CN114163342B - 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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- 239000011572 manganese Substances 0.000 title claims abstract description 59
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 54
- 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 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 42
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 28
- 238000001694 spray drying Methods 0.000 claims abstract description 21
- 239000004471 Glycine Substances 0.000 claims abstract description 19
- 239000003112 inhibitor Substances 0.000 claims abstract description 19
- 239000006227 byproduct Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011575 calcium Substances 0.000 claims abstract description 11
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 11
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 11
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 11
- 235000007079 manganese sulphate Nutrition 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
- 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 8
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 7
- 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
- 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
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract 3
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000004090 dissolution Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 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
- RUECTJATXCACED-UHFFFAOYSA-N 2-aminoacetic acid;hydrate Chemical compound [OH-].[NH3+]CC(O)=O RUECTJATXCACED-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 5
- 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
- 239000002351 wastewater Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 14
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000011573 trace mineral Substances 0.000 description 7
- 235000013619 trace mineral Nutrition 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 241001465754 Metazoa Species 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 210000003608 fece Anatomy 0.000 description 4
- 150000001413 amino acids Chemical class 0.000 description 3
- YAECNLICDQSIKA-UHFFFAOYSA-L calcium;sulfanide Chemical compound [SH-].[SH-].[Ca+2] YAECNLICDQSIKA-UHFFFAOYSA-L 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 241000287828 Gallus gallus Species 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 230000029142 excretion Effects 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 2
- 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 2
- 239000012452 mother liquor Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 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
- 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
- 230000007812 deficiency Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000002550 fecal effect Effects 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003895 organic fertilizer Substances 0.000 description 1
- 235000019629 palatability Nutrition 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
- 239000002699 waste material Substances 0.000 description 1
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
- A23K20/142—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 feed with high manganese content. The invention takes glycine and manganese sulfate as raw materials to react, a calcium source (calcium oxide or calcium hydroxide) and an inhibitor (calcium sulfite or calcium bisulfate) are added in the reaction process to continue the reaction, and the reaction liquid and a byproduct of calcium sulfate are obtained by filtering after the reaction is finished; and (3) spray-drying the reaction solution to obtain manganese glycinate for feed, wherein the manganese content of the manganese glycinate is more than or equal to 26%. In the process of synthesizing manganese glycinate, a calcium source is added to precipitate sulfate radical to obtain a byproduct calcium sulfate, the problem that salt-containing wastewater is difficult to treat is solved, trivalent manganese generated by oxidation in a solution is reduced to divalent manganese by adding an inhibitor, side reaction is eliminated, and the inhibitor is oxidized to the byproduct calcium sulfate. The method is 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) for feed with high manganese content.
Background
Manganese is one of essential trace elements of animal body, and is widely dispersed in bones and livers of animals. The manganese content in the feed raw material can not meet the requirements of animals, and the feed raw material needs to be additionally supplemented when the feed is prepared. In recent years, manganese, an organic trace element, has been used in production as a feed additive. The study proves that: the effect of adding organic manganese into the feed is obvious. The traditional trace elements manganese are added in the form of inorganic salts such as manganese sulfate, manganese chloride and the like, and although the manganese sulfate is low in cost, the manganese sulfate and the manganese chloride are easy to absorb moisture and low in bioavailability, and meanwhile, a large amount of inorganic trace elements are discharged along with animal manure, so that the trace elements are wasted, and a large amount of trace elements enter the land in the form of organic fertilizer to affect the harvest of crops. The amino acid chelated manganese obtained by the reaction of the amino acid serving as a ligand and manganese has the advantages of good stability, high absorption efficiency, high biological potency, low toxicity and good palatability, and can completely replace inorganic manganese to serve as a manganese supplement in the future, and manganese glycinate serving as a chelate which has the minimum molecular weight and is most easily absorbed in the amino acid manganese has a wide application prospect.
At present, a few methods for synthesizing manganese glycinate are reported, for example, in patent CN112876372A, manganese salt is reacted with glycine, pH is adjusted by ammonia water to obtain light pink manganese glycinate with high chelating degree, but the document does not mention the treatment condition of salt-containing mother liquor, and it is known that the salt-containing mother liquor is difficult and expensive to treat in production. CN103739509B is prepared by synthesizing manganese hydroxide firstly and then reacting with glycine to generate micro-white to light brown manganese glycinate without anions, but the reaction is performed in vacuum, so that the production cost of the product is greatly increased, meanwhile, manganese hydroxide is unstable, divalent manganese is easily oxidized in alkaline solution to damage the quality of the product, and the byproduct sodium sulfate is difficult to post-treat, so that the mass production of manganese glycinate is limited.
According to analysis, manganese glycinate sold in the market is mainly divided into two types: one type is manganese glycinate containing sulfate radical, the manganese content is relatively high, about 22%, and the other type is manganese glycinate without sulfate radical, the manganese content is relatively low, and only about 15%. The molecular formula of manganese glycinate of type 2:1 should be Mn (C 2 H 4 NO 2 ) 2 The manganese content was 27.1%. The deficiency of manganese content indicates that the chelation rate of the product is low, and a preparation method of manganese glycinate (2:1 type) with high manganese content needs to be developed.
