obtaining a crystal product.
Example 10:
a preparation method of betaine metal chelate crystals (betaine zinc crystals) comprises the following steps:
the difference between the embodiment and the embodiment 6 lies in that the temperature and the pH are different, 50g of betaine powder is dissolved in 42ml of water, diluted hydrochloric acid is added to adjust the pH to be 3, the stirring speed is 90 revolutions per minute, and the stirring time is 30 minutes for standby; then dissolving 30g of zinc chloride in 42ml of water, stirring at the speed of 100 revolutions per minute for 20 minutes, adding the zinc chloride into the solution, continuously stirring and refluxing, adjusting the pH to 3, wherein the reaction temperature of the whole system is 15 ℃, the pressure is 0.1MPa, the stirring time is 8 hours, and the rotating speed is 100 revolutions per minute; and then, carrying out suction filtration on the reacted solution through a Buchner funnel, standing the obtained filtrate for 1 day, and obtaining a crystal product.
Example 11:
a preparation method of betaine metal chelate crystals (betaine zinc crystals) comprises the following steps:
the difference between the example and the example 6 lies in that the temperature and the reaction time are different, 50g of betaine powder is dissolved in 42ml of water, diluted hydrochloric acid is added to adjust the pH value to be 2, the stirring speed is 90 revolutions per minute, and the stirring time is 30 minutes for standby; then dissolving 30g of zinc chloride in 42ml of water, stirring at the speed of 100 revolutions per minute for 20 minutes, adding the zinc chloride into the solution, continuously stirring and refluxing, adjusting the pH to 3, wherein the reaction temperature of the whole system is 100 ℃, the pressure is 0.1MPa, the stirring time is 12 hours, and the rotating speed is 100 revolutions per minute; the reacted solution was then filtered with suction through a buchner funnel, and the resulting filtrate was left to stand for 7 days. A crystalline product is obtained.
The results of the tests conducted on the crystals obtained in examples 6 to 11 of the present invention are shown in FIGS. 4 to 6 and tables 4 to 6.
FIG. 4 shows the resulting crystal, which has a hexagonal prism-like appearance; FIG. 5 is a molecular structure diagram of a chelate crystal showing that the structure is a mononuclear structure, and a single crystal of 0.20 mm. times.0.30 mm. times.0.4 mm is placed on a Bruker Smart 1000CCD type single crystal diffractometer and irradiated with a Mo Ka (λ. 0.071073nm) monochromated with graphite at a light sourceUnder 293K, theta is between 2.56 and 26.37 degrees, 6147 independent diffraction points are collected in total, and 3335 observable points are obtained. The crystal structure is given by a direct method, all non-hydrogen atom coordinates and anisotropic parameters are corrected by a full matrix least square method, as shown in table 4, the crystal is a monoclinic system, the space group is P121/c 1(14),
β＝90.70(2)°，Z＝4，
Dc＝1.64164g/cm3，F(000)＝624，F(000)‘＝627.08，R1＝0.0650(1698)，wR2＝0.2253(2179)。
TABLE 4 betaine Zinc chelate Crystal parameters
Table 5 lists all the atomic parameters of the chelate; table 6 lists the major bond lengths and angles of the molecules of the chelate, betaine providing 1 coordinating atom, 1 oxygen atom in the carboxyl group. As can be seen from fig. 5 in conjunction with the data in table 6, the atoms coordinated to the central zinc ion are from three sites, one from 2 chlorine atoms on zinc chloride, one from chlorine atoms provided on hydrochloric acid, and one from oxygen atoms on betaine, satisfying the saturation state of the coordination number of the central ion of 4, and forming an octahedral complex in the complex, the whole system is mesoscopic, and therefore, the structure formed by the quadridentate zinc is 1 negatively charged, and therefore 1 positively charged in free water. The main bond length and angle of the molecule are Zn (1) -Cl 1
Zn(1)—Cl2
Zn(1)—Cl3
Zn(1)—O1
O1W—H1WD
O1W—H1WB
O1W—H1WC
Cl1—Zn(1)—Cl2111.39°，Cl2—Zn(1)—Cl3111.28°，Cl1—Zn(1)—O1113.3°，Cl3—Zn(1)—O1108.2°。
TABLE 5 coordinates of each atom of betaine Zinc chelate
TABLE 6 bond length of betaine Zinc chelate complexes
Comparative example 1:
dissolving 50g of betaine powder in 42ml of water, adding dilute hydrochloric acid to adjust the pH to 2, and stirring at 90 revolutions per minute for 30min for later use; then dissolving 30g of manganese chloride in 42ml of water, stirring at 100 r/min for 20min, adding the solution, continuously stirring and refluxing, adjusting the pH to 6, wherein the reaction temperature of the whole system is 80 ℃, the pressure is 0.1MPa, the stirring time is 8h, and the rotating speed is 100 r/min; and then, carrying out suction filtration on the reacted solution through a Buchner funnel, and standing the obtained filtrate for several days to obtain no crystal product.
