CN106397234B - A kind of preparation method of the ferrous bisglycinate chelate without interfering ion - Google Patents
A kind of preparation method of the ferrous bisglycinate chelate without interfering ion Download PDFInfo
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- CN106397234B CN106397234B CN201610802004.0A CN201610802004A CN106397234B CN 106397234 B CN106397234 B CN 106397234B CN 201610802004 A CN201610802004 A CN 201610802004A CN 106397234 B CN106397234 B CN 106397234B
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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 the preparation methods of the ferrous bisglycinate chelate without interfering ion, include the following steps：1. prepared by active oxidation ferrous iron：In the case where completely cutting off air conditions, it is ferrous that active oxidation is made in heating ferrous oxalate；2. synthetic reaction：In the case where completely cutting off air conditions, by glycine, active oxidation is ferrous, water and antioxidant put into reaction kettle reaction by a certain percentage, stir and heat a period of time reaction solution；3. separating-purifying：Filtrate and filter residue is obtained by filtration in reaction solution, filter residue reuse to reaction kettle carries out synthetic reaction, and filtrate is analysed liquid with alcohol carries out alcohol analysis processing, stands, centrifugal treating, obtains mixed liquor and precipitate, and dry precipitate obtains ferrous bisglycinate chelate product；4. post-processing：Mixed liquor is subjected to rectification process, the alcohol obtained after rectifying and kettle liquid return to reaction kettle and carry out reuse.The present invention provides a kind of technique and the economically feasible method for preparing the ferrous bisglycinate chelate without interference anion.
Description
Technical field
The present invention relates to the preparation methods of the preparing technical field of ferrous amino acid chelate, especially ferrous bisglycinate chelate.
Background technology
Iron is one of required trace element of growth in humans's development, is the important set of ferroheme, myogen and cytochromes
At the work agent of part and redox reaction enzyme, it is distributed in human body very extensively, nearly all tissue has iron, is human development
" construction material ".When human body duration iron deficiency three to five months, iron, which cannot supply normocytic growth needs, to be caused
Iron-deficient is poor, not only affects the eubolism of human erythrocyte, also reduces the immune function of human body, causes body work energy
The decline of power and endurance.Status of iron deficiency in pregnant women can to fetus reach maturity and childbirth adversely affects, teenager
Virgin asiderosis will damage its cognitive ability, influence its normal growth and development, and subsequently mend iron and be difficult to restore.
Hypoferric anemia is that the deficiency disease of developing country's generally existing is especially in world wide.Iron in food
When element is through digesting and assimilating, infusible precipitate easily is formed with some oxalates, phytate etc., reduces the absorptivity of iron.Ammonia
Base acid iron is third generation source of iron additive, has biological value height, absorptivity height, steady chemical structure, strengthen immunity, profit
It is current develop both at home and abroad and the hot spot of development and application in the environmental protection the features such as.Medical research shows that amino acid chelated iron is in animal
There is very high biology utilization rate in vivo, be equivalent to the 125-185% of same level ferrous sulfate.Amino acid and ferrous ion chela
The dipeptides complex compound of synthesis enters mucomembranous cell in a manner of active transport from enteron aisle, can be directly absorbed by the body by small intestine,
It is a kind of very promising ferrous supplement method.Glycine is the amino acid of molecular weight minimum, should be easier to be absorbed profit in vivo
With being ideal of new generation iron supplementary at present.
Currently, use of the domestic amino acid ferrous chelate compound mainly as feed addictive.This is because current production
Amino acid ferrous chelate compound mainly prepared as source of iron using ferrous sulfate, frerrous chloride in technique, be difficult after reaction by product and
Sulfate radical, chlorion separation.With going deep into for research, people start to carry out glycine as raw material using reduced iron powder, ferrous carbonate
Ferrous synthesis, the ferrous content of product is up to 20% or more, but the reaction time is long, product yield is undesirable.This hair
It is bright to prepare active oxidation ferrous iron through completely cutting off air heating using ferrous oxalate as source of iron then sub- with glycine chelate generation glycine
Iron, the reaction time is short, product yield is high and is free of interfering ion.
