CN109456239A - A kind of production technology of a-amino acid chelated chromium (III) - Google Patents

A kind of production technology of a-amino acid chelated chromium (III) Download PDF

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CN109456239A
CN109456239A CN201811329503.8A CN201811329503A CN109456239A CN 109456239 A CN109456239 A CN 109456239A CN 201811329503 A CN201811329503 A CN 201811329503A CN 109456239 A CN109456239 A CN 109456239A
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amino acid
chromium
iii
methionine
glycine
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周荣超
廖常福
粟宇
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Lufeng Tianbao Phosphorus Chemical Co Ltd
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Lufeng Tianbao Phosphorus Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a kind of production technologies of a-amino acid chelated chromium (III), the process is the following steps are included: to certain temperature and keep the temperature a period of time for the mother liquor containing a-amino acid and alkali Hybrid Heating, it is subsequently cooled to 60 DEG C~90 DEG C, concentration is carried out under condition of negative pressure, it is concentrated into a certain concentration, active carbon is added and carries out decolorization；Then a certain amount of inorganic chromic salt compound is added, reaction a period of time is sufficiently stirred under the conditions of 75 DEG C~95 DEG C, after fully reacting, reaction mixture is cooled to room temperature, a large amount of solid is precipitated, is filtered, washed, dries, obtains a-amino acid chelated chromium (III) compound.The invention realizes remaining a-amino acid and alpha-amino acid derivatives in a-amino acid crystalline mother solution and has obtained effective comprehensive utilization, reduces in a-amino acid production process the discharge of " three wastes " and its waste of resource, green, environmental protection, cleaning.

Description

A kind of production technology of a-amino acid chelated chromium (III)
Technical field
The invention belongs to feed addictive preparation fields, and in particular to a kind of production work of a-amino acid chelated chromium (III) Skill.
Technical background
Chromium is a kind of important strategic resource, and chromic salts series of products are widely used, are related to the commodity product of national economy about 10% Kind, there is irreplaceability.Chromic salts major product include sodium dichromate, chromic anhybride, potassium bichromate, chromium oxide, chromium sulfate basic, Chromium chloride.Domestic common inorganic chromate salt product variety has more than 30 kinds, wherein sodium dichromate is the base for preparing serial chromium compound Plinth product, most of other chromic salts products are derived by parent of sodium dichromate.But at present there is production in China's Chrome Salt Industry The defects of product less varieties, added value is low, and multidigit Cr VI product, and toxicity is big.The research and development of high added value chromium product have become Chromic salts industry urgent technology in China's needs and market orientation guiding.
Trivalent chromium is that animal body maintains normal sugar metabolism and the necessary microelement of lipid metaboli.Organic Chromium product and inorganic chromium It compares, there is higher absorptivity, bioactivity and safety, as the auxiliary element of antidiabetic drug, nutritional supplement and flesh Meat moulding agent is widely used.Organic Chromium product, which is synthesized, as ligand using natural bioactivity substance has become research hotspot With product development direction.
Currently, Organic Chromium product is used for feed, food and pharmaceuticals industry mainly as additive.It, can be in feed Effectively increase lean meat percentage, improve the price of deed, improve growth of animals or poultry performance, reduces carcass lipid and back-fat thickness, Yi Jizeng Add lean meat percentage, the stress reaction of animal can also be reduced.Organic Chromium product is added in daily ration can significantly improve farrowing rate and breeding Rate improves the reproductive performance of animal.It, will necessarily very big development again in feedstuff industry with the raising of people's quality of the life Prospect.
Methionine also known as methionine are one of the essential amino acids for constituting human body, are a kind of antioxidant, can be effectively clear Except the intracorporal free radical of biology.The native ligand of it or chromium, the sulphur atom (S) in methionine molecule is metallic ion coordination Most common most important coordinating group.The complex that methionine and trivalent chromium are formed is able to suppress in physiological conditions The olation of chromium acts on, and guarantees the biological activity of trivalent chromium and methionine.Methionine and trivalent chromium all have removing free radical With the effect for inhibiting free radical to generate, the two enhances the synergistic effect of the two after forming complex.
A-amino acid chelated chromium (III) be used as a kind of Organic Chromium product, be mainly used on the market at present feed, food and In pharmaceuticals industry.It is used as its additive in feed, the price of deed can be effectively improved, improves growth of animals or poultry performance, drop Low carcass lipid and back-fat thickness；The stress reaction of animal can be reduced, promotes growth, addition can significantly improve farrowing in daily ration Rate improves breeding rate, improves the breeding body condition of animal, can be used as the reason that country prohibites the clenbuterol hydrochloride used in feedstuff industry Think substitute.With the raising of people's quality of the life, the increase of animal feeding, before feedstuff industry necessarily has very big development Scape.A-amino acid chelated chromium (III) is mainly used for assisting in the treatment of type-2 diabetes mellitus in food and medicine industry, also serves as weight-reducing and protects The auxiliary element of health food.
