CN106278916B - A kind of preparation method of cupric glycinate - Google Patents
A kind of preparation method of cupric glycinate Download PDFInfo
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- CN106278916B CN106278916B CN201610802216.9A CN201610802216A CN106278916B CN 106278916 B CN106278916 B CN 106278916B CN 201610802216 A CN201610802216 A CN 201610802216A CN 106278916 B CN106278916 B CN 106278916B
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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
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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
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
Abstract
The invention discloses a kind of preparation method of cupric glycinate, comprise the following steps：1. aoxidize copper dissolution：Cupric oxide is dissolved in ammonium hydroxide, forms cupric ammine complex；2. synthetic reaction：Glycine is put into reaction kettle by a certain percentage with cupric ammine complex and is reacted, heating reaction a period of time, obtains reaction solution；3. purification of products：Reaction solution is cooled down and centrifuged, obtains cupric glycinate solid 1 and filtrate, then filtrate decompression distilled to obtain cupric glycinate solid 2 and liquid distillate, product is obtained after cupric glycinate solid 1 and cupric glycinate solid 2 are dried；4. recovery ammonia：1. the ammonia that is produced during by the use of absorbent absorbing reaction and as recovered liquid, ammonia solvent cupric oxide is replaced by recovered liquid reuse to step.The present invention provides a kind of interference for being not only avoided that foreign ion, but also the preparation method of the cupric glycinate of reaction rate can be improved.
Description
Technical field
The present invention relates to a kind of preparation method of cupric glycinate, especially a kind of ammonia catalysis method prepares the side of cupric glycinate
Method, belongs to the preparing technical field of cupric glycinate.
Background technology
Important trace element necessary to copper is a kind of human body and animal, is supported in body hematopoiesis function, metabolism, body
Drag and reproductive performance etc. play a significant role.Under normal circumstances, the intake of infantile period copper for daily 0.4~
1.0mg, is grown up as 1.5~3.0mg, copper in people's in-vivo content about 100~150mg, 100~120 μ g/dl of serum copper normal value,
It is the essential trace element that content occupies second.Copper, which lacks, can cause anaemia, osteoporosis, coronary heart disease, leucoderma disease, infertility
Etc. disease.Due to absorption of the alimentary canal to copper and using it is most of be with stable composite form, rather than with ion
Form, therefore there is obvious advantage, phase with third generation copper supplement copper amino acid chelate existing for stable chelate
Than the first generation (such as copper sulphate) and the second generation (such as copper gluconate) copper supplement, it can alleviate the antagonism between mineral,
Stability is good, and biological value is high, the advantages that easily absorption.
At present, industrially the technique of synthesis cupric glycinate mainly has two major class of liquid phase method and solid phase method, and liquid phase method is mainly
Using water as solvent, using glycine and mantoquita as raw material, since the addition of mantoquita have also been introduced new anionic impurity, the party
The purification difficulty of method is larger；Solid phase method mainly using glycine and copper acetate as raw material, by the acetic acid generated in reaction process and
When volatilize away, but since raw material is difficult to mix visibly homogeneous, the reaction time of the technique is longer.Therefore, present market
On lack a kind of interference for being not only avoided that and introducing new foreign ion, but also the preparation method of the cupric glycinate of reaction rate can be improved.
The content of the invention
The technical problem to be solved in the invention is to provide a kind of interference for being not only avoided that foreign ion, but also can improve reaction
The preparation method of the cupric glycinate of speed.
In order to solve the above technical problems, the technical solution adopted in the present invention is：
A kind of preparation method of cupric glycinate, comprises the following steps：
1. aoxidize copper dissolution：Cupric oxide is dissolved in ammonium hydroxide, forms cupric ammine complex；
2. synthetic reaction：Glycine is put into reaction kettle by a certain percentage with cupric ammine complex and is reacted, heating reaction
For a period of time, reaction solution is obtained；
3. purification of products：Reaction solution is cooled down and centrifuged, obtains cupric glycinate solid 1 and filtrate, then filtrate decompression is steamed
Evaporate to obtain cupric glycinate solid 2 and liquid distillate, product is obtained after cupric glycinate solid 1 and cupric glycinate solid 2 are dried；
4. recovery ammonia：The ammonia that is produced during by the use of absorbent absorbing reaction and as recovered liquid, by recovered liquid reuse extremely
1. step replaces ammonia solvent cupric oxide.