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 process of synthesizing manganese glycinate, a calcium source is added to precipitate sulfate radical to obtain a byproduct calcium sulfate, the problem that salt-containing wastewater is difficult to treat is solved, trivalent manganese generated by oxidation is reduced to divalent manganese by adding an inhibitor, side reaction is eliminated, and the inhibitor is oxidized to the byproduct calcium sulfate. The method is environment-friendly and is convenient for industrial production.
The technical scheme of the invention is as follows: the preparation method of the manganese glycinate for the feed 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, a reaction solution and a byproduct calcium sulfate are obtained by filtration; and (3) spray-drying the reaction solution to obtain manganese glycinate for feed, wherein the manganese content of the manganese glycinate is more than or equal to 26%.
The method specifically comprises the following steps (the 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 dissolution, adding manganese sulfate after dissolution is completed, heating to 70-90 ℃, and continuing to react for 0.5-2h;
(2) Purifying and removing impurities: adding a calcium source and an inhibitor into a reaction kettle, continuously reacting for 0.5-2h, and filtering while the reaction is hot to obtain a reaction solution and a byproduct calcium sulfate;
(3) Spray drying: and (3) carrying out spray drying on the reaction liquid to obtain the manganese glycinate for the feed, wherein the manganese content of the manganese glycinate is more than or equal to 26%.
Wherein, foretell reation kettle is enamel reation 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 bisulfate.
Wherein, the molar ratio of glycine to manganese sulfate is preferably 2:1.01-2:1.1.
Wherein, the molar ratio of glycine to calcium oxide or calcium hydroxide is preferably 2:1.05-2:1.5.
Wherein, preferably, the mol ratio of the glycine to the inhibitor is 300:1-1000:1.
Wherein, preferably, the water added in the step (1) is 200-350L per thousand moles of glycine water.
Wherein, preferably, the air inlet temperature of spray drying in the step (3) is 160-250 ℃, the air outlet temperature is 80-125 ℃, and the rotating speed is 8000-20000r/min.
The reaction mechanism in the invention takes calcium oxide as an example:
MnSO 4 +2Gly→Mn(Gly) 2 SO 4
Mn(Gly) 2 SO 4 +CaO→Mn(Gly) 2 +CaSO 4 +H 2 O
side reaction:
4Mn 2+ +8OH - +O 2 →4MnO(OH)+2H 2 O
the inhibitor is exemplified by calcium sulfite:
CaSO 3 +2MnO(OH)+4Gly→CaSO 4 +2Mn(Gly) 2 +3H 2 O
the beneficial effects of the invention are as follows:
in the process of synthesizing manganese glycinate, a calcium source is added to precipitate sulfate radical, the reaction solution is further purified, the solution is alkaline due to the addition of the calcium source, divalent manganese is extremely easy to oxidize into trivalent manganese, and trivalent manganese generated by oxidation is reduced into divalent manganese by adding an inhibitor, so that side reaction is eliminated, meanwhile, the inhibitor is oxidized into byproduct calcium sulfate, and the byproduct calcium sulfate can be used as a binder, an anti-caking agent, a stabilizer and an emulsifier to be added into feed, so that waste is changed into valuable, and environment is protected. The method solves the problem that the salt-containing wastewater is difficult to treat, and can obtain high-purity 2:1 manganese glycinate. The spray drying greatly improves the production efficiency, is easy for industrial production, and 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 thermogravimetric plot of manganese glycinate prepared in example 1 of the present invention;
figure 4 shows the faecal excretion of groups during different periods.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with specific embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a preparation method of manganese glycinate for feed, 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 dissolution, adding 177.5kg of manganese sulfate monohydrate after the dissolution is completed for 12min, heating to 80 ℃, and continuing to react for 0.5h to obtain a clear reaction solution;
(2) Purifying and removing impurities: adding 81.4kg of calcium hydroxide and 240g of inhibitor calcium sulfite into a reaction kettle, continuously reacting for 1h, and filtering while the reaction is hot to obtain a reaction solution and byproduct calcium sulfate;
(3) Spray drying: and (3) spray-drying the reaction solution, wherein the air inlet temperature of the spray-drying is 220 ℃, the air outlet temperature is 110 ℃, and the rotating speed is 10000r/min, so as to obtain 195.2kg of light brown manganese glycinate product. The yield was 95.2% and the manganese content was 26.86%.
As can be seen from the infrared absorption spectrum of manganese glycinate prepared in example 1 shown in FIG. 2, glycine was located at 2130cm -1 The characteristic absorption peak of N-H disappears, which indicates that N atom in glycine participates in coordination reaction and is 450cm in length -1 Mn-N stretching vibration absorption peaks appear, which shows that glycine and manganese are indeed chelated.
