CN114163342A - Preparation method of manganese glycinate for feed with high manganese content - Google Patents
Preparation method of manganese glycinate for feed with high manganese content Download PDFInfo
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- CN114163342A CN114163342A CN202111628183.8A CN202111628183A CN114163342A CN 114163342 A CN114163342 A CN 114163342A CN 202111628183 A CN202111628183 A CN 202111628183A CN 114163342 A CN114163342 A CN 114163342A
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- 239000011572 manganese Substances 0.000 title claims abstract description 65
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 60
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 59
- JNMKPXXKHWQWFB-UHFFFAOYSA-L 2-aminoacetate;manganese(2+) Chemical compound [Mn+2].NCC([O-])=O.NCC([O-])=O JNMKPXXKHWQWFB-UHFFFAOYSA-L 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 48
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 32
- 239000004471 Glycine Substances 0.000 claims abstract description 22
- 238000001694 spray drying Methods 0.000 claims abstract description 22
- 239000003112 inhibitor Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000006227 byproduct Substances 0.000 claims abstract description 16
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011575 calcium Substances 0.000 claims abstract description 12
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 12
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000000292 calcium oxide Substances 0.000 claims abstract description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 10
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 10
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 6
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 claims abstract description 5
- 235000010261 calcium sulphite Nutrition 0.000 claims abstract description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- JXRVKYBCWUJJBP-UHFFFAOYSA-L calcium;hydrogen sulfate Chemical compound [Ca+2].OS([O-])(=O)=O.OS([O-])(=O)=O JXRVKYBCWUJJBP-UHFFFAOYSA-L 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract description 6
- 238000007086 side reaction Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 18
- 239000011573 trace mineral Substances 0.000 description 9
- 235000013619 trace mineral Nutrition 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 241001465754 Metazoa Species 0.000 description 4
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- LVGQIQHJMRUCRM-UHFFFAOYSA-L calcium bisulfite Chemical compound [Ca+2].OS([O-])=O.OS([O-])=O LVGQIQHJMRUCRM-UHFFFAOYSA-L 0.000 description 3
- 235000010260 calcium hydrogen sulphite Nutrition 0.000 description 3
- 210000003608 fece Anatomy 0.000 description 3
- 238000001757 thermogravimetry curve Methods 0.000 description 3
- 241000287828 Gallus gallus Species 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 229910052925 anhydrite Inorganic materials 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 230000029142 excretion Effects 0.000 description 2
- 230000002550 fecal effect Effects 0.000 description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- RUECTJATXCACED-UHFFFAOYSA-N 2-aminoacetic acid;hydrate Chemical compound [OH-].[NH3+]CC(O)=O RUECTJATXCACED-UHFFFAOYSA-N 0.000 description 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-M Aminoacetate Chemical compound NCC([O-])=O DHMQDGOQFOQNFH-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910018648 Mn—N Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 239000010828 animal waste Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 210000001320 hippocampus Anatomy 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- -1 manganese amino acid Chemical class 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 235000019629 palatability Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/142—Amino acids; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/20—Inorganic substances, e.g. oligoelements
-
- 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
- A23K20/24—Compounds of alkaline earth metals, e.g. magnesium
-
- 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
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- 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
- C07C227/44—Stabilisation; Use of additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/80—Food processing, e.g. use of renewable energies or variable speed drives in handling, conveying or stacking
- Y02P60/87—Re-use of by-products of food processing for fodder production
Abstract
The invention discloses a preparation method of manganese glycinate for feeds with high manganese content. The method comprises the steps of taking glycine and manganese sulfate as raw materials to react, adding a calcium source (calcium oxide or calcium hydroxide) and an inhibitor (calcium sulfite or calcium hydrogen sulfate) to continue to react in the reaction process, and filtering after the reaction is finished to obtain a reaction liquid and a byproduct calcium sulfate; and spray drying the reaction solution to obtain the manganese glycinate for the feed, the manganese content of which is more than or equal to 26 percent. In the method, a calcium source is added in the process of synthesizing manganese glycinate to precipitate sulfate radicals to obtain a byproduct calcium sulfate, so that the problem that salt-containing wastewater is difficult to treat is solved, trivalent manganese generated by oxidation in a solution is reduced into divalent manganese by adding an inhibitor, side reactions are eliminated, and the inhibitor is oxidized into the byproduct calcium sulfate. The method is green and environment-friendly, and is convenient for industrial production.