Technical solution of the present invention further improvement lies in that：Step 1. middle ammonium hydroxide mass fraction be 5%~50%, oxidation
The reaction molar ratio of copper and ammonia is 1:2~1:10.
Technical solution of the present invention further improvement lies in that：The reaction mole of step 2. middle glycine and step 1. cupric oxide
Than for 1:1~3:1, heating-up temperature is 30~100 DEG C, and the reaction time is 30~200min.
Technical solution of the present invention further improvement lies in that：3. middle reaction solution is cooled to 20~50 DEG C to step, cupric glycinate
The drying temperature of solid 1 and cupric glycinate solid 2 is 50~150 DEG C.
Technical solution of the present invention further improvement lies in that：Pressure -0.06~-0.1MPa of step 3. middle vacuum distillation,
Temperature is 70~100 DEG C.
Technical solution of the present invention further improvement lies in that：Step 4. middle absorbent using deionized water or decompression
Distill obtained liquid distillate.
Technical solution of the present invention further improvement lies in that：Step 4. it is middle be evaporated under reduced pressure obtained liquid distillate replace going from
The ratio of sub- water is 1:1~3:2.
Technical solution of the present invention further improvement lies in that：The absorbent dosage of step 4. is 30~100ml/mol ammonias.
By adopting the above-described technical solution, the technological progress that the present invention obtains is：
The present invention provides the preparation method that a kind of operating procedure is simple, raw material availability is high, reaction rate is fast, effectively contracting
Short reaction time, improves product yield, reduces production cost.
Ammonia Catalytic processes are employed in the present invention, first carry out complex reaction with cupric oxide and ammonia, then by complex compound and sweet ammonia
Acid reaction, generates cupric glycinate and releases ammonia so that ammonia is in gaseous form by absorbent absorption and directly departing from anti-
System is answered, the interfering ion in product will not be increased；Meanwhile absorbent can be used as recovered liquid to continue reuse after ammonia is absorbed
Instead of ammonia solvent cupric oxide, production cost is saved.
The present invention carries out centrifugal treating after chelatropic reaction to reaction solution, accelerates the sinking speed of particle in liquid, molten
Occur certain density gradient in liquid from liquid level to bottom, the material of different sedimentation coefficients and buoyant density in sample is separated
Open, accelerate separated speed, improve reaction rate.
The present invention has carried out the filtrate after centrifugal treating vacuum distillation operation so that a small number of sweet ammonia disperseed in filtrate
Sour copper solid separates out, and adds the yield of product；Meanwhile reduce pressure in system by means of vacuum pump, you can to reduce filter
The boiling point of liquid, suitable for not reaching boiling point, that is, decomposed product in air-distillation, it is therefore prevented that product decomposes in the case of heated,
Oxidation or the generation of polymerization, and then improve the purification rate of organic compound.
The recycling to ammonia in the present invention employs Ammonia recovery bottle and device for absorbing tail gas, and in Ammonia recovery bottle
In also add cupric oxide so that responseless ammonia can continue to be absorbed in Ammonia recovery bottle in reaction bulb, ginseng
With the reaction of next round, not only reduce the discharge of waste liquid, waste residue, waste liquid will not be produced, avoid environmental pollution, and favorably
In the raising of reaction conversion ratio and yield, cost is reduced, shortens reaction time.
The yield of the present invention is compared to traditional liquid phase and the process of synthesis in solid state cupric glycinate, during the reaction
The interfering ion for being difficult to purify will not be introduced, the reaction time shortens so that products obtained therefrom stability is strong, cupric glycinate credit rating
Height, copper content is more than 20%, and lead and arsenic free element is nontoxic, can meet national standard, reaches food-grade, feed grade；Together
When, the compound absorption that can promote copper of amino acid and mantoquita prepared by method of the invention, improves biological value.
Brief description of the drawings
Fig. 1 is the process flow chart of the present invention；
Fig. 2 is the reaction unit figure of the present invention；
Wherein, 1, U-tube differential manometer, 2, reaction bulb, 3, Ammonia recovery bottle, 4, exhaust gas processing device, 5, magnetic stirring apparatus.