Comparative example 2:
dissolving 50g of betaine powder in 42ml of water, adding dilute hydrochloric acid to adjust the pH to 2, and stirring at 90 revolutions per minute for 30min for later use; then dissolving 28g of manganese chloride in 40ml of water, stirring at the speed of 100 r/min for 20min, adding the solution, continuously stirring and refluxing, adjusting the pH to 8, wherein the reaction temperature of the whole system is 80 ℃, the pressure is 0.1MPa, the stirring time is 8h, and the rotating speed is 100 r/min; and then, carrying out suction filtration on the reacted solution through a Buchner funnel, and standing the obtained filtrate for several days to obtain no crystal product.
Comparative example 3:
dissolving 50g of betaine powder in 42ml of water, adding dilute hydrochloric acid to adjust the pH to 2, and stirring at 90 revolutions per minute for 30min for later use; according to the mol ratio of betaine to manganese chloride of 10:1, dissolving manganese chloride of 5.4g in water of 40ml, stirring at 100 r/min for 20min, adding the solution, continuously stirring and refluxing, adjusting the pH to 4, wherein the reaction temperature of the whole system is 110 ℃, the pressure is 0.1MPa, the stirring time is 8h, and the rotating speed is 100 r/min; and then, carrying out suction filtration on the reacted solution through a Buchner funnel, and standing the obtained filtrate for several days to obtain no crystal product.
Comparative example 4:
the difference between the comparative example and the example 1 is that the temperature and the proportional concentration are different, 50g of betaine powder is dissolved in 42ml of water, diluted hydrochloric acid is added to adjust the pH value to be 2, the stirring speed is 90 revolutions per minute, and the stirring time is 30 minutes for standby; dissolving 540g of manganese chloride in 40ml of water according to the molar ratio of 1:10 of betaine to manganese chloride, stirring at 100 r/min for 20min, adding the solution, continuously stirring and refluxing, adjusting the pH to 2, wherein the reaction temperature of the whole system is 15 ℃, the pressure is 0.1MPa, the stirring time is 8h, and the rotating speed is 100 r/min; and then, carrying out suction filtration on the reacted solution through a Buchner funnel, and standing the obtained filtrate for several days to obtain no crystal product.
Comparative example 5:
the difference between the comparative example and the example 1 is that the pH and the reaction time are different, 50g of betaine powder is dissolved in 42ml of water, diluted hydrochloric acid is added to adjust the pH to 3, the stirring speed is 90 revolutions per minute, and the stirring time is 30 minutes for standby; then dissolving 28g of manganese chloride in 40ml of water, stirring at the speed of 100 r/min for 20min, adding the solution, continuously stirring and refluxing, adjusting the pH to 1, wherein the reaction temperature of the whole system is 60 ℃, the pressure is 0.1MPa, the stirring time is 12h, and the rotating speed is 100 r/min; the reacted solution was then filtered with suction through a buchner funnel, and the resulting filtrate was left to stand for several days. The filtrate left standing still did not give a single crystal.
Comparative example 6:
the difference between the comparative example and the example 6 is that the temperature is different, 50g of betaine powder is dissolved in 42ml of water, diluted hydrochloric acid is added to adjust the pH value to 2, the stirring speed is 90 revolutions per minute, and the stirring time is 30 minutes for standby; then dissolving 30g of zinc chloride in 42ml of water, stirring at the speed of 100 revolutions per minute for 20 minutes, adding the zinc chloride into the solution, continuously stirring and refluxing, adjusting the pH to 2, wherein the reaction temperature of the whole system is 110 ℃, the pressure is 0.1MPa, the stirring time is 8 hours, and the rotating speed is 100 revolutions per minute; the reacted solution was then filtered with suction through a buchner funnel, and the resulting filtrate was left to stand for several days.