Description
Technical Field
The invention relates to the technical field of organic trace element synthesis, in particular to a preparation method of manganese glycinate (2:1 type) with high manganese content for feed.
Background
Manganese is one of indispensable trace elements of animal organisms and is generally dispersed in bones and livers of animals. The manganese content in the feed raw materials can not meet the requirements of animals, and the feed needs to be additionally supplemented during the preparation of the feed. In recent years, the organic trace element manganese has been used as a feed additive in production. The research proves that: the effect of adding organic manganese in the feed is obvious. Traditional trace element manganese is added in the form of inorganic salts such as manganese sulfate and manganese chloride, although the traditional trace element manganese is low in price, the traditional trace element manganese is easy to absorb moisture and low in bioavailability, meanwhile, a large amount of inorganic trace elements can be discharged along with animal wastes, the trace elements are wasted in utilization, and the trace elements can enter the land in the form of organic fertilizers to influence the harvest of crops. The amino acid chelated manganese obtained by taking the amino acid as the ligand to react with manganese has good stability, high absorption efficiency, high biological value, low toxicity and good palatability, and can completely replace inorganic manganese as a manganese supplement in the future, and the manganese glycinate has wide application prospect as a chelate which has the smallest molecular weight and is most easily absorbed in the manganese amino acid.
There are also many reports of manganese glycinate synthesis methods, such as patent CN112876372A, in which manganese salt is reacted with glycine to adjust pH by ammonia water to obtain light pink manganese glycinate with high chelating degree, but this document does not mention the handling of salt-containing mother liquor, and it is known that it is very difficult and expensive to handle salt-containing mother liquor in production. CN103739509B adopts manganese hydroxide firstly synthesized and then reacts with glycine to generate tiny white to light brown manganese glycinate without anions, but the reaction process needs to be carried out in vacuum, the production cost of the product is greatly improved, simultaneously, the manganese hydroxide is unstable, divalent manganese is easily oxidized in an alkaline solution to destroy the quality of the product, and the post-treatment of a byproduct sodium sulfate is difficult, thereby limiting the large-scale production of the manganese glycinate.
By analysis, the manganese glycinate sold in the market is mainly divided into two types: one is manganese glycinate containing sulfate radicals, the manganese content is higher and is about 22 percent, and the other is manganese glycinate without sulfate radicals, the manganese content is lower and is only about 15 percent. The molecular formula of the 2:1 manganese glycinate is Mn (C)2H4NO2)2The manganese content was 27.1%. The shortage of manganese content indicates that the chelating rate of the product is low, and the development of a preparation method of manganese glycinate (2:1 type) with high manganese content is needed.
Disclosure of Invention
The invention overcomes the defects of the prior art and provides a preparation method of manganese glycinate for feed with high manganese content. In the method, a calcium source is added in the process of synthesizing manganese glycinate to precipitate sulfate radicals to obtain a byproduct calcium sulfate, so that the problem that salt-containing wastewater is difficult to treat is solved, trivalent manganese generated by oxidation is reduced into divalent manganese by adding an inhibitor, side reactions are eliminated, and the inhibitor is also oxidized into the byproduct calcium sulfate. The method is green and environment-friendly, and is convenient for industrial production.
The technical scheme of the invention is as follows: a preparation method of manganese glycinate for feeds with high manganese content is characterized in that glycine and manganese sulfate are used as raw materials for reaction, a calcium source and an inhibitor are added in the reaction process for continuous reaction, and after the reaction is finished, reaction liquid and a byproduct calcium sulfate are obtained by filtration; and spray drying the reaction solution to obtain the manganese glycinate for the feed, the manganese content of which is more than or equal to 26 percent.