Embodiment
The preparation method of cupric glycinate in the present invention is described in further details below, is comprised the following steps：
1. aoxidize copper dissolution：It is 1 according to the reaction molar ratio of cupric oxide and ammonia:2~1：10 ratio, cupric oxide is dissolved in
Mass fraction is in 5%~50% ammonium hydroxide, forms cupric ammine complex；
CuO+4NH3·H2O→Cu(NH3)4(OH)2+3H2O
2. synthetic reaction：It is 1 that glycine and cupric ammine complex are pressed reaction molar ratio:1~3:1 input reaction, heating temperature
Spend for 30~100 DEG C, react 30~200min, obtain reaction solution；
3. purification of products：Above-mentioned reaction solution is cooled to 20~50 DEG C, centrifugation, obtains cupric glycinate solid 1 and filtrate,
Filtrate decompression is distilled again to obtain cupric glycinate solid 2 and liquid distillate, the pressure -0.08MPa of vacuum distillation, temperature 85
DEG C, the then drying at 50~150 DEG C by cupric glycinate solid 1 and cupric glycinate solid 2, obtains product；
4. recovery ammonia：The liquid distillate obtained using the filtrate or vacuum distillation of deionized water or centrifugation gained is as absorption
Agent, the ammonia produced during absorbing reaction are recycled liquid, 1. recovered liquid reuse to step are replaced ammonia solvent cupric oxide,
It is 1 that the filtrate of centrifugation gained, which replaces the ratio of deionized water,:1~3:2, the liquid distillate being evaporated under reduced pressure replaces deionized water
Ratio be 1:1~3:2, absorbent dosage is that every moles of ammonia aspiration agent dosage is 30~100ml.
The reaction mechanism of this method is as follows：Using using ammonia as catalyst, glycine and cupric oxide synthesize in water phase,
Complex reaction first is carried out with cupric oxide and ammonia, then complex compound and glycine reactant, generation cupric glycinate are simultaneously released into ammonia, can
Reaction rate can be improved again by avoiding the interference of new foreign ion.
Elaborate with reference to embodiment to the present invention：
Embodiment 1,
As shown in Fig. 2, 8g cupric oxide, the ammonium hydroxide of 100ml mass fractions 15% are added into reaction bulb 2, after stirring 40min
It is completely dissolved, is slowly heated after adding 15g glycine, meanwhile, 70ml water and 8g cupric oxide are added in Ammonia recovery bottle 3,
Stirred under room temperature with magnetic stirring apparatus 5.With the rising of reaction temperature, the ammonia that is produced at leisure in reaction bulb 2 and with it is sweet
Propylhomoserin reacts, at the same time；The ammonia overflowed from reaction bulb 2 enters in Ammonia recovery bottle 3 and forms cuprammonium network with cupric oxide
Compound, remaining ammonia are absorbed by exhaust gas processing device 4.By observing the liquid level difference of U-tube differential manometer 1 with judgement system
Pressure, can adjust the generating rate of controlling reaction temperature ammonia.After 90min is reacted, reaction temperature rises to 90 DEG C, reaction
Produced substantially without gas in bottle 2, stop reaction, reaction solution is cooled to room temperature suction filtration, obtains cupric glycinate solid 1 and filtrate,
Filtrate obtains cupric glycinate solid 2, cupric glycinate solid 1 and cupric glycinate solid 2 is mixed, 85 through being evaporated under reduced pressure 30min
Drying box 180min is put at DEG C, obtains product 22.2g, yield 96.5%.Contain cupric glycinate 99.1%, copper in product after testing
Content 23.3%, unleaded and arsenic element.
Embodiment 2,
16g cupric oxide is added in Ammonia recovery bottle 3 into embodiment 1, slowly adds the ammonium hydroxide of mass fraction 25%
Reaction bulbs 2 of the 125ml as a new round, is sufficiently stirred 50min, cupric oxide is added after being completely dissolved after 45g glycine slowly
Heating, meanwhile, the liquid distillate being evaporated under reduced pressure in embodiment 1 is all added in clean Ammonia recovery bottle 3 and mended
Add deionized water to 210ml, while add 24g cupric oxide, stirred under room temperature, to the ammonia produced in absorbing reaction bottle 2, led to
The liquid level difference of observation U-tube differential manometer 1 is crossed with the pressure in judgement system, the generation of controlling reaction temperature ammonia can be adjusted
Speed.After 120min is reacted, reaction temperature rises to 95 DEG C, is produced substantially without gas in reaction bulb 2, stops reaction, will react
Liquid is cooled to room temperature suction filtration, obtains cupric glycinate solid 1 and filtrate, and filtrate is carried out vacuum distillation 40min, obtains cupric glycinate
Solid 2 and liquid distillate, the cupric glycinate solid 1 and cupric glycinate solid 2 of gained mix, and drying box is put at 85 DEG C
180min, obtains product 66.8g, yield 96.8%.Contain cupric glycinate 99.2%, copper content 23.7%, nothing in product after testing
Lead and arsenic element.