Invention content
The technical problem to be solved in the invention is to overcome the influence of interfering ion, provides a kind of technique and viable economically
Preparation without interference anion ferrous bisglycinate chelate method.
In order to solve the above technical problems, the technical solution adopted in the present invention is：
A kind of preparation method of the ferrous bisglycinate chelate without interfering ion, includes the following steps,
1. prepared by active oxidation ferrous iron：In the case where completely cutting off air conditions, it is ferrous that active oxidation is made in heating ferrous oxalate；
2. synthetic reaction：In the case where completely cutting off air conditions, by glycine, active oxidation ferrous iron, water and antioxidant by certain
Ratio put into reaction kettle reaction, stir and heat a period of time reaction solution；
3. separating-purifying：Filtrate and filter residue is obtained by filtration in reaction solution, filter residue reuse to reaction kettle carries out synthetic reaction, will
Filtrate analyses liquid with alcohol and carries out alcohol analysis processing, stands, centrifugal treating, obtains mixed liquor and precipitate, and dry precipitate obtains glycine Asia
Iron product；
4. post-processing：Mixed liquor is subjected to rectification process, the alcohol obtained after rectifying and kettle liquid return to reaction kettle and carry out reuse.
Technical solution of the present invention further improvement lies in that：Step 1. 300~400 DEG C of heating temperature, the reaction time 15~
60 minutes.
Technical solution of the present invention further improvement lies in that：Step 2. in glycine, active oxidation be ferrous and the reaction of water
Molar ratio is 2~3：1：15~30, the addition of antioxidant is the 3%~15% of glycine quality, reaction temperature 50~
80 DEG C, 3~9 hours reaction time.
Technical solution of the present invention further improvement lies in that：Step 2. in isolation air condition be using atoleine or
Vegetable oil carries out fluid-tight or is filled with nitrogen, argon gas or helium atmosphere.
Technical solution of the present invention further improvement lies in that：2. middle antioxidant is vitamin C, citric acid, apple to step
It is one or more in acid, reduced iron powder, acetic acid.
Technical solution of the present invention further improvement lies in that：3. middle alcohol analysis liquid is methanol or ethyl alcohol to step, and alcohol is analysed liquid and filtered
The volume ratio of liquid is 3~10:1.
Technical solution of the present invention further improvement lies in that：3. middle time of repose is 2~4 hours to step, and drying temperature is
50~70 DEG C, drying time is 4~8 hours.
Technical solution of the present invention further improvement lies in that：Step 4. in alcohol after rectifying replace alcohol analysis liquid to carry out in proportion
Alcohol is analysed, and rectifying kettle liquid replaces the water in synthetic reaction.
Technical solution of the present invention further improvement lies in that：Step 4. in alcohol after rectifying and the volume ratio that replaces alcohol analysis liquid
It is 1:1~2:3, rectifying kettle liquid is 1 with the volume ratio instead of water:4~3:5.
Technical solution of the present invention further improvement lies in that：4. middle rectification temperature is 60~100 DEG C to step.
By adopting the above-described technical solution, the technological progress that the present invention obtains is：
This method is used prepares active oxidation ferrous iron as source of iron using ferrous oxalate, contains instead of frerrous chloride, ferrous sulfate etc.
There are the low sources of iron of reactivities such as source of iron and fe, the ferrous carbonate of interference anion, the reaction time can be effectively reduced, carried
The amino acid-ferrous preparation method of high yield, products obtained therefrom stability is strong, and ferrous content is more than 20%, has reached national standard and has wanted
It asks, the compound absorption that can promote molysite of amino acid and ferrous salt improves biological value.
The present invention is not suitable for during chelatropic reaction in installation valve, and the inside and outside differential pressure of sealing is not very big and seals
It is required that it is relatively high, thereby using the mode of hydraulic seal, or it has been added and has been free of under the mode of inert gas shielding
The antioxidant of interfering ion prevents activated ferrous ion from being aoxidized and being inactivated in air, easy to operate.