The synthetic method of a-amino acid chromium (III) chelate reported at present is typically all by a-amino acid and solubility three After valence chromic salts such as chromium chloride is stirred sufficiently in water, strong caustic adjusting pH value of solution is added dropwise under stiring to be made to give birth to At a-amino acid chromium (III) chelate precipitate and be precipitated, stand cooled and filtered, it is sufficiently dry after filter cake water and ethanol washing It is dry to obtain a-amino acid chromium product.The method operation is cumbersome, and keeps product heavy by the way that sodium hydroxide solution adjusting pH is added dropwise The method in shallow lake industrially without utility value, cannot achieve continuous production；Organic solvent is used in process of production, causes to have Solvent recycling and its loss, cause its production energy consumption higher, increase the production cost of product；It is several in Conventional process It is all using the a-amino acid of the pharmaceutical grade of high-purity, food-grade or feed grade, and some a-amino acids are more expensive , thus this necessarily result in a-amino acid chromium (III) chelate the market price it is higher, answered on a large scale to affect it With.
In a-amino acid production process, a-amino acid crystallization is inevitable operating process, and a-amino acid crystallization is α-ammonia One important means of base acid purifying, this will generate a large amount of crystalline mother solution, and crystalline mother solution can regular quantitative extraction portion Point, purity after the crystallization of a-amino acid is influenced to prevent so-called impurities accumulation in mother liquor.The common processing of the mother liquor of extraction Means are concentration, burning disposal, and such processing mode not only causes the waste of resource, and also cause the dirt of environment Dye, it is not only uneconomical but also not cost-effective.Therefore, the comprehensive utilization of a-amino acid crystalline mother solution is the difficult point studied at present.
Summary of the invention
The present invention is directed to the drawbacks of synthetic method of traditional a-amino acid chromium (III) chelate and combines our company Products characteristics are developed and a kind of utilize a-amino acid crystalline mother solution and chromic salt production a-amino acid chromium (III) chelate Production technology.
The technique of production a-amino acid chelated chromium (III) provided by the present invention, includes the following steps:
By the mother liquor containing a-amino acid and alkali Hybrid Heating to certain temperature and heat preservation a period of time, it is subsequently cooled to 60 DEG C ~90 DEG C, concentration is carried out under condition of negative pressure, is concentrated into a certain concentration, and active carbon is added and carries out decolorization, then again A certain amount of chromic salt compound is added, reaction a period of time is sufficiently stirred under the conditions of 75 DEG C~95 DEG C, after fully reacting, Reaction mixture is cooled to room temperature, and a large amount of solid is precipitated, and is filtered, washed, is dried, and a-amino acid chelated chromium (III) chemical combination is obtained Object.
A-amino acid used in production technology is the crystalline mother solution containing DL- METHIONINE, glycine and L-threonine, and These so-called crystalline mother solutions are the aqueous solutions that outlet is needed in amino acid crystallization process, and why outlet is because of amino Purity after the crystallization of amino acid of impurity effect in acid mother liquor, its impurities accumulation, needs outlet mother liquor in order to prevent.Cause This, a-amino acid raw material used in the present invention is discarded a-amino acid crystalline mother solution.Although in a-amino acid crystalline mother solution Other than a-amino acid, also containing other as a-amino acid dipeptides, a-amino acid diketopiperazine compound, a-amino acid ammonium salt, The impurity such as alpha-amino acid amides are can not effectively to chelate with trivalent chromium, and therefore, these useful impurity are can to pass through certain Kind mode is effectively converted into utilizable a-amino acid.There are many this transform mode, but effective mode is exactly Hydrolysis, these impurity are that can be fully converted to a-amino acid under hydrolysising condition.
Further, in the DL- METHIONINE crystalline mother solution, DL- METHIONINE, DL- METHIONINE dipeptides, DL- METHIONINE diketone Diethylenediamine compound, DL- METHIONINE ammonium salt or DL- METHIONINE amide or methionine glycolylurea or methionine hydantoic acid 3%~9wt% of the sum of content, the pH of mother liquor are 3.5~8.0.The molecular structure of impurity is such as in the DL- METHIONINE crystalline mother solution Under:
DL- METHIONINE crystalline mother solution described above is, therefore the crystallization of DL- METHIONINE relevant to its methionine production technology Mother liquor can be the recrystallization mother liquor or traditional Luo Na-Planck egg ammonia of the methionine of cyanalcohol glycolylurea sylvite method production The crystalline mother solution that the methionine recrystallization mother liquor or pure methionine that acid production process obtains are further purified, it is described These mother liquors pH be it is entirely different, therefore, impurities are different in mother liquor, but the common feature of these impurity is Hydrolysis can be converted into DL- METHIONINE under alkalinity and hot conditions.