Embodiment 3,
Solidliquid mixture in Ammonia recovery bottle 3 into embodiment 2 moves into reaction bulb of the big four-hole bottle as a new round
2, then 56g cupric oxide is added thereto, the ammonium hydroxide 600ml of mass fraction 25% is slowly added, is sufficiently stirred 50min, cupric oxide
It is slowly heated after adding 150g glycine after being completely dissolved, the liquid distillate liquid being evaporated under reduced pressure in embodiment 2 is all added
Enter into clean Ammonia recovery bottle 3 and add deionized water 700ml, while add 80g cupric oxide, stirred under room temperature, to
The ammonia produced in absorbing reaction bottle 2, by observing the liquid level difference of U-tube differential manometer 1 with the pressure in judgement system, can adjust
Save the generating rate of controlling reaction temperature ammonia.After 150min is reacted, reaction temperature rises to 97 DEG C, when base in reaction bulb 2
This without gas produce, stop reaction, reaction solution is cooled to room temperature suction filtration, obtains cupric glycinate solid 1 and filtrate, by filtrate into
Row vacuum distillation 70min, obtains cupric glycinate solid 2 and liquid distillate, the cupric glycinate solid 1 and cupric glycinate of gained is consolidated
Body 2 mixes, and drying box 210min is put at 90 DEG C, obtains product 220g, yield 95.7%.Contain sweet ammonia in product after testing
Sour copper 99.1% (containing remaining product section in embodiment 2).Contain copper content 23.4%, unleaded and arsenogen in product after testing
Element.
Embodiment 4,
Reaction bulb 2 using the Ammonia recovery bottle 3 in embodiment 3 as a new round, slowly adds mass fraction thereto
30% ammonium hydroxide 50ml, is sufficiently stirred 40min, and remaining cupric oxide is slowly heated after adding 150g glycine after being completely dissolved,
The liquid distillate being evaporated under reduced pressure in embodiment 3 is all added in clean Ammonia recovery bottle 3 and adds deionized water
To 700ml, while 80g cupric oxide is added, stirred under room temperature, it is U-shaped by observing to the ammonia produced in absorbing reaction bottle 2
The liquid level difference of pipe differential manometer 1 can adjust the generating rate of controlling reaction temperature ammonia with the pressure in judgement system.When anti-
After answering 150min, reaction temperature rises to 97 DEG C, when being produced substantially without gas in reaction bulb 2, stops reaction, reaction solution is down to room
Filtered after temperature, obtain cupric glycinate solid 1 and filtrate, filtrate is subjected to vacuum distillation 60min, obtain 2 He of cupric glycinate solid
Liquid distillate, cupric glycinate solid 1 and cupric glycinate solid 2 are mixed, and drying box 210min is put at 90 DEG C, are produced
Product 221g, yield 96.1.0%.Contain cupric glycinate 99.2%, copper content 23.6%, unleaded and arsenic element in product after testing.
Embodiment 5,
The present embodiment is reference examples, with liquid phase process method using glycine and copper chloride as Material synthesis cupric glycinate.
Embodiment 6,
The present embodiment is reference examples, with liquid process method using glycine and copper acetate as Material synthesis cupric glycinate.
By the reaction time in embodiment 1~6, yield, cupric glycinate content, copper content, whether there is the items such as interfering ion
Parameter is contrasted, and specific data are shown in Table 1.
Table 1
To sum up, acetic acid is had after copper acetate solid phase reaction, but moisture and free acid can be complete after the drying of high temperature again
Portion vapors away, its copper content is up to standard, and product purity is also very high, but milling time and drying time are very long；And liquid phase reactor
Interfering ion can be introduced, purification difficulty is larger.Compared to both the above method,
In the method for the cupric glycinate of present invention process synthesis, the reaction time shortens, product yield is high and without interference from
Son so that products obtained therefrom stability is strong, and copper content has reached national standard more than 20%, and the compound of amino acid and mantoquita can be with
Promote the absorption of copper, improve biological value.
