CN1280260C - Method for preparing glycine iron(II) chelate for fortified food - Google Patents
Method for preparing glycine iron(II) chelate for fortified food Download PDFInfo
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- CN1280260C CN1280260C CN 200410065260 CN200410065260A CN1280260C CN 1280260 C CN1280260 C CN 1280260C CN 200410065260 CN200410065260 CN 200410065260 CN 200410065260 A CN200410065260 A CN 200410065260A CN 1280260 C CN1280260 C CN 1280260C
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Abstract
The present invention relates to a preparation method for ferrous glycine chelate used as food enrichment, and the present invention belongs to the technical field of preparation of ferrous amino acid chelate. In the method, glycine and ferrous chloride or ferrous carbonate, etc. are used as raw material; in the process of chelation reaction, an antioxidant is added and nitrogen is filled for protection; in the process of separation and purification of products, different organic solvent is adopted to carry out sequential sedimentation and elution, and consequently chelating ferrous iron and inorganic iron in the product are effectively separated; impurity anions are favorably removed to obtain products which have good oxidation stability and water solubility. The content of ferrous glycine chelate in the synthetic product surpasses 80%; the rehydration rate of the ferrous glycine chelate is larger than 95%; the oxidation stability and the water solution stability of the ferrous glycine chelate are much better than those of ferrous sulfate. The method of the present invention has the advantages of commercial scale production, reaction products which are easy to separate and purify, simple operation, low cost, stable rationalizing performance of the product, etc.
Description
Technical Field
The invention discloses a preparation method of a glycine ferrous chelate as a food nutrition enhancer, and relates to the technical field of preparation of amino acid ferrous chelates.
Background
Iron is one of the essential trace elements of the human and animal body, and iron must be relied upon for the production of heme, myoglobin, and cytochrome. The content of iron in normal human body is 35-60 mg/kg. Of these, 65 to 70% are present in circulating red blood cell hemoglobin, 25 to 30% are stored iron, and are present in the reticuloendothelial system (liver, spleen, bone marrow, etc.) in the form of ferritin and iron-containing heme, and about 5% are present in myoglobin and various iron-containing enzymes (catalase, peroxidase, cytochrome, etc.). Iron is only about 0.1% transported in plasma.
The stability constants of the amino acid chelated ferrous iron are all between 104 and 1010, which is beneficial to the absorption, transportation and utilization of iron. When EDTA is a ligand, the stability constant is too high, thereby rendering it less advantageous in food applications. Animal experiments have demonstrated the effectiveness of glycine in chelating ferrous iron, which has a molecular weight of 204. Glycine is the amino acid with the smallest molecular weight, and ferrous glycine has the best molecular structure for intestinal absorption, and is more easily absorbed by the body. Ferrous glycinate chelate is a relatively good iron-supplementing compound.
The iron glycine chelate includes ferrous glycine chelate, ferrous glycine sulfate chelate, ferrous glycine hydrochloride chelate and the like.
The trace element amino acid chelates were studied in the last 60 s. Most of the studies on the application of the amino acid chelated ferrous iron as a feed additive in animal nutrition, but the studies on the synthesis process and the physicochemical property of the amino acid chelated ferrous iron as a food iron enhancer are not common. In recent years, studies on the application of ferrous amino acid chelate as an iron nutrition enhancer in foods have been increasing by some researchers in the uk and the us.