The method specifically comprises the following steps (a production process flow chart is shown in figure 1):
(1) and (3) synthesis reaction: adding a certain amount of water into a reaction kettle, starting stirring, heating to 40-60 ℃, adding glycine into the kettle for dissolving, adding manganese sulfate after completely dissolving, heating to 70-90 ℃, and continuing to react for 0.5-2 h;
(2) purifying and removing impurities: putting a calcium source and an inhibitor into a reaction kettle, continuously reacting for 0.5-2h, and filtering while hot after the reaction is finished to obtain a reaction solution and a byproduct calcium sulfate;
(3) spray drying: and carrying out spray drying on the reaction solution to obtain the manganese glycinate for the feed, wherein the manganese content of the manganese glycinate is more than or equal to 26%.
Wherein, the reaction kettle is an enamel reaction kettle.
Wherein, all the raw materials are feed grade.
Wherein the calcium source is calcium oxide or calcium hydroxide.
Wherein the inhibitor is calcium sulfite or calcium hydrogen sulfate.
Wherein, the preferable molar ratio of the glycine to the manganese sulfate is 2:1.01-2: 1.1.
Wherein, the mol ratio of the glycine to the calcium oxide or the calcium hydroxide is preferably 2:1.05-2: 1.5.
Wherein, the preferable molar ratio of the glycine to the inhibitor is 300:1-1000: 1.
Wherein, the water addition amount in the step (1) is preferably 200-350L per thousand moles of glycine water.
Wherein, preferably, the air inlet temperature of the spray drying in the step (3) is 160-.
The reaction mechanism in the invention takes calcium oxide as an example:
MnSO4+2Gly→Mn(Gly)2SO4
Mn(Gly)2SO4+CaO→Mn(Gly)2+CaSO4+H2O
side reaction:
4Mn2++8OH-+O2→4MnO(OH)+2H2O
the inhibitor is exemplified by calcium sulfite:
CaSO3+2MnO(OH)+4Gly→CaSO4+2Mn(Gly)2+3H2O
the invention has the beneficial effects that:
in the process of synthesizing manganese glycinate, the calcium source is added to precipitate sulfate radicals, the reaction liquid is further purified, the solution is alkaline due to the addition of the calcium source, divalent manganese is easily oxidized into trivalent manganese, the trivalent manganese generated by oxidation is reduced into the divalent manganese by adding the inhibitor, so that side reactions are eliminated, the inhibitor is oxidized into calcium sulfate byproducts, and the calcium sulfate byproducts can be used as a binder, an anti-caking agent, a stabilizer and an emulsifier to be added into the feed, so that the waste is changed into valuable, and the method is green and environment-friendly. The method solves the problem that the salt-containing wastewater is difficult to treat, and can obtain the high-purity 2:1 manganese glycinate. Through spray drying, the production efficiency is greatly improved, the industrial production is easy to realize, and the method has obvious economic and social benefits.
Drawings
FIG. 1 is a flow chart of the manganese glycinate production process of the invention.
FIG. 2 is an infrared absorption spectrum of manganese glycinate prepared in example 1 of the present invention;
FIG. 3 is a thermogram of manganese glycinate prepared in example 1 of the present invention;
fig. 4 fecal excretion for various groups of cycles.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a preparation method of manganese glycinate for feeds, which specifically comprises the following steps:
(1) and (3) synthesis reaction: adding 450.0L of water into the reaction kettle, starting stirring, heating to 55 ℃, adding 150.0kg of glycine into the kettle for dissolving, adding 177.5kg of manganese sulfate monohydrate after completely dissolving for 12min, heating to 80 ℃, and continuously reacting for 0.5h to obtain a clear reaction solution;
(2) purifying and removing impurities: putting 81.4kg of calcium hydroxide and 240g of inhibitor calcium sulfite into a reaction kettle, continuously reacting for 1 hour, and filtering while hot after the reaction is finished to obtain reaction liquid and a byproduct calcium sulfate;
(3) spray drying: and (3) carrying out spray drying on the reaction solution, wherein the air inlet temperature of the spray drying is 220 ℃, the air outlet temperature is 110 ℃, and the rotation speed is 10000r/min, so that 195.2kg of light brown manganese glycinate products are obtained. The yield was 95.2% and the manganese content was 26.86%.