Due to the relatively high reaction temperature, a precipitate is obtained after the reaction, resulting in the formation of a nearly saturated solution in the filtrate, which upon cooling rapidly obtained a precipitate without obtaining a crystalline product.
Comparative example 7:
the comparative example is different from example 6 in pH, 50g of betaine powder is dissolved in 42ml of water, diluted hydrochloric acid is added to adjust the pH to 2, the stirring speed is 90 revolutions per minute, and the stirring time is 30 minutes for standby; then dissolving 30g of zinc chloride in 42ml of water, stirring at 100 revolutions per minute for 20 minutes, adding the zinc chloride into the solution, continuously stirring and refluxing, adjusting the pH to 6, wherein the reaction temperature of the whole system is 80 ℃, the pressure is 0.1MPa, the stirring time is 8 hours, and the rotating speed is 100 revolutions per minute; the reacted solution was then filtered with suction through a buchner funnel, and the resulting filtrate was left to stand for several days.
The filtrate left standing still did not yield a single crystal due to the change in pH.
Comparative example 8:
the difference between the comparative example and the example 6 is that the pH is different, 50g of betaine powder is dissolved in 42ml of water, diluted hydrochloric acid is added to adjust the pH to be 2, the stirring speed is 90 revolutions per minute, and the stirring time is 30 minutes for standby; then dissolving 30g of zinc chloride in 42ml of water, stirring at the speed of 100 revolutions per minute for 20 minutes, adding the zinc chloride into the solution, continuously stirring and refluxing, adjusting the pH to 8, wherein the reaction temperature of the whole system is 80 ℃, the pressure is 0.1MPa, the stirring time is 8 hours, and the rotating speed is 100 revolutions per minute; the reacted solution was then filtered with suction through a buchner funnel, and the resulting filtrate was left to stand for several days.
Due to the change of pH, the system is alkaline, and once the system is added, the zinc hydroxide precipitate is formed immediately, and no chelate of betaine zinc is formed, so that the filtrate which is placed still does not obtain a single crystal.
Comparative example 9:
the difference between the comparative example and the example 6 is that the temperature and the pH are different, 50g of betaine powder is dissolved in 42ml of water, diluted hydrochloric acid is added to adjust the pH to be 2, the stirring speed is 90 revolutions per minute, and the stirring time is 30 minutes for standby; then dissolving 30g of zinc chloride in 42ml of water, stirring at the speed of 100 revolutions per minute for 20 minutes, adding the zinc chloride into the solution, continuously stirring and refluxing, adjusting the pH to 1, wherein the reaction temperature of the whole system is 100 ℃, the pressure is 0.1MPa, the stirring time is 8h, and the rotating speed is 100 revolutions per minute; the reacted solution was then filtered with suction through a buchner funnel, and the resulting filtrate was left standing for several days without crystal generation.
Comparative example 10:
the difference between the comparative example and the example 6 is that the temperature is different, 50g of betaine powder is dissolved in 42ml of water, diluted hydrochloric acid is added to adjust the pH value to 2, the stirring speed is 90 revolutions per minute, and the stirring time is 30 minutes for standby; then dissolving 30g of zinc chloride in 42ml of water, stirring at the speed of 100 revolutions per minute for 20 minutes, adding the zinc chloride into the solution, continuously stirring and refluxing, adjusting the pH to 2, wherein the reaction temperature of the whole system is 10 ℃, the pressure is 0.1MPa, the stirring time is 8 hours, and the rotating speed is 100 revolutions per minute; the reacted solution was then filtered with suction through a buchner funnel, and the resulting filtrate was left to stand for several days. No crystal is generated.
Application example 1:
the feed additive prepared in example 1 was added to crucian feed.