Further, in the glycine crystallization mother liquid, glycine, glycine dimer, glycine diketopiperazine, glycine The sum of content of ammonium salt or glycine amide or hydantoins or hydantoic acid is 10%~30wt%, and the pH of mother liquor is 3.5 ~7.5.The molecular structure of impurity is as follows in the glycine crystallization mother liquid:
When glycin mother liquid described above can prepare glycine for chloroactic acid method, the recrystallization mother liquor of glycine, Huo Zhewei When direct glycolylurea method prepares glycine, the recrystallization mother liquor of glycine, or prepare for the direct ammonification alkaline hydrolysiss of hydroxyacetonitrile sweet When propylhomoserin, the recrystallization mother liquor of glycine.Different methods prepares the crystalline mother solution of glycine, and the pH of mother liquor is entirely different , it is completely different including the impurity in mother liquor, but the common feature of these impurity is in alkalinity and high temperature Under the conditions of hydrolysis can be converted into glycine.
Further, in the L-threonine crystalline mother solution, threonine, threonine dimer, threonine diketopiperazine or 12%~25wt% of the sum of threonine ammonium salt or threonine amide content, the pH of mother liquor are 3.5~7.0.The L-threonine The molecular structure of impurity is as follows in crystalline mother solution:
It is different according to technique for above-mentioned L-threonine crystalline mother solution, and impurity is also different in mother liquor, and pH is also different.But in mother liquor Impurity has the characteristics that common, that is, these so-called impurity are hydrolysis can be converted into L- Soviet Union ammonia under alkalinity and hot conditions Acid and be used.
Further, the alkali is sodium carbonate, in potassium carbonate, sodium bicarbonate, saleratus, sodium hydroxide, potassium hydroxide One or more, preferred sodium hydroxide, particularly preferred sodium hydrate aqueous solution.
Further, the reaction temperature of the mother liquor of the a-amino acid and alkali be 80 DEG C~170 DEG C, preferably 120 DEG C~170 DEG C, particularly preferred 150 DEG C~170 DEG C, the reaction time is 20~180min, preferably 30~60min, particularly preferred 30~40min.
Further, it is 20%~50wt% that the a-amino acid crystalline mother solution is concentrated into the concentration of a-amino acid after hydrolysis.
Further, chromium (III) salt is the anhydrous compound or hydrated compound of chromium sulfate or chromium chloride.
Further, the molar ratio of the a-amino acid, alkali and chromium ion (III) are as follows: alpha-amido acid/base/chromium ion (III)=1.0:1.0:3.0, reaction temperature are 75 DEG C~95 DEG C, preferably 75 DEG C~90 DEG C, particularly preferred 80 DEG C~90 DEG C, are reacted Time is 60~180min, preferably 90~120min.
Further, the molecular formula of the a-amino acid chelated chromium (III) is respectively DL- METHIONINE chelated chromium [Cr (C5H10NO2S)3], glycine chelate chromium [Cr(C2H4NO2)3.H2O], L-threonine chelated chromium [Cr(C4H8NO3)3]。
Compared with prior art, the method have the advantages that:
(1) present invention establishes new a-amino acid chelated chromium (III) production technology, with traditional production technology and newest organic Synthetic method is compared in solvent: the present invention uses a-amino acid crystalline mother solution for raw material, plays waste utilization, avoids money The waste in source, create Social benefit and economic benefit, the very good solution processing problem of a-amino acid crystalline mother solution.
(2) present invention and traditional organic solvent method ratio, use water not, to avoid the steaming of organic solvent as reaction medium Hair, recycling and rectification process, either the consumption of energy consumption or material all well below use organic solvent as reaction Jie Matter；
(3) the method for the present invention have simple operations, reaction temperature is low, the operating time is short, the yield of product can reach 92% or more, The purity of product can reach 99% or more, and the process flow for producing a-amino acid chelated chromium (III) is simple, easily realize industrialization, The industry of process stabilizing, key equipment is highly reliable.
(4) method of the present invention avoids conventional method and uses tune during sodium hydrate aqueous solution again chelatropic reaction The tedious steps for saving pH, simplify operation, more easily realization industrialized production；
(5) combination of the crystallization of a-amino acid and a-amino acid chelated chromium (III) production technology, both can solve a-amino acid The wasting of resources caused by the discharge of crystalline mother solution avoids the processing modes such as traditional concentration, burning, and utilizes crystalline mother solution Production a-amino acid chelated chromium (III) has reached economic and environment-friendly.