The infrared absorption spectrum of manganese glycinate prepared in the example 1 is shown in figure 2, and the infrared absorption spectrum shows that glycine is located at 2130cm-1The characteristic absorption peak of the glycine at N-H disappears, which indicates that the N atom in the glycine participates in the coordination reaction and is 450cm-1And a Mn-N stretching vibration absorption peak appears, which indicates that glycine and manganese do have chelation reaction.
The thermogram of manganese glycinate chelate prepared in this example 1 is shown in FIG. 3, and it can be seen from the thermogram that: the weight loss of manganese glycinate is started from about 200 ℃, the ash content of the final product is 35.2 percent, the content of MnO is consistent, the weight loss of crystal water is not found, and the molecular formula of the product is Mn (C)2H5NO2)2。
Example 2
The embodiment provides a preparation method of manganese glycinate for feed, which comprises the following steps:
(1) and (3) synthesis reaction: adding 350.0L of water into the reaction kettle, starting stirring, heating to 55 ℃, adding 150.0kg of glycine into the kettle, dissolving, adding 177.5kg of manganese sulfate monohydrate after completely dissolving for 15min, heating to 70 ℃, and continuously reacting for 0.5h to obtain a clear reaction solution;
(2) purifying and removing impurities: putting 61.6kg of calcium oxide and 242g of inhibitor calcium hydrogen sulfite into a reaction kettle, continuously reacting for 2 hours, and filtering while hot after the reaction is finished to obtain a reaction solution and a byproduct calcium sulfate;
(3) spray drying: and (3) carrying out spray drying on the reaction solution, wherein the air inlet temperature of the spray drying is 230 ℃, the air outlet temperature is 115 ℃, and the rotating speed is 8000r/min, so as to obtain 193.3kg of light brown manganese glycinate product. The yield was 94.3% and the manganese content was 26.54%.
Example 3
The embodiment provides a preparation method of manganese glycinate for feed, which comprises the following steps:
(1) and (3) synthesis reaction: adding 3000L of water into reaction kettle, stirring, heating to 55 ℃, adding 750.0kg of glycine into the kettle, dissolving, adding 870.5kg of manganese sulfate monohydrate after completely dissolving for 10min, heating to 90 ℃, and continuously reacting for 1h to obtain a clear reaction solution;
(2) purifying and removing impurities: 294.0kg of calcium oxide and 1172.0g of inhibitor calcium hydrogen sulfite are put into a reaction kettle and continuously reacted for 2 hours, and after the reaction is finished, the reaction solution and the by-product calcium sulfate are obtained by filtering while the reaction solution is hot;
(3) spray drying: and (3) carrying out spray drying on the reaction solution, wherein the air inlet temperature of the spray drying is 200 ℃, the air outlet temperature is 100 ℃, and the rotating speed is 15000r/min, so that 986.1kg of light brown manganese glycinate products are obtained. The yield was 96.2% and the manganese content was 26.87%.
Example 4
The embodiment provides a preparation method of manganese glycinate for feed, which comprises the following steps:
(1) and (3) synthesis reaction: adding 2800L of water into the reaction kettle, starting stirring, heating to 55 ℃, adding 750.0kg of glycine into the kettle, dissolving, adding 870.5kg of manganese sulfate monohydrate after completely dissolving for 10min, heating to 90 ℃, and continuously reacting for 1h to obtain a clear reaction solution;
(2) purifying and removing impurities: 294.0kg of calcium oxide and 1172.0g of inhibitor calcium hydrogen sulfite are put into a reaction kettle and continuously reacted for 2 hours, and after the reaction is finished, the reaction solution and the by-product calcium sulfate are obtained by filtering while the reaction solution is hot;
(3) spray drying: and (3) carrying out spray drying on the reaction solution, wherein the air inlet temperature of the spray drying is 250 ℃, the air outlet temperature is 125 ℃, and the rotating speed is 16000r/min, so that 990.2kg of light brown manganese glycinate products are obtained. The yield was 96.6% and the manganese content was 26.72%.