In the present invention because in experiment ferrous salt be easily oxidized to the molysite of trivalent, become di-iron trioxide precipitation, so need
Antioxidant is added, to prevent the oxidation of ferrous salt.But the amino acid-ferrous product of commercial type largely all contains
" interference anion ", for example, being prepared in ferrous bisglycinate chelate as raw material using ferrous sulfate or frerrous chloride, metal sulfate or chlorine
Salt dissolving and amino acid are difficult to that the reaction was complete, and in the product after reacting, sulfate ion or chlorion are difficult separation, this
The anion pair that a little interference anion lead to that the ferrous bisglycinate chelate product of high Fe content cannot be obtained, and are not completely segregated
Organism is harmful, it is necessary to be spent largely into the salt of these hardly possible separation of present treatment.The present invention considers the factor of this respect,
And in view of under the conditions of not influencing the complexing rate of amino acid, use vitamin C, citric acid, malic acid, reduced iron powder,
One or more combinations in acetic acid can form chelate with ferrous ion.The present invention is made using above-mentioned reducing agent
Ferrous salt is protected for antioxidant.
The ratio between the molal quantity of different coordination ratio, that is, ligands and metal ion be influence chelatropic reaction an important factor for it
One.Glycine the react molar ratio ferrous with active oxidation is 2~3 in the present invention：1, if coordination ratio is too small, cannot be formed
The stability of stable cyclic structure, chelate is poor；If coordination ratio is too big, it is unworthy from the point of view of economy, causes
Cost waste.Therefore, present invention employs the minimum coordination ratio that one can reach chelating degree, product cost has both been saved
, and can fully utilize glycine.
Ferrous glycinate does not form precipitation in organic solvent in the present invention, but forms crystal and be precipitated, so,
The time of crystallization has a great impact to the formation of crystal.For the present invention, the time of standing is 2~4 hours so that brilliant
Body crystallization is more fully.
The present invention in filtered filtrate to being added in alcohol analysis liquid so that can be big insoluble in the substance in alcohol analysis liquid
Amount is fully precipitated, and the solution after alcohol is analysed then is carried out rectification process again, i.e., increases a reflux on the basis of distillation
Process, the alcohol after the temperature by controlling rectifying analyses alcohol in solution can be steamed out, and can recycle previous step
Alcohol analysis during, save production cost, refining effect is more preferable.In traditional ferrous bisglycinate chelate preparation process, do not relate to
And to the reuse problem to raw material, and in the present invention, by replacing alcohol to analyse liquid the alcohol liquid of recycling according to a certain percentage, return
In filter residue during being analysed to alcohol, and after filtration, also contains the antioxidant for not participating in reaction and active oxidation is ferrous,
By the reaction was continued in its reuse to reaction kettle, reaction cost has been saved, meanwhile, the kettle liquid Jing Guo rectifying is dissolved into glycine, is made
The concentration of reactant increases when must react starting, promotes the positive of reaction and carries out.In conclusion filtrate, rectifying kettle liquid, rectifying
Fraction alcohol reuse operation, saved cost, product average weight yield improve 0.94%.Produce 1000 tons of glycine Asias per year
Iron product, yield often increase 0.1 percentage point, year 200000 yuan of additional income, after the project application, increase by 1,880,000 yuan of benefit/
Year.Meanwhile experimental condition of the invention is mild, the solvent in production process is all non-toxic, pollution is small, while reducing pollution
Discharge, it may have certain social benefit.
Description of the drawings
Fig. 1 is the process flow chart of the present invention.
Specific implementation mode
The present invention is described in further details with reference to embodiment, specific technical process is as shown in Figure 1.