Claims (5)
1. a kind of preparation method of cupric glycinate, comprises the following steps：
1. aoxidize copper dissolution：Cupric oxide is dissolved in ammonium hydroxide, forms cupric ammine complex；
2. synthetic reaction：Glycine is put into reaction kettle by a certain percentage with cupric ammine complex and is reacted, one section of heating reaction
Time, obtains reaction solution；
The reaction molar ratio of glycine and step 1. cupric oxide is 1:1~3:1, heating-up temperature is 30~100 DEG C, and the reaction time is
30~200min；
3. purification of products：Reaction solution is cooled down and centrifuged, obtains cupric glycinate solid 1 and filtrate, then filtrate decompression is distilled
To cupric glycinate solid 2 and liquid distillate, product is obtained after cupric glycinate solid 1 and cupric glycinate solid 2 are dried；
4. recovery ammonia：The ammonia that is produced during by the use of absorbent absorbing reaction and as recovered liquid, by recovered liquid reuse to step
1. instead of ammonia solvent cupric oxide；
The liquid distillate that absorbent is obtained using deionized water or vacuum distillation；
It is 1 to be evaporated under reduced pressure obtained liquid distillate and replace the ratio of deionized water:1~3:2.
A kind of 2. preparation method of cupric glycinate according to claim 1, it is characterised in that：The quality of step 1. middle ammonium hydroxide
Fraction is 5%~50%, and the reaction molar ratio of cupric oxide and ammonia is 1:2~1:10.
A kind of 3. preparation method of cupric glycinate according to claim 1, it is characterised in that：Step 3. middle reaction solution cooling
To 20~50 DEG C, the drying temperature of cupric glycinate solid 1 and cupric glycinate solid 2 is 50~150 DEG C.
A kind of 4. preparation method of cupric glycinate according to claim 1, it is characterised in that：Step 3. middle vacuum distillation
Pressure -0.06~-0.1MPa, temperature are 70~100 DEG C.
A kind of 5. preparation method of cupric glycinate according to claim 1, it is characterised in that：The absorbent dosage of step 4.
For 30~100ml/mol ammonias.
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| US10596193B2 (en) * | 2013-03-07 | 2020-03-24 | C Lab Pharma International, S.A. | Copper (I) complexes with glycine, pyruvate, and succinate |
| CN111394587B (en) * | 2020-04-26 | 2022-01-04 | 郑州大学 | Method for leaching copper from acid-washed copper slag of zinc hydrometallurgy |
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| US4830716B1 (en) * | 1986-07-03 | 1999-12-07 | Albion Int | Preparation of pharmaceutical grade amino acid chelates |
| US6670494B1 (en) * | 2001-12-17 | 2003-12-30 | J H Brotech, Inc. | Method for preparation of metal organic acid chelates |
| WO2008105983A1 (en) * | 2007-02-27 | 2008-09-04 | Albion International, Inc. | Mineral absorption from the stomach |
| CN101139300A (en) * | 2007-09-06 | 2008-03-12 | 广州天科生物科技有限公司 | Method for preparing copper zinc aminoacetic acid complex by grinding solid phase |
| CN101139299B (en) * | 2007-09-06 | 2010-07-14 | 广州天科生物科技有限公司 | Method for preparing copper zinc aminoacetic acid complex by ball milling solid state |
| FR2935383B1 (en) * | 2008-08-26 | 2010-10-01 | Pancosma Sa Pour L Ind Des Pro | METHOD AND DEVICE FOR THE PRODUCTION OF ORGANOMETALLIC COMPLEXES IN POWDER. |
| DE102011011924B4 (en) * | 2011-02-17 | 2012-12-27 | Isf Gmbh | Process for the preparation of amino acid chelate compounds, amino acid chelate compounds and use of amino acid chelate compounds |
| EP2720540A4 (en) * | 2011-06-17 | 2015-06-03 | Arrowhead Madison Inc | Disubstituted maleic anhydrides with altered kinetics of ring closure |
| CN102766062A (en) * | 2012-04-18 | 2012-11-07 | 上海市七宝中学 | Simple preparation method of copper glycine |
| HUP1200394A2 (en) * | 2012-06-29 | 2014-02-28 | Bata Zrt Dr | Bactericidal effect of metal chelate |
| RU2553471C2 (en) * | 2013-11-14 | 2015-06-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Астраханский государственный технический университет" | Method for producing copper (ii) glycinate (ii) in presence of acetophenoneoxime |
| CN103772224B (en) * | 2014-02-25 | 2015-04-15 | 成都百事兴科技实业有限公司 | Preparation method of D-threonine |
| CN104829479A (en) * | 2015-04-23 | 2015-08-12 | 山西新源华康化工股份有限公司 | Copper glycine chelating technology |
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