In China, the research on the microelement amino acid chelate is started in the middle of the 80 s, and great progress is made in the aspect of amino acid chelate ferrous. The preparation of compound amino acid chelated ferrous iron by chelating reaction of compound amino acid solution obtained by acidolysis of bean cake and ferrous sulfate was reported in the early 90 s of the polypropylene and the fenugreek. On the basis of the method, Qinwandong et al (2003) study a process for preparing compound amino acid chelated ferrous by using defatted soybean meal to carry out enzymolysis to obtain compound amino acid solution and chelating with ferrous salt. Xuhaiqing and Mingxian (2001) describe the preparation of complex iron amino acid complexes from chicken feathers by hydrolysis with hydrochloric acid and complexation with iron salts. The above reports are all about the preparation research of the compound amino acid chelated ferrous iron. In the application aspect, old and clean people use ferrous sulfate to compound the compound amino acid to carry out feeding experiments of rats, and researches show that the compound amino acid can obviously promote the absorption of iron. The biological potency of ferrous sulfate, ferrous glycinate and ferrous lysine is compared by using the osmanthus fragrans and the like, and the results show that the biological potency of the ferrous glycinate and the ferrous lysine is 11.85 percent and 24.3 percent higher than that of the ferrous sulfate. Some researchers have also reported preparation processes and methods for synthesizing ferrous amino acid chelates with a single amino acid. In the middle of the 90 s, Zhang Xiaoming and Du Xuanli (1995) studied the synthesis process of ferrous glycinate; yellow eupatorium et al (2000) reported the synthesis of ferrous methionine; zhao Hui Min (2000) and so on have primarily studied the synthesis of ferrous glycinate chelate.
The inventor's published "synthetic process of ferrous glycinate" (Wuxi university of light industry, Proc. 2004No.2) discusses the synthetic process of ferrous glycinate, but the proposal is not complete and does not meet the requirement of producing food-grade products.
At present, quite a plurality of feed-grade amino acid chelated ferrous products are available in domestic markets, such as composite and monomer amino acid iron complexes of ADM company in the United states, 3D products of Chengdu Erili biotechnology research institute, and Fei Korea of Zhoushan Edia nutrition technology Co. Food grade products have not been reported.
Disclosure of Invention
The invention aims to provide a preparation method of a glycine ferrous chelate as a food nutrition enhancer, which can realize industrial scale production and provide a food nutrition enhancer, namely an excellent iron supplement compound for people.
The technical scheme of the invention is as follows: taking glycine and ferrous chloride or ferrous carbonate and the like as raw materials, adding a certain amount of antioxidant into a water medium, introducing nitrogen, carrying out chelation reaction on the two raw materials under the condition of stirring, wherein the molar ratio of the glycine to the ferrous salt is 2-3: 1, the reaction temperature is 20-80 ℃, the reaction time is 10-60 minutes, filtering, and then carrying out separation and purification: adding an absolute ethyl alcohol solvent into the filtered reaction solution for precipitation extraction, washing, dehydrating and removing impurities of the precipitate extract by using methanol, drying and crushing to prepare the food-grade ferrous glycine chelate product.
The antioxidants added during the chelation reaction were: the additive comprises vitamin C, citric acid, malic acid, reduced iron powder, acetic acid, aspartic acid or a mixture of the two, and the addition amount of the vitamin C, the citric acid, the malic acid, the reduced iron powder, the acetic acid and the aspartic acid is 10-20% of the molar amount of glycine.
And continuously introducing nitrogen in the chelation reaction process until the reaction is finished.
In the separation and purification process, different organic solvents are adopted for sequential precipitation and elution, absolute ethyl alcohol solvent with the volume of 4 to 10 times of the volume of the reaction system is used for precipitation and extraction, and then methanol is used for washing, dehydration and impurity removal.