Test example 1: broiler absorption test
Experiment time: 10/18/2021, site: hippocampus Temminck Biotech Ltd
100 laying hens aged 7 days are selected and divided into 4 groups, each group comprises 25 laying hens, basic daily ration is configured according to NY/T33-2004 chicken feeding standards, other components in the daily ration are unchanged, different manganese sources are added, the adding amount of the manganese is 60mg/kg, one group is inorganic manganese sulfate, the other group is commercially available manganese glycinate containing sulfate radicals (the content of the manganese is 22%), the other group is commercially available low-content manganese glycinate (the content of the manganese is 15%), and the four groups are 2:1 type manganese glycinate prepared in embodiment 1 of the invention.
Manganese absorption was measured by collecting animal feces, and each group of feces was collected once a week for 4 weeks. From fig. 4 we can observe that the overall manganese excretion in the faeces gradually decreases with the passage of the feeding cycle, which is related to the different manganese requirements during the growth period of the layers of different age on days, as can be seen by comparison of the different manganese addition groups: the fecal discharge of the three manganese glycinates is lower than that of inorganic manganese sulfate, and the comparison of the three manganese glycinates shows that: the lowest discharge of manganese in the excrement of the invention indicates that the utilization rate of the manganese 2:1 glycinate in the laying hens is the highest.
Claims (9)
1. A preparation method of manganese glycinate for feeds with high manganese content is characterized in that glycine and manganese sulfate are used as raw materials for reaction, a calcium source and an inhibitor are added in the reaction process for continuous reaction, and after the reaction is finished, reaction liquid and a byproduct calcium sulfate are obtained by filtration; and spray drying the reaction solution to obtain the manganese glycinate for the feed, the manganese content of which is more than or equal to 26 percent.
2. The method for preparing manganese glycinate for feed with high manganese content as claimed in claim 1, wherein the calcium source is calcium oxide or calcium hydroxide.
3. The method of claim 2, wherein the inhibitor is calcium sulfite or calcium hydrogen sulfate.
4. The preparation method of manganese glycinate for feeds with high manganese content as claimed in claim 3, which is characterized by comprising the following steps:
(1) and (3) synthesis reaction: adding water into a reaction kettle, starting stirring, heating to 40-60 ℃, putting glycine into the kettle for dissolving, adding manganese sulfate after complete dissolution, heating to 70-90 ℃, and continuing to react for 0.5-2 h;
(2) purifying and removing impurities: putting a calcium source and an inhibitor into a reaction kettle, continuously reacting for 0.5-2h, and filtering while hot after the reaction is finished to obtain a reaction solution and a byproduct calcium sulfate;
(3) spray drying: and carrying out spray drying on the reaction solution to obtain the manganese glycinate for the feed, wherein the manganese content of the manganese glycinate is more than or equal to 26%.
5. The method for preparing manganese glycinate for feeds with high manganese content as claimed in claim 4, wherein the molar ratio of the glycine to the manganese sulfate is 2:1.01-2: 1.1.
6. The method for preparing manganese glycinate for feeds with high manganese content according to claim 4, wherein the molar ratio of the glycine to the calcium source calcium oxide or calcium hydroxide is 2:1.05-2: 1.5.
7. The method for preparing manganese glycinate for feeds with high manganese content in claim 4, wherein the molar ratio of the glycine to the inhibitor is 300:1-1000: 1.
8. The method for preparing manganese glycinate for feed with high manganese content as claimed in claim 4, wherein the water addition amount in the step (1) is 200-350L per thousand mol of the water for glycine.