A kind of preparation method of the ferrous bisglycinate chelate without interfering ion, includes the following steps：
1. prepared by active oxidation ferrous iron：In the case where completely cutting off air conditions, active oxidation ferrous iron, heating is made in heating ferrous oxalate
300~400 DEG C of temperature, 15~60 minutes reaction time；
2. synthetic reaction：In a kettle, glycine is dissolved in water to obtain lysate, activity is added in lysate
The reaction molar ratio of ferrous oxide, glycine, active oxidation ferrous iron and water is 2~3：1：15~30, then, using paraffin or
Vegetable oil fluid-tight or antioxidant vitamin C, lemon of the addition without interfering ion under conditions of being filled with nitrogen, argon gas or helium
It is one or more in lemon acid, malic acid, reduced iron powder, acetic acid, the addition of antioxidant be glycine quality 3%~
15%, then, 50~80 DEG C are stirred and heated to, reaction obtains reaction solution after 3~9 hours；
3. separating-purifying：Filtrate and filter residue is obtained by filtration in reaction solution, filter residue, which is returned to reaction kettle, to be recycled, then
Filtrate ethyl alcohol or methanol are carried out alcohol analysis processing, it is 3~10 that alcohol, which analyses liquid and the volume ratio of filtrate,:1, after standing 2~4 hours,
Mixed liquor is centrifuged, solution and precipitate are obtained, dry precipitate, dry under conditions of temperature is 50~70 DEG C
Time is 4~8 hours, obtains ferrous bisglycinate chelate product；
4. post-processing：Solution after alcohol is analysed carries out rectification process, and rectification temperature is 60~100 DEG C, recycles rectification process
Rear alcohol fraction is simultaneously re-used for alcohol analysis, and rectifying kettle liquid replaces the water in synthetic reaction, the alcohol after rectifying with replace alcohol analysis liquid
Volume ratio is 1:1~2:3, rectifying kettle liquid is 1 with the volume ratio for replacing the water in synthetic reaction:4~3:5.
The present invention is described in further details with reference to embodiment：
Embodiment 1,
It weighs 0.1mol ferrous oxalates and is heated to 300 DEG C in the case where completely cutting off air, keep being reacted for 60 minutes, instead
It should be cooled to room temperature to obtain active oxidation ferrous iron after the completion；By active oxidation ferrous iron and the 0.25mol glycine, the 0.75g that weigh
Citric acid is put into the conical flask of 250ml, then the deionized water of 50ml is added thereto, and adds a certain amount of liquid in the water surface
Paraffin fluid-tight.To 70 DEG C, constant temperature stirs 6 hours heating water bath.After reaction, with separatory funnel by reaction solution and atoleine
It separates, reaction solution is filtered, then 400ml ethyl alcohol is added into filtrate, precipitate is obtained after standing 4 hours, to precipitate
It is dried 8 hours at 50 DEG C, obtains ferrous bisglycinate chelate product 18.2g, yield 75.9%.Total iron content is 21.0% after testing, sub-
Iron content 20.5%.Alcohol analyses liquid in 60 DEG C of rectifying 1.5 hours, obtains recycling ethyl alcohol, remaining as rectifying kettle liquid, will recycling ethyl alcohol again
It is analysed for alcohol, rectifying kettle liquid carries out reuse with filter residue.
1g products are taken to be dissolved in 100ml deionized waters, system pH 6.0, transparent no precipitation.
Embodiment 2,
It weighs 1mol ferrous oxalates and is heated to 350 DEG C in the case where completely cutting off air, keep being reacted for 30 minutes, react
It is cooled to room temperature to obtain active oxidation ferrous iron after the completion；Ferrous oxide and the 3mol glycine, the 10gVc that weigh are put into the three of 1L
In mouth flask, then the deionized water of 300mL is added thereto, and a certain amount of soybean oil fluid-tight is added in the water surface.Heating water bath
To 60 DEG C, constant temperature stirs 9 hours.After reaction, reaction solution and soybean oil are separated with separatory funnel, reaction solution was carried out
Filter, then 1000mL methanol is added into filtrate, precipitate is obtained after standing 2 hours, precipitate is dried 5 hours at 70 DEG C, is obtained
Ferrous bisglycinate chelate product 392g, yield 80.4%.Total iron content is 20.7% after testing, ferrous content 20.4%.Alcohol analysis liquid exists
80 rectifying 1 hour, obtain recycling methanol, and remaining as rectifying kettle liquid, recycling methanol is re-used for alcohol analysis, rectifying kettle liquid and filter residue into
Row reuse.