Detailed description of the invention
Fig. 1 is a-amino acid chelated chromium (III) production technological process.
Specific embodiment
The present invention is described in further detail below by specific embodiment, it is not to limit that following embodiment, which is descriptive, Property, this does not limit the scope of protection of the present invention.
The production procedure of process units system of the present invention is as follows:
A certain amount of a-amino acid crystalline mother solution and sodium hydrate aqueous solution are added in static mixer by metering pump and carried out Adequately mixing, is then preheated to 150 DEG C~170 DEG C by heat exchanger, is transferred in tubular reactor and reaction is hydrolyzed, and keeps Certain temperature and residence time, obtained hydrolyzate, which is transferred in concentration kettle, carries out reduced pressure processing, it is concentrated into 20%~ 50wt% is added a certain amount of active carbon and carries out decolorization, and filter activity charcoal obtains a-amino acid sodium water solution, is transferred to chelating In reaction kettle, inorganic chromic salt is then added, chelatropic reaction is carried out at certain temperature and reaction time, reaction terminates Afterwards, 20 DEG C~30 DEG C are cooled to, is then centrifuged for, washs, dries, obtains a-amino acid chelated chromium (III) compound, centrifuge mother liquor It can be discharged after sewage treatment is qualified.Process is as shown in Figure 1.It will illustrate the present invention with specific embodiment below, just In understanding that technical solution of the present invention, typical but non-limiting embodiment of the invention are as follows:
Embodiment 1
DL- METHIONINE crystalline mother solution 1910.25kg is taken, wherein methionine, methionylmethionine, methionine diketopiperazine, egg are analyzed Propylhomoserin amide, methionine ammonium salt amount to 7.8wt%, and the pH of crystalline mother solution is 4.0.By DL- METHIONINE crystalline mother solution and 50wt% hydrogen Aqueous solution of sodium oxide 80kg passes through flowmeter respectively and is added in static mixer, is heated to 150 DEG C by heat exchanger, then into Enter in tubular reactor, 30min, reaction pressure 0.8Mpa are kept the temperature in tubular reactor, the material flowed out from tubular reactor Liquid is transferred in concentration kettle and is concentrated under reduced pressure, and the content for being concentrated into methionine is 28wt%, obtains Sodium L-methioninate aqueous solution, Then the active carbon that feed liquid 0.5wt% is added carries out decolorization, is centrifuged off active carbon, and centrifugate is transferred in chelatropic reaction kettle, 75 DEG C are warming up to, six 65.36kg(166.67 moles of the hydrated sulfuric acid chromium of feed grade of content 99% is then added), after adding, immediately 90 DEG C are warming up to, is stirred to react 3 hours, a large amount of purple red precipitate is precipitated, is cooled to 25 DEG C, centrifugation, washing, drying obtain DL- METHIONINE chelated chromium (III) product 153.66kg, DL- METHIONINE chelated chromium (III) yield are 92.0%, and main content is 99wt%, Chelating chromium content is 10.44wt%, and the molecular formula of the DL- METHIONINE chelated chromium (III) is [Cr(C5H10NO2S)3]。
Embodiment 2
DL- METHIONINE crystalline mother solution 1910.25kg is taken, wherein methionine, methionylmethionine, methionine diketopiperazine, egg are analyzed Propylhomoserin amide, methionine glycolylurea, methionine ammonium salt, methionine hydantoic acid amount to 7.8wt%, and the pH of DL- METHIONINE crystalline mother solution is 8.0.DL- METHIONINE crystalline mother solution and 50wt% sodium hydrate aqueous solution 80kg are passed through into flowmeter respectively and are added to static mixing In device, 165 DEG C are heated to by heat exchanger, subsequently into 30min in tubular reactor, is kept the temperature in tubular reactor, is reacted Pressure is 0.89Mpa, and the feed liquid flowed out from tubular reactor, which is transferred in concentration kettle, to be concentrated under reduced pressure, and is concentrated into containing for methionine Amount is 30wt%, obtains Sodium L-methioninate aqueous solution, and the active carbon that feed liquid 0.5wt% is then added carries out decolorization, centrifugation Active carbon is removed, centrifugate is transferred in chelatropic reaction kettle, is warming up to 75 DEG C, and the feed grade anhydrous slufuric acid of content 99% is then added 47.84kg(166.67 moles of chromium), after adding, it is warming up to 95 DEG C immediately, is stirred to react 2.5 hours, a large amount of aubergine is precipitated Precipitating, is cooled to 30 DEG C, and centrifugation, washing, drying obtain DL- METHIONINE chelated chromium (III) product 151.21kg, DL- METHIONINE Chelated chromium (III) yield is 91.0%, and main content is 99.5wt%, and chelating chromium content is 10.44wt%, the DL- METHIONINE chelated chromium (III) molecular formula is [Cr(C5H10NO2S)3]。