9. The method as claimed in claim 4, wherein the inlet air temperature of the spray drying in step (3) is 160-250 ℃, the outlet air temperature is 80-125 ℃, and the rotation speed is 8000-20000 r/min.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6407138B1 (en) * | 2000-10-11 | 2002-06-18 | Albion International, Inc. | Composition and method for preparing electrically neutral amino acid chelates free of interfering ions |
| US6426424B1 (en) * | 2000-10-11 | 2002-07-30 | Albion International, Inc. | Composition and method for preparing granular amino acid chelates and complexes |
| US20110077193A1 (en) * | 2007-01-01 | 2011-03-31 | Bioderm Research | Artemisinin Derivatives with Natural Amino Acids, Peptides, and Amino Sugars for the Treatment of Infection and Topical Condition in Mammals |
| CN103082088A (en) * | 2011-11-03 | 2013-05-08 | 青岛康地恩药业股份有限公司 | Preparation method of glycine trace element chelate with high purity |
| CN103492394A (en) * | 2011-02-17 | 2014-01-01 | Isf有限公司 | Process for preparing amino acid chelate compounds, amino acid chelate compounds and use of amino acid chelate compounds |
| CN103739509A (en) * | 2014-01-09 | 2014-04-23 | 山东祥维斯生物科技有限公司 | Industrial production and preparation process of glycine chelated manganese |
| CN107501371A (en) * | 2017-08-22 | 2017-12-22 | 南宁市泽威尔饲料有限责任公司 | A kind of complex compound of secondary complexing manganese and its production and use |
| WO2018037115A1 (en) * | 2016-08-25 | 2018-03-01 | Sil'innov Scrl | Composition comprising silicon and method for preparing same |
| US20180162803A1 (en) * | 2016-12-12 | 2018-06-14 | Novus International, Inc. | Metal complexes |
| CN111635331A (en) * | 2020-05-27 | 2020-09-08 | 天宝动物营养科技股份有限公司 | Method for preparing glycine chelate and microelement fertilizer/efficient slow-release fertilizer by using glycine mother liquor |
| CN112876372A (en) * | 2021-01-08 | 2021-06-01 | 邵阳学院 | Preparation method of manganese glycinate with high chelating degree |
-
2021
- 2021-12-28 CN CN202111628183.8A patent/CN114163342B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6407138B1 (en) * | 2000-10-11 | 2002-06-18 | Albion International, Inc. | Composition and method for preparing electrically neutral amino acid chelates free of interfering ions |
| US6426424B1 (en) * | 2000-10-11 | 2002-07-30 | Albion International, Inc. | Composition and method for preparing granular amino acid chelates and complexes |
| US20110077193A1 (en) * | 2007-01-01 | 2011-03-31 | Bioderm Research | Artemisinin Derivatives with Natural Amino Acids, Peptides, and Amino Sugars for the Treatment of Infection and Topical Condition in Mammals |
| CN103492394A (en) * | 2011-02-17 | 2014-01-01 | Isf有限公司 | Process for preparing amino acid chelate compounds, amino acid chelate compounds and use of amino acid chelate compounds |
| CN103082088A (en) * | 2011-11-03 | 2013-05-08 | 青岛康地恩药业股份有限公司 | Preparation method of glycine trace element chelate with high purity |
| CN103739509A (en) * | 2014-01-09 | 2014-04-23 | 山东祥维斯生物科技有限公司 | Industrial production and preparation process of glycine chelated manganese |
| WO2018037115A1 (en) * | 2016-08-25 | 2018-03-01 | Sil'innov Scrl | Composition comprising silicon and method for preparing same |
| US20180162803A1 (en) * | 2016-12-12 | 2018-06-14 | Novus International, Inc. | Metal complexes |
| CN107501371A (en) * | 2017-08-22 | 2017-12-22 | 南宁市泽威尔饲料有限责任公司 | A kind of complex compound of secondary complexing manganese and its production and use |
| CN111635331A (en) * | 2020-05-27 | 2020-09-08 | 天宝动物营养科技股份有限公司 | Method for preparing glycine chelate and microelement fertilizer/efficient slow-release fertilizer by using glycine mother liquor |
| CN112876372A (en) * | 2021-01-08 | 2021-06-01 | 邵阳学院 | Preparation method of manganese glycinate with high chelating degree |
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