Crucian carps with bright body color, no diseases and no injury on the body surface, strong physique and basically consistent body type and weight are selected in a trial, the weight is 344g, and the total weight is 1200. And (4) random average distribution. The experiment was designed to have 4 treatments, 6 replicates each, and 50 replicates each, with treatment 1, treatment 2, treatment 3, and treatment 4. The additive prepared in example 1 was added to the basal diet to achieve manganese levels of 0, 60, 80, and 100ppm for treatment 1, treatment 2, treatment 3, and treatment 4, respectively. Pulverizing all feed materials, sieving with 60 mesh sieve, mixing, making into hard granule feed with particle size of 3-6mm with a feed granulator, air drying, packaging into a sealed bag, and storing in a 4 deg.C refrigerator. The conventional salt water method is adopted to disinfect the fish body, and all crucian carps are domesticated for 15 days by using manganese-free basic feed before a test so as to adapt to the test feed. The cultivation experiment was carried out in a net cage with the water source being the local reservoir (natural water, no feed). Flowing water 24h a day, inflating for 24h, changing water 1/2 every week, feeding for 4 times (08: 00, 11: 00, 13: 30 and 16: 30) each day, and feeding for 30min each time, wherein the daily feeding amount is 2% -4% of the fish body mass. The water body temperature is measured every day, and the ingestion and activity conditions of the test fish are observed and recorded. The feeding amount is adjusted in time every week according to the weight and the food intake condition of the fish body. After 120 days of feeding, various indexes are measured.
1. Detection indexes are as follows:
and (3) measuring growth performance indexes: the number and total weight of each repeated crucian before the start were recorded. During the test, daily feeding and number of deaths, as well as body weight at death, were recorded. After the test was completed, the weight was repeated for each time after fasting for 24 hours.
The weight gain (%) × 100 [ (final average weight (g) — initial average weight (g) + dead fish weight (g))/initial average weight (g) ];
specific growth rate (%) [ (last average weight (g) of Ln — first average weight (g)) of Ln/day of culture ] × 100;
the feed coefficient is the total feed intake/(final weight-initial weight).
2. As a result:
the data in table 7 show that different levels of copper glycinate added have some effect on the growth performance of crucian. The final weight and specific growth rate of the treated 2 groups of experiments are remarkably higher than those of other groups (P is less than 0.01); compared with the treatment group 1, the treatment group 2 has extremely obviously reduced feed coefficient (P is less than 0.01); mortality was significantly lower in treatment 2 than in the other groups (P < 0.05).
TABLE 7 measurement results of growth Performance of Carassius auratus
And (4) conclusion:
the feed additive prepared in the embodiment 1 is added into crucian feed, so that the growth performance and the feed conversion rate of crucian are obviously improved, and the effect is best when the feed additive is added until the manganese content reaches 60 ppm.
Application example 2:
the feed additive prepared in example 6 was added to litopenaeus vannamei feed.
The test adopts a single-factor random grouping design, and the same shrimp larvae artificially hatched in the current year are selected. After the test shrimps are fasted for 24 hours, selecting healthy shrimps with strong physique, similar specifications, complete body surface and initial body mass (0.340 +/-0.001) g, dividing the healthy shrimps into a control group and 3 test groups, and processing 4 replicates each by each group, and repeating 40 shrimps by each group. Wherein, the control group was fed with a zinc-free basal diet (containing zinc 36.15mg/kg), and the test 1-3 groups were added with the composite bags prepared in example 1 respectively to make the zinc content: 30. 50 and 70 mg/kg. Each group of basic daily ration takes fish meal, bean pulp, peanut meal and corn protein powder as main protein sources. During the culture period, feeding the prawns with satiation at 8:00, 12:00, 17:00 and 21:00 every day, regularly observing the feeding condition of the prawns and recording the death number, adjusting the feeding amount according to the feeding condition and the weather, changing water for 1 time every two days, continuously oxygenating the water body during the culture period, and continuing the culture test for 8 weeks.
Detection indexes are as follows:
(1) and (3) measuring growth performance indexes: the number and total weight of each duplicate prawns before the start were recorded. During the test, daily feeding and number of deaths, as well as body weight at death, were recorded. After the test was completed, the weight was repeated for each time after fasting for 24 hours.
Survival rate (%) (shrimp tail at the end of test/shrimp tail at the beginning of test) × 100%;
the weight gain (%) is [ (end average weight (g) — initial average weight (g))/initial average weight (g) ] × 100%;
the bait coefficient is the total feeding amount (g)/(total final weight (g) — total initial weight (g) + dead shrimp weight (g))%;
specific growth rate (%) [ (ln last average weight-ln initial average weight)/day of cultivation ] × 100%.