Embodiment 3
DL- METHIONINE crystalline mother solution 1910.25kg is taken, wherein methionine, methionylmethionine, methionine diketopiperazine are total for analysis 7.8wt%, the pH of DL- METHIONINE crystalline mother solution are 5.8.By DL- METHIONINE crystalline mother solution and 50wt% sodium hydrate aqueous solution 80kg passes through flowmeter respectively and is added in static mixer, 170 DEG C is heated to by heat exchanger, subsequently into tubular reactor In, 30min, reaction pressure 1.0Mpa are kept the temperature in tubular reactor, the feed liquid flowed out from tubular reactor is transferred to concentration kettle In be concentrated under reduced pressure, be concentrated into methionine content be 30wt%, obtain Sodium L-methioninate aqueous solution, feed liquid be then added The active carbon of 0.5wt% carries out decolorization, is centrifuged off active carbon, and centrifugate is transferred in chelatropic reaction kettle, is warming up to 75 DEG C, Then 53.32kg(333.33 moles of the feed grade anhydrous chromium trichloride of content 99% is added), after adding, it is warming up to 95 DEG C immediately, It is stirred to react 2.5 hours, a large amount of purple red precipitate is precipitated, be cooled to 30 DEG C, centrifugation, washing, drying obtain DL- METHIONINE Chelated chromium (III) product 151.21kg, DL- METHIONINE chelated chromium (III) yield are 91.0%, and main content is 99.5wt%, chelated chromium Content is 10.44wt%, and the molecular formula of the DL- METHIONINE chelated chromium (III) is [Cr(C5H10NO2S)3]。
Embodiment 4
DL- METHIONINE crystalline mother solution 1910.25kg is taken, wherein methionine, methionylmethionine, methionine diketopiperazine, egg are analyzed Propylhomoserin amide, methionine glycolylurea, methionine ammonium salt, methionine hydantoic acid amount to 7.8wt%, and the pH of DL- METHIONINE crystalline mother solution is 7.8.DL- METHIONINE crystalline mother solution and 50wt% sodium hydrate aqueous solution 80kg are passed through into flowmeter respectively and are added to static mixing In device, 160 DEG C are heated to by heat exchanger, subsequently into 30min in tubular reactor, is kept the temperature in tubular reactor, is reacted Pressure is 0.85Mpa, and the feed liquid flowed out from tubular reactor, which is transferred in concentration kettle, to be concentrated under reduced pressure, and is concentrated into containing for methionine Amount is 30wt%, obtains Sodium L-methioninate aqueous solution, and the active carbon that feed liquid 0.5wt% is then added carries out decolorization, centrifugation Active carbon is removed, centrifugate is transferred in chelatropic reaction kettle, is warming up to 75 DEG C, and the hydration of feed grade six three of content 99% is then added 98.80kg(333.33 moles of chromium chloride), after adding, it is warming up to 95 DEG C immediately, is stirred to react 2.5 hours, is precipitated a large amount of purple Red precipitate, is cooled to 30 DEG C, and centrifugation, washing, drying obtain DL- METHIONINE chelated chromium (III) product 153.66kg, DL- egg Propylhomoserin chelated chromium (III) yield is 92.0%, and main content is 99wt%, and chelating chromium content is 10.41wt%, DL- METHIONINE chelating The molecular formula of chromium (III) is [Cr(C5H10NO2S)3]。
Embodiment 5
Glycine crystallization mother liquid 500kg is taken, wherein glycine, glycine dipeptidase, glycine diketopiperazine, glycine acyl are analyzed Amine, hydantoins, glycine ammonium, glycolylurea hydrochlorate amount to 15wt%, when which is glycolylurea method glycine recrystallization Mother liquor, the pH of mother liquor are 7.4.Glycine crystallization mother liquid and 50wt% sodium hydrate aqueous solution 80kg are added by flowmeter respectively Enter into static mixer, is heated to 170 DEG C by heat exchanger, subsequently into tubular reactor, is protected in tubular reactor Warm 40min, reaction pressure 1.0Mpa, the feed liquid flowed out from tubular reactor, which is transferred in concentration kettle, to be concentrated under reduced pressure, and is concentrated Content to glycine is 50wt%, obtains Sodium Glycinate aqueous solution, and the active carbon that feed liquid 0.5wt% is then added is taken off Color processing, is centrifuged off active carbon, and centrifugate is transferred in chelatropic reaction kettle, is warming up to 75 DEG C, and the feed of content 99% is then added Six 65.36kg(166.67 moles of hydrated sulfuric acid chromium of grade), after adding, it is warming up to 90 DEG C immediately, is stirred to react 3 hours, is precipitated big The rose of amount precipitates, and is cooled to 25 DEG C, and centrifugation, washing, drying obtain glycine chelate chromium (III) product 86.37kg, sweet ammonia Sour chelated chromium (III) yield is 94.0%, and main content is 99.4wt%, and chelating chromium content is 17.80wt%, the glycine chelate chromium (III) molecular formula is [Cr(C2H4NO2)3.H2O]。