The thermogravimetric diagram of the manganese glycinate chelate prepared in this example 1 is shown in fig. 3, from which it can be seen that: the weight loss of manganese glycinate from about 200 ℃ is not found, the ash content of the final product is 35.2%, the content of the final product is consistent with that of MnO, the weight loss of crystal water is not found, and the molecular formula of the final product is Mn (C) 2 H 5 NO 2 ) 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 for dissolution, adding 177.5kg of manganese sulfate monohydrate after the dissolution is completed for 15min, heating to 70 ℃, and continuing to react for 0.5h to obtain a clear reaction solution;
(2) Purifying and removing impurities: 61.6kg of calcium oxide and 242g of inhibitor calcium bisulfide are put into a reaction kettle to continue to react for 2 hours, and the reaction liquid and byproduct calcium sulfate are obtained by filtering when the reaction is hot;
(3) Spray drying: and (3) spray-drying the reaction liquid, 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 that 193.3kg of light brown manganese glycinate product is obtained. 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 the reaction kettle, starting stirring, heating to 55 ℃, adding 750.0kg of glycine into the kettle, dissolving for 10min, adding 870.5kg of manganese sulfate monohydrate after complete dissolution, heating to 90 ℃, and continuing to react for 1h to obtain a clear reaction solution;
(2) Purifying and removing impurities: adding 294.0kg of calcium oxide and 1172.0g of inhibitor calcium bisulfide into a reaction kettle, continuously reacting for 2 hours, and filtering while the reaction is hot to obtain a reaction solution and byproduct calcium sulfate;
(3) Spray drying: and (3) spray-drying the reaction liquid, 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 as to obtain 986.1kg of light brown manganese glycinate product. 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 for 10min, adding 870.5kg of manganese sulfate monohydrate after complete dissolution, heating to 90 ℃, and continuing to react for 1h to obtain a clear reaction solution;
(2) Purifying and removing impurities: adding 294.0kg of calcium oxide and 1172.0g of inhibitor calcium bisulfide into a reaction kettle, continuously reacting for 2 hours, and filtering while the reaction is hot to obtain a reaction solution and byproduct calcium sulfate;
(3) Spray drying: and (3) spray-drying the reaction liquid, 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 as to obtain 990.2kg of light brown manganese glycinate. The yield was 96.6% and the manganese content was 26.72%.
Test example 1: broiler chicken absorption test
Experimental time: 2021, 10 months, 18 days, location: mountain east Asian Taihai Hua Biotechnology Co.Ltd
100 laying hens of 7 days old are selected and divided into 4 groups, 25 laying hens in each group are allocated with basic daily ration according to NY/T33-2004 chicken feeding standards, other components in the daily ration are unchanged, different manganese is added from different experimental groups, the addition amount of manganese is 60mg/kg, one group is inorganic manganese sulfate, the other group is commercially available manganese glycinate containing sulfate radical (manganese content is 22%), the other group is commercially available manganese glycinate with low content (manganese content is 15%), and the other group is manganese glycinate of type 2:1 prepared in the embodiment 1 of the invention.
The absorption of manganese was detected by collecting animal faeces, each group of faeces was collected once a week for a total of 4 weeks. From fig. 4 we can observe that the total manganese excretion in the faeces gradually decreases over the feeding period, which is related to the different manganese demands of different day-old layers in the growth period, as can be seen by comparison of the different manganese addition groups: the fecal discharge of the three manganese glycinates was lower than the inorganic manganese sulfate content, as can be seen by comparison of the three groups of manganese glycinates: the discharge of manganese in the excrement is the lowest, which shows that the utilization rate of the 2:1 manganese glycinate in the laying hen is the highest.
Claims (6)
1. The preparation method of the manganese glycinate for the feed with high manganese content is characterized by comprising the following steps of:
(1) And (3) synthesis reaction: adding water into a reaction kettle, starting stirring, heating to 40-60 ℃, adding glycine into the kettle for dissolution, adding manganese sulfate after complete dissolution, heating to 70-90 ℃, and continuing to react for 0.5-2h;
(2) Purifying and removing impurities: adding a calcium source and an inhibitor into a reaction kettle, continuously reacting for 0.5-2h, and filtering while the reaction is hot to obtain a reaction solution and a byproduct calcium sulfate; the calcium source is calcium oxide or calcium hydroxide; the inhibitor is calcium sulfite or calcium bisulfate;
(3) Spray drying: and (3) carrying out spray drying on the reaction liquid to obtain the manganese glycinate for the feed, wherein the manganese content of the manganese glycinate is more than or equal to 26%.
2. The method for preparing manganese glycinate for feed with high manganese content according to claim 1, wherein the molar ratio of glycine to manganese sulfate is 2:1.01-2:1.1.
3. The method for preparing manganese glycinate for feed with high manganese content according to claim 1, wherein the molar ratio of glycine to calcium source calcium oxide or calcium hydroxide is 2:1.05-2:1.5.
4. The method for preparing manganese glycinate for feed with high manganese content according to claim 1, wherein the molar ratio of glycine to inhibitor is 300:1-1000:1.
5. The method for preparing manganese glycinate for feed with high manganese content according to claim 1, wherein the water added in the step (1) is 200-350L per thousand moles of glycine water.
6. The method for preparing manganese glycinate for feed with high manganese content according to claim 1, wherein the air inlet temperature of spray drying in the step (3) is 160-250 ℃, the air outlet temperature is 80-125 ℃ and the rotating speed is 8000-20000r/min.
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