(2) Blood index: weighing after the test is finished, randomly selecting 8 prawns from each repetition to collect blood samples, placing the blood samples into a 1.5mL centrifuge tube, standing overnight in a refrigerator at 4 ℃, centrifuging at 8000r/min for 10min, separating serum, subpackaging, and storing at-80 ℃ for later use. The activities of superoxide dismutase, acid phosphatase and alkaline phosphatase in serum are measured by using a kit provided by Nanjing institute of bioengineering, and the specific operations are performed according to the instructions.
As a result:
(1) growth performance indexes are as follows: as can be seen from table 8, the feed additive prepared in example 1 significantly improved the weight gain rate and specific growth rate of litopenaeus vannamei (P <0.05), significantly reduced the bait coefficient (P <0.05), and also reduced the mortality rate to some extent, wherein the survival rate was the highest when the test 2 groups were fed.
TABLE 8 Effect of betaine Zinc on Litopenaeus vannamei growth Performance
(2) Blood index: from table 9, the feed additive prepared in example 6 significantly improved the activities of total superoxide dismutase, acid phosphatase and alkaline phosphatase of litopenaeus vannamei (P < 0.05).
TABLE 9 influence of betaine Zinc on blood indices of Litopenaeus vannamei
And (4) conclusion:
the feed additive prepared in the embodiment 6 is added into the litopenaeus vannamei feed, so that the production performance and the non-specific immunoenzyme activity of the litopenaeus vannamei can be obviously improved, and the feed additive prepared in the embodiment 6 has good effects of promoting growth and improving immune function.
Claims (10)
1. A preparation method of a betaine metal chelate crystal is characterized by comprising the following steps:
(1) dissolving betaine powder in water, adding hydrochloric acid to adjust the pH value to be acidic, and stirring to form a betaine solution;
(2) dissolving divalent metal salt powder in water, and stirring to form a metal salt solution;
(3) adding the metal salt solution into the betaine solution, continuously adjusting the pH value to be acidic, heating, stirring and refluxing uniformly to form a reaction system, and reacting to obtain a reaction solution;
(4) and filtering unreacted raw materials from the reaction solution to obtain filtrate, and standing to obtain the betaine metal chelate crystal.
2. The method according to claim 1, wherein in the step (1), the concentration of the betaine solution is 10 to 100 mM; the adding amount of the water is calculated by mixing 42-84 mL of water with 50-100 g of betaine; adjusting the pH value to 2-4; the stirring conditions are as follows: stirring for 15-60 min at 50-120 rpm.
3. The preparation method according to claim 1, wherein in the step (2), the divalent metal salt comprises any one or more of zinc oxide, zinc chloride hydroxide, zinc sulfate, manganese oxide, manganese chloride tetrahydrate, manganese chloride hydroxide, manganese sulfate; the molar ratio of the divalent metal salt to the betaine is 1: 10-10: 1, the concentration of the metal salt solution is 20-200 mM, and the stirring conditions are as follows: stirring for 15-30 min at 90-120 rpm.
4. The method according to claim 1, wherein in the step (3), the pH is adjusted to 2 to 4; the stirring conditions are as follows: stirring for 4-12 h at 90-120 r/min; the volume of the reaction system is more than 50 mL; the reaction conditions are as follows: the pressure is 0.1-1 MPa, the reaction temperature is 15-100 ℃, and the reaction time is 4-12 h.
5. The method according to claim 1, wherein in the step (4), the standing time is 0.5 to 7 days.
6. A betaine metal chelate crystal produced by the production method according to any one of claims 1 to 5.
7. The betaine metal chelate crystal according to claim 6, wherein the betaine metal chelate crystal is a betaine manganese crystal or a betaine zinc crystal; the betaine manganese crystal comprises the following molecular structural formula:
the betaine zinc crystal comprises the following molecular structural formula:
8. use of the crystal of betaine metal chelate complex produced by the production method according to any one of claims 1 to 5 for producing an animal feed additive.