Embodiment 6
Glycine crystallization mother liquid 500kg is taken, wherein glycine, glycine dipeptidase, glycine diketopiperazine, glycine acyl are analyzed Amine, hydantoins, glycine ammonium salt, hydantoic acid amount to 15wt%.By glycine crystallization mother liquid and 50wt% sodium hydrate aqueous solution 80kg passes through flowmeter respectively and is added in static mixer, 168 DEG C is heated to by heat exchanger, subsequently into tubular reactor In, 40min, reaction pressure 1.0Mpa are kept the temperature in tubular reactor, the feed liquid flowed out from tubular reactor is transferred to concentration kettle In be concentrated under reduced pressure, be concentrated into glycine content be 45wt%, obtain Sodium Glycinate aqueous solution, feed liquid be then added The active carbon of 0.5wt% carries out decolorization, is centrifuged off active carbon, and centrifugate is transferred in chelatropic reaction kettle, is warming up to 75 DEG C, Then 98.80kg(333.33 moles of six hydrated chromium trichloride of feed grade of content 99% is added), after adding, it is warming up to 90 immediately DEG C, it is stirred to react 3 hours, a large amount of rose precipitating is precipitated, be cooled to 20 DEG C, centrifugation, washing, drying obtain glycine chela Chromium (III) product 82.69kg is closed, glycine chelate chromium (III) yield is 94.0%, and main content is 99.4wt%, and chelating chromium content is 17.80wt%, the molecular formula of the glycine chelate chromium (III) are [Cr(C2H4NO2)3.H2O]。
Embodiment 7
Glycine crystallization mother liquid 500kg is taken, wherein glycine, glycine dipeptidase, glycine diketopiperazine, glycine ammonium salt are analyzed Total 15wt%, the glycine crystallization mother liquid are the recrystallization mother liquor that chloroactic acid method prepares glycine, and the pH of mother liquor is 5.9.It will be sweet Propylhomoserin crystalline mother solution and 50wt% sodium hydrate aqueous solution 80kg pass through flowmeter respectively and are added in static mixer, by changing Hot device is heated to 168 DEG C, and subsequently into tubular reactor, keeping the temperature 40min in tubular reactor, reaction pressure is 1.0Mpa, the feed liquid flowed out from tubular reactor, which is transferred in concentration kettle, to be concentrated under reduced pressure, and the content for being concentrated into glycine is 45wt% obtains Sodium Glycinate aqueous solution, and the active carbon that feed liquid 0.5wt% is then added carries out decolorization, is centrifuged off Active carbon, centrifugate are transferred in chelatropic reaction kettle, are warming up to 75 DEG C, and six trichloride hydrate of feed grade of content 99% is then added 98.80kg(333.33 moles of chromium), after adding, it is warming up to 90 DEG C immediately, is stirred to react 3 hours, it is heavy that a large amount of rose is precipitated It forms sediment, is cooled to 20 DEG C, centrifugation, washing, drying obtain glycine chelate chromium (III) product 82.69kg, glycine chelate chromium (III) Yield is 94.0%, and main content is 99.4wt%, and chelating chromium content is 17.80wt%, and the molecular formula of the glycine chelate chromium (III) is [Cr(C2H4NO2)3.H2O]。
Embodiment 8
Glycine crystallization mother liquid 500kg is taken, wherein glycine, glycine dipeptidase, glycine diketopiperazine, glycine ammonium salt are analyzed Total 15wt%, which is the glycine recrystallization mother liquor that hydroxyacetonitrile ammonification alkaline hydrolysiss prepare glycine, female The pH of liquid is 4.5.Glycine crystallization mother liquid and 50wt% sodium hydrate aqueous solution 80kg are passed through into flowmeter respectively and are added to static state In mixers, 168 DEG C are heated to by heat exchanger, subsequently into tubular reactor, 40min is kept the temperature in tubular reactor, Reaction pressure is 1.0Mpa, and the feed liquid flowed out from tubular reactor, which is transferred in concentration kettle, to be concentrated under reduced pressure, and is concentrated into glycine Content be 45wt%, obtain Sodium Glycinate aqueous solution, then be added feed liquid 0.5wt% active carbon carry out decolorization, It is centrifuged off active carbon, centrifugate is transferred in chelatropic reaction kettle, is warming up to 75 DEG C, and six water of feed grade of content 99% is then added Close 98.80kg(333.33 moles of chromium trichloride), after adding, it is warming up to 90 DEG C immediately, is stirred to react 3 hours, is precipitated a large amount of Rose precipitating, is cooled to 20 DEG C, and centrifugation, washing, drying obtain glycine chelate chromium (III) product 82.69kg, glycine chela Closing chromium (III) yield is 94.0%, and main content is 99.4wt%, and chelating chromium content is 17.80wt%, the glycine chelate chromium (III) Molecular formula is [Cr(C2H4NO2)3.H2O]。