1g products are taken to be dissolved in 100ml deionized waters, system pH 5.8, transparent no precipitation.
Embodiment 3,
It weighs 2mol ferrous oxalates and is heated to 380 DEG C in the case where completely cutting off air, keep being reacted for 20 minutes, react
It is cooled to room temperature to obtain active oxidation ferrous iron after the completion；Ferrous oxide is put into 3mol glycine, the 10g reduced iron powders weighed
In the three-necked flask of 1L, then the deionized water of 300mL is added thereto, and a certain amount of soybean oil fluid-tight is added in the water surface.Water
Bath is heated to 50 DEG C, and constant temperature stirs 3 hours.After reaction, reaction solution and soybean oil are separated with separatory funnel, by reaction solution
It is filtered, then 1000mL methanol is added into filtrate, precipitate is obtained after standing 3 hours, it is small that 7 are dried at 60 DEG C to precipitate
When, obtain ferrous bisglycinate chelate product 392g, yield 81.2%.Total iron content is 20.3% after testing, ferrous content 20.1%.Alcohol is analysed
Liquid obtained recycling methanol in 70 DEG C of rectifying 1.5 hours, and remaining as rectifying kettle liquid, recycling methanol is re-used for alcohol analysis, rectifying kettle liquid
Reuse is carried out with filter residue.
1g products are taken to be dissolved in 100ml deionized waters, system pH 5.9, transparent no precipitation.
Embodiment 4,
It weighs 5mol ferrous oxalates and is heated to 400 DEG C in the case where completely cutting off air, keep being reacted for 15 minutes, react
It is cooled to room temperature to obtain active oxidation ferrous iron after the completion；By ferrous oxide and the 11mol glycine, 25g malic acid, the 25g that weigh
Iron powder is put into the three-necked flask of 2L capacity, then the deionized water of 1500ml is added thereto, and nitrogen is passed through into three-necked flask
Gas is to completely cut off air.To 80 DEG C, constant temperature stirs 4 hours heating water bath.After reaction, reaction solution is filtered, then to filter
5000ml ethyl alcohol is added in liquid, obtains precipitate after standing 2 hours, precipitate is dried 4 hours at 70 DEG C, obtains ferrous bisglycinate chelate
Product 980g, yield 82.1%.Total iron content is 20.7% after testing, ferrous content 20.1%.Alcohol analyses liquid in 100 DEG C of rectifying 4
Hour, recycling ethyl alcohol is obtained, remaining as rectifying kettle liquid, recycling ethyl alcohol is re-used for alcohol analysis, rectifying kettle liquid carries out reuse with filter residue
1g products are taken to be dissolved in 100ml deionized waters, system pH 6.1, transparent no precipitation.
Embodiment 5,
The present embodiment is reference examples, and using the ferrous sulfate in background technology as source of iron, amino acid is prepared using traditional handicraft
Ferrous chelate compound.
Embodiment 6,
The present embodiment is reference examples, and using the ferrous carbonate in background technology as source of iron, amino acid is prepared using traditional handicraft
Ferrous chelate compound.
By the parameters such as reaction time, yield, ferrous content, iron content total amount, interfering ion in Examples 1 to 6 into
Row comparison, specific data are shown in Table 1.
Table 1
To sum up, in the method for the ferrous bisglycinate chelate of present invention process synthesis for traditional handicraft, when reaction
Between shorten, product yield is high and is free of interfering ion so that products obtained therefrom stability is strong, and ferrous content is more than 20%, is reached
The compound absorption that can promote molysite of national standard, amino acid and ferrous salt, improves biological value.