Taking water as a medium, taking glycine and ferrous salt as raw materials, carrying out chelation reaction to generate a glycine ferrous chelate compound which is easy to dissolve in water, filtering, and adding an organic solvent to precipitate the glycine ferrous chelate compound which is not dissolved in the organic solvent, thereby realizing the effective separation of a product and other substances and achieving the purpose of purifying the product. The reaction formula of the above chelation reaction is as follows:
the invention has the beneficial effects that: compared with the 'synthesis process of ferrous glycinate chelating' (No. 2004No.2 of university of stannless light industry), which is published by the inventor, in the technical scheme of the invention, the molar ratio of glycine to ferrous chloride is 2-3: 1 in the chelating reaction, so that the concentration of ferrous salt in the reaction liquid is properly increased, the impurity content of the product can be reduced, and the ferrous content of the product can be increased. The reaction temperature is 20-80 ℃, the reaction time is 10-60 minutes, the chelation reaction of metal ions is a rapid reaction at room temperature, the temperature and the time have little influence on the reaction, and the proper heating is used for improving the solubility of the glycine. Adding a certain amount of antioxidant before the reaction, wherein the variety and the addition amount of the added antioxidant are specified. Nitrogen was continuously introduced during the reaction. After the reaction is finished, unreacted substances are filtered, and then organic solvent absolute ethyl alcohol is added to precipitate the product, which is because of free Fe2+Or Fe3+The chelated ferrous iron is dissolved in the ethanol and precipitated in the absolute ethanol, so that the separation of organic iron and inorganic iron can be realized, and the purity of the product is improved. The methanol is used for washing and dehydration, so that impurity anions in the product can be better removed, and the oxidation resistance and the hydrolysis resistance of the product are improved. Drying at low temperature under vacuum condition to obtain solid, and crushing to obtain brown ferrous glycinate chelate powder, wherein the total iron content in the product is 10-30%, the ferrous content is 8-25%, and no other anions exist in the product, so that the food-grade requirement is met.
The ferrous glycinate chelate content in the product synthesized by the method of the invention exceeds 80%, and the rehydration rate of the ferrous glycinate chelate is more than 95%. Compared with ferrous sulfate as a reference substance, the ferrous glycinate chelate has better oxidation stability than ferrous sulfate, and the stability of the aqueous solution is far higher than that of the ferrous sulfate. The method of the invention has the advantages of industrial scale production, easy separation and purification of reaction products, simple operation, low cost, stable physical and chemical properties of products and the like.
Detailed Description
Example 1
0.3mol of glycine was weighed out and dissolved in a three-necked flask containing 60ml of ultrapure water, and heated in a water bath to 80 ℃ at a constant temperature. After the glycine is completely dissolved, 0.05mol VC is added, and nitrogen is filled to ensure that the solution in the three-necked flask is in an oxygen-free state. Adding 0.15mol of ferrous chloride, adjusting the pH value to 6.0 by using 40% sodium hydroxide solution, reacting for 10 minutes, centrifuging the reaction solution for 30 minutes at 8000 rpm, adding 280ml of absolute ethyl alcohol into supernate to obtain precipitate, washing the precipitate for a plurality of times by using methanol, placing the precipitate in a closed dryer for drying for 24 hours, crushing, and placing the product in a sealed sample bag for preservation.
1g of the product is dissolved in 100ml of ultrapure water, the pH value of the system is 6.1, the product is transparent and has no precipitate, the total iron content is 18.7 percent, and the ferrous iron content is 17.2 percent.
Example 2
0.25mol of glycine was weighed out and dissolved in a three-necked flask containing 50ml of ultrapure water, and heated in a water bath to 50 ℃ and kept at a constant temperature. After the glycine is completely dissolved, 0.01mol of malic acid and 0.015mol of reduced iron powder are added, and nitrogen is filled to ensure that the solution in the three-necked bottle is in an oxygen-free state. Adding 0.1mol of ferrous chloride, adjusting the pH value to 6.5 by using 40% sodium hydroxide solution, reacting for 35 minutes, centrifuging the reaction solution for 30 minutes at 8000 rpm, adding 300ml of absolute ethyl alcohol into supernate to obtain precipitate, washing the precipitate for a plurality of times by using methanol, placing the precipitate in a closed dryer for drying for 24 hours, crushing, and placing the product in a sealed sample bag for preservation.
1g of the product is dissolved in 100ml of ultrapure water, the pH value of the system is 6.4, the product is transparent and has no precipitate, the total iron content is 19.2 percent, and the ferrous iron content is 18.0 percent.