Embodiment 9
L-threonine crystalline mother solution 794.13kg is taken, wherein L-threonine, L-threonine dipeptides, L-threonine diketone piperazine are analyzed Piperazine, L-threonine ammonium salt amount to 15wt%, and the pH of the crystalline mother solution is 4.5.By L-threonine crystalline mother solution and 50wt% hydroxide Sodium water solution 80kg passes through flowmeter respectively and is added in static mixer, 170 DEG C is heated to by heat exchanger, subsequently into pipe In formula reactor, 40min, reaction pressure 1.0Mpa are kept the temperature in tubular reactor, the feed liquid flowed out from tubular reactor turns Entering in concentration kettle and is concentrated under reduced pressure, the content for being concentrated into L-threonine is 40wt%, L-threonine sodium water solution is obtained, Then the active carbon that feed liquid 0.5wt% is added carries out decolorization, is centrifuged off active carbon, and centrifugate is transferred in chelatropic reaction kettle, 75 DEG C are warming up to, six 65.36kg(166.67 moles of the hydrated sulfuric acid chromium of feed grade of content 99% is then added), after adding, immediately 90 DEG C are warming up to, is stirred to react 3 hours, a large amount of pink precipitate is precipitated, is cooled to 25 DEG C, centrifugation, washing, drying obtain L-threonine chelated chromium (III) product 123.14kg, L-threonine chelated chromium (III) yield are 90.0%, and main content is 99.0wt%, Chelating chromium content is 12.75wt%, and the molecular formula of the L-threonine chelated chromium (III) is [Cr(C4H8NO3)3]。
Embodiment 10
L-threonine crystalline mother solution 794.13kg is taken, wherein L-threonine, L-threonine dipeptides, L-threonine diketone piperazine are analyzed Piperazine, L-threonine amide amount to 15wt%, and the pH of the crystalline mother solution is 6.5.By L-threonine crystalline mother solution and 50wt% hydroxide Sodium water solution 80kg passes through flowmeter respectively and is added in static mixer, 170 DEG C is heated to by heat exchanger, subsequently into pipe In formula reactor, 40min, reaction pressure 1.0Mpa are kept the temperature in tubular reactor, the feed liquid flowed out from tubular reactor turns Entering in concentration kettle and is concentrated under reduced pressure, the content for being concentrated into L-threonine is 40wt%, L-threonine sodium water solution is obtained, Then the active carbon that feed liquid 0.5wt% is added carries out decolorization, is centrifuged off active carbon, and centrifugate is transferred in chelatropic reaction kettle, 75 DEG C are warming up to, 98.80kg(333.33 moles of six hydrated chromium trichloride of feed grade of content 99% is then added), after adding, stand 90 DEG C are warming up to, is stirred to react 3 hours, a large amount of pink precipitate is precipitated, is cooled to 25 DEG C, centrifugation, washing, drying obtain To L-threonine chelated chromium (III) product 123.14kg, L-threonine chelated chromium (III) yield is 90.0%, and main content is 99.0wt%, chelating chromium content are 12.75wt%, and the molecular formula of the L-threonine chelated chromium (III) is [Cr(C4H8NO3)3]。
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this In the scope of the claims of invention.

Claims (10)

1. a kind of production technology of a-amino acid chelated chromium (III), which is characterized in that pass through step: by the mother containing a-amino acid Liquid and alkaline solution are blended in 80 DEG C~170 DEG C 20~180min of heat preservation, 60 DEG C~90 DEG C are subsequently cooled to, under condition of negative pressure Be concentrated into 20~50wt%, active carbon be added and carries out decolorization, then adds inorganic chromic salt compound, 75 DEG C~ Reaction is sufficiently stirred under the conditions of 95 DEG C, is cooled to room temperature reaction mixture after fully reacting, a large amount of solid can be precipitated at this time, It is filtered, washed, dries to get a-amino acid chelated chromium (III) compound is arrived.
2. a kind of production technology of a-amino acid chelated chromium (III) according to claim 1, which is characterized in that the α-ammonia Base acid is that perhaps the L-threonine a-amino acid mother liquor is DL- METHIONINE, glycine or L- for DL- METHIONINE, glycine The crystalline mother solution of threonine.