Claims (5)
1. a kind of preparation method of the ferrous bisglycinate chelate without interfering ion, it is characterised in that include the following steps：1. active oxygen
Change ferrous prepare：In the case where completely cutting off air conditions, it is ferrous that active oxidation is made in heating ferrous oxalate；
2. synthetic reaction：In the case where completely cutting off air conditions, by a certain percentage by glycine, active oxidation ferrous iron, water and antioxidant
Put into reaction kettle reaction, stir and heat a period of time reaction solution；
3. separating-purifying：Filtrate and filter residue is obtained by filtration in reaction solution, filter residue reuse to reaction kettle carries out synthetic reaction, by filtrate
Alcohol analysis processing is carried out with alcohol analysis liquid, is stood, centrifugal treating, mixed liquor and precipitate are obtained, dry precipitate obtains ferrous bisglycinate chelate production
Product；
4. post-processing：Mixed liquor is subjected to rectification process, the alcohol obtained after rectifying and kettle liquid return to reaction kettle and carry out reuse；
1. 300~400 DEG C of heating temperature, 15~60 minutes reaction time are cooled to room temperature to obtain the step after the completion of reaction
Active oxidation is ferrous；
The step 2. in glycine, active oxidation be ferrous and the reaction molar ratio of water is 2~3：1：15~30, antioxidant
Addition be the 3%~15% of glycine quality, 50~80 DEG C of reaction temperature, 3~9 hours reaction time, antioxidant be dimension
It is one or more in raw element C, citric acid, malic acid, reduced iron powder, acetic acid；
The step 4. in alcohol after rectifying replace alcohol analysis liquid to carry out alcohol analysis in proportion, rectifying kettle liquid replaces in synthetic reaction
The volume ratio of water, alcohol and replacement alcohol analysis liquid after rectifying is 1:1~2:3, rectifying kettle liquid is 1 with the volume ratio instead of water:4~
3:5。
2. a kind of preparation method of ferrous bisglycinate chelate without interfering ion according to claim 1, it is characterised in that：Step
Suddenly 2. the condition of middle isolation air is to carry out fluid-tight using atoleine or vegetable oil or be filled with nitrogen, argon gas or helium atmosphere.
3. a kind of preparation method of ferrous bisglycinate chelate without interfering ion according to claim 1, it is characterised in that：Step
Suddenly 3. middle alcohol analysis liquid is methanol or ethyl alcohol, and it is 3 ~ 10 that alcohol, which analyses liquid and the volume ratio of filtrate,:1.
4. a kind of preparation method of ferrous bisglycinate chelate without interfering ion according to claim 1, it is characterised in that：Step
Suddenly 3. middle time of repose is 2~4 hours, and drying temperature is 50~70 DEG C, and drying time is 4~8 hours.
5. a kind of preparation method of ferrous bisglycinate chelate without interfering ion according to claim 1, it is characterised in that：Step
Suddenly 4. middle rectification temperature is 60~100 DEG C.
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| US5504055A (en) * | 1994-03-15 | 1996-04-02 | J.H. Biotech, Inc. | Metal amino acid chelate |
| AU2002213105A1 (en) * | 2000-10-11 | 2002-04-22 | Albion International, Inc. | Compositions and methods of preparing amino acid chelates and complexes |
| CN101173764A (en) * | 2006-10-30 | 2008-05-07 | 廖树汉 | Boiler without generating acid rain by dedusting in stove and device for producing protein by boiler waste gas |
| CN101606715A (en) * | 2008-06-17 | 2009-12-23 | 浙江科技学院 | A kind of preparation method who disturbs anionic food-grade amino acid ferrous chelate compound that do not contain |
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| CN102130334B (en) * | 2011-01-15 | 2013-12-04 | 中国矿业大学 | Graphene-based nano iron oxide composite material and preparation method thereof |
| 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 |
| US9775824B2 (en) * | 2014-06-04 | 2017-10-03 | National Taiwan University | Magnetic nanoparticle composition and manufacturing method and use thereof |
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