9. Use according to claim 8, wherein the animal feed supplement is an aquaculture feed supplement.
10. Use according to claim 9, wherein the betaine metal chelate crystals are added to the aquaculture feed additive in an amount of 60-100ppm as manganese and 30-70ppm as zinc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210518469.9A CN114957023A (en) | 2022-05-12 | 2022-05-12 | Preparation method of betaine metal chelate crystal, product and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210518469.9A CN114957023A (en) | 2022-05-12 | 2022-05-12 | Preparation method of betaine metal chelate crystal, product and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114957023A true CN114957023A (en) | 2022-08-30 |
Family
ID=82983300
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210518469.9A Pending CN114957023A (en) | 2022-05-12 | 2022-05-12 | Preparation method of betaine metal chelate crystal, product and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114957023A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289412A (en) * | 2008-05-23 | 2008-10-22 | 南昌大学 | Method for preparing chelates of zinc threonine |
| CN112409200A (en) * | 2020-11-27 | 2021-02-26 | 长沙兴嘉生物工程股份有限公司 | Preparation method and application of isoleucine chelated metal |
| WO2021245148A1 (en) * | 2020-06-04 | 2021-12-09 | BIOCHEM Zusatzstoffe Handels- und Produktionsgesellschaft mbH | Complex containing betaine, transition metal and sulfate |
-
2022
- 2022-05-12 CN CN202210518469.9A patent/CN114957023A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289412A (en) * | 2008-05-23 | 2008-10-22 | 南昌大学 | Method for preparing chelates of zinc threonine |
| WO2021245148A1 (en) * | 2020-06-04 | 2021-12-09 | BIOCHEM Zusatzstoffe Handels- und Produktionsgesellschaft mbH | Complex containing betaine, transition metal and sulfate |
| CN112409200A (en) * | 2020-11-27 | 2021-02-26 | 长沙兴嘉生物工程股份有限公司 | Preparation method and application of isoleucine chelated metal |
Non-Patent Citations (16)
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0377526B1 (en) | Use of copper complexes of alpha-amino acids that contain terminal amino groups as nutritional supplements | |
| EP1556336B1 (en) | Metal complexes of alpha amino dicarboxylic acids | |
| CN101289412B (en) | Method for preparing chelates of zinc threonine | |
| US11666071B2 (en) | Compound salt of N,N-dimethylglycine and an organic acid and composition and use thereof | |
| US9427001B2 (en) | Enhanced bioavailable iodine molecules | |
| CN114957023A (en) | Preparation method of betaine metal chelate crystal, product and application thereof | |
| JP2983171B2 (en) | New method for producing picolinic acid-chromium composite | |
| CN109123101B (en) | Preparation method of manganese nicotinate | |
| CN101289411B (en) | Method for preparing zinc threonine | |
| CN102550830A (en) | Method for applying and preparing gamma-aminobutyric acid complex compound | |
| CN102627585A (en) | Carbamyl glycine dipeptide chelated zinc and preparation method thereof | |
| JP6227762B2 (en) | Use of ethylenediamine metal complexes to deliver superabsorbent metals for animal nutrition | |
| JP7392976B2 (en) | mineral supplement | |
| KR20050083679A (en) | Use of metal chelates in human or animal feeding | |
| JP6956250B2 (en) | Methionine-metal chelate and its manufacturing method | |
| RU2695368C1 (en) | Method for obtaining highly digestible chelate colloid form of essential microelement of zinc | |
| JP2020526563A (en) | Methionine-metal chelate and its manufacturing method | |
| CN103497133A (en) | Method for preparing N-methylol group-D,L-calcium methionine microelement chelates by means of saponification liquid produced through D,L- methionine | |
| KR20030006877A (en) | Feed additive containing methionine-fe chelate | |
| CN103497135B (en) | One prepares N-methylol-D, the method for L-Methionine microelement chelate | |
| AU2018449359B2 (en) | Application of acylated derivative of amino acid in preparation of animal feed additive | |
| CN101891607B (en) | Production method for synthesizing zinc fumarate feed addictive by using secondary zinc oxide | |
| CN1105819A (en) | Amino-acid rare earth forage additive | |
| CN115160168A (en) | Zinc glycinate crystal and preparation method and application thereof | |
| CN116573999A (en) | Alpha-hydroxy organic acid-amino acid and analogue divalent metal co-salt compound thereof, 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 |