3. a kind of production technology of a-amino acid chelated chromium (III) according to claim 2, which is characterized in that the DL- egg In propylhomoserin crystalline mother solution, DL- METHIONINE, DL- METHIONINE dipeptides, DL- METHIONINE diketopiperazine compound or DL- METHIONINE The sum of content of ammonium salt or DL- METHIONINE amide or DL- METHIONINE glycolylurea or DL- METHIONINE hydantoic acid be 3~ 9wt%, the pH of mother liquor are 3.5~8.0.
4. a kind of production technology of a-amino acid chelated chromium (III) according to claim 2, which is characterized in that the glycine In crystalline mother solution, glycine, glycine dimer, glycine tripolymer or glycine ammonium salt or glycine amide or The sum of content of hydantoins or hydantoic acid is 10~30wt%, and the pH of mother liquor is 3.5~7.5.
5. a kind of production technology of a-amino acid chelated chromium (III) according to claim 2, which is characterized in that L- Soviet Union ammonia In acid crystal mother liquor, the sum of threonine, threonine dimer, threonine polymer, threonine ammonium salt, threonine amide content are 12~25wt%, the pH of mother liquor are 3.5~7.0.
6. a kind of production technology of a-amino acid chelated chromium (III) according to claim 1, which is characterized in that the alkalinity Solution is the molten of one or more of containing sodium carbonate, potassium carbonate, sodium bicarbonate, saleratus, sodium hydroxide, potassium hydroxide Liquid.
7. a kind of production technology of a-amino acid chelated chromium (III) according to claim 1, which is characterized in that the alpha-amido The mother liquor of acid and the reaction temperature of alkaline solution are preferably 120 DEG C~170 DEG C, reaction time preferably 30~60min.
8. a kind of production technology of a-amino acid chelated chromium (III) according to claim 1, which is characterized in that the chromic salts is The anhydrous compound or hydrated compound of chromium sulfate or chromium chloride.
9. a kind of production technology of a-amino acid chelated chromium (III) according to claim 1, which is characterized in that the alpha-amido The molar ratio of acid, alkali and chromium ion (III) are as follows: alpha-amido acid/base/chromium ion (III)=1.0:1.0:3.0, reaction temperature are excellent 80 DEG C~90 DEG C are selected, reaction time preferably 90~120min.
10. a kind of production technology of a-amino acid chelated chromium (III) according to claim 1, which is characterized in that the α-ammonia The molecular formula of base acid chelated chromium (III) is respectively DL- METHIONINE chelated chromium [Cr(C5H10NO2S)3], glycine chelate chromium [Cr (C2H4NO2)3.H2O], L-threonine chelated chromium [Cr(C4H8NO3)3]。
CN201811329503.8A 2018-11-09 2018-11-09 A kind of production technology of a-amino acid chelated chromium (III) Pending CN109456239A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102516142A (en) * 2011-11-01 2012-06-27 中国科学院过程工程研究所 Preparation method of chromium methionine chelate
CN102898338A (en) * 2012-10-16 2013-01-30 中国科学院过程工程研究所 Alpha-amino acid chromium (III) chelate and preparation method thereof
CN102924351A (en) * 2012-11-12 2013-02-13 天津市化学试剂研究所 Preparation method of chromium methionine
CN103224461A (en) * 2013-04-22 2013-07-31 广州天科生物科技有限公司 Preparation method of large granule crystal form methionine metal chelate and application thereof
CN105949097A (en) * 2016-06-03 2016-09-21 宁夏紫光天化蛋氨酸有限责任公司 Method for reducing methionine hybridization exhaust and impurities in methionine crystallization mother liquor
CN108003077A (en) * 2017-12-21 2018-05-08 河北威远生物化工有限公司 A kind of preparation of amino-acid compound and purification process

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102516142A (en) * 2011-11-01 2012-06-27 中国科学院过程工程研究所 Preparation method of chromium methionine chelate
CN102898338A (en) * 2012-10-16 2013-01-30 中国科学院过程工程研究所 Alpha-amino acid chromium (III) chelate and preparation method thereof
CN102924351A (en) * 2012-11-12 2013-02-13 天津市化学试剂研究所 Preparation method of chromium methionine
CN103224461A (en) * 2013-04-22 2013-07-31 广州天科生物科技有限公司 Preparation method of large granule crystal form methionine metal chelate and application thereof
CN105949097A (en) * 2016-06-03 2016-09-21 宁夏紫光天化蛋氨酸有限责任公司 Method for reducing methionine hybridization exhaust and impurities in methionine crystallization mother liquor
CN108003077A (en) * 2017-12-21 2018-05-08 河北威远生物化工有限公司 A kind of preparation of amino-acid compound and purification process

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