Example 3
0.3mol of glycine was weighed out and dissolved in a three-necked flask containing 60ml of ultrapure water, and the mixture was heated in a water bath to 20 ℃ and kept at a constant temperature. Afterthe glycine is completely dissolved, 0.06mol of citric acid is added, and nitrogen is filled to ensure that the solution in the three-necked bottle is in an oxygen-free state. Adding 0.1mol of ferrous chloride, adjusting the pH value to 6.7 by using 40% sodium hydroxide solution, reacting for 60 minutes, centrifuging the reaction solution for 30 minutes at 8000 rpm, adding 500ml of absolute ethyl alcohol into supernate to obtain precipitate, washing the precipitate for a plurality of times by using methanol, placing the precipitate in a closed dryer for drying for 24 hours, crushing, and placing the product in a sealed sample bag for preservation.
1g of the product is dissolved in 100ml of ultrapure water, the pH value of the system is 6.8, the product is transparent and has no precipitate, the total iron content is 18.9 percent, and the ferrous content is 16.5 percent.
Example 4
0.3mol of glycine was weighed out and dissolved in a three-necked flask containing 60ml of ultrapure water, and the mixture was heated in a water bath to 20 ℃ and kept at a constant temperature. After the glycine is completely dissolved, 0.025mol of acetic acid and 0.025mol of aspartic acid are added, and nitrogen is filled to ensure that the solution in the three-necked bottle is in an oxygen-free state. Adding 0.1mol of ferrous carbonate, adjusting the pH value to 6.2 by using 40% sodium hydroxide solution, reacting for 60 minutes, centrifuging the reaction solution for 30 minutes at 8000 rpm, adding 550ml of absolute ethyl alcohol into supernate to obtain precipitate, washing the precipitate for a plurality of times by using methanol, placing the precipitate in a closed dryer for drying for 24 hours, crushing, and placing the product in a sealed sample bag for preservation.
1g of the product is dissolved in 100ml of ultrapure water, the pH value of the system is 6.7, the product is transparent andhas no precipitate, the total iron content is 18.6 percent, and the ferrous content is 16.9 percent.
Claims (4)
1. A preparation method of ferrous glycinate chelate is characterized in that glycine and ferrous chloride or ferrous carbonate are used as raw materials, a certain amount of antioxidant is added into an aqueous medium, nitrogen is introduced into the aqueous medium, the two raw materials are subjected to chelation reaction under the condition of stirring, the molar ratio of the glycine to the ferrous chloride or the ferrous carbonate is 2-3: 1, the reaction temperature is 20-80 ℃, the reaction time is 10-60 minutes, and then the raw materials are filtered, separated and purified: adding an absolute ethyl alcohol solvent into the filtered reaction solution for precipitation extraction, washing, dehydrating and removing impurities of the precipitate extract by using methanol, drying and crushing to prepare the food-grade ferrous glycine chelate product.
2. The method for preparing ferrous glycine chelate according to claim 1, wherein the antioxidants added during the chelation reaction are: the additive comprises vitamin C, citric acid, malic acid, reduced iron powder, acetic acid, aspartic acid or a mixture of the above, and the addition amount of the vitamin C, the citric acid, the malic acid, the reduced iron powder, the acetic acid and the aspartic acid is 10-20% of the mol amount of glycine in terms of mol.
3. The method for preparing ferrous glycine chelate according to claim 1, wherein the introduction of nitrogen gas is continued during the chelation reaction until the reaction is completed.
4. The method for preparingferrous glycine chelate according to claim 1, wherein in the separation and purification process, different organic solvents are used for precipitation and elution in sequence, absolute ethanol solvent with the volume of 4 to 10 times of the volume of the reaction system is used for precipitation and extraction, and methanol is used for washing, dehydration and impurity removal.
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| CN 200410065260 CN1280260C (en) | 2004-11-02 | 2004-11-02 | Method for preparing glycine iron(II) chelate for fortified food |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11213505B2 (en) * | 2015-07-17 | 2022-01-04 | Laboratori Baldacci S.P.A. | Product based on iron bis-glycinate chelate and alginic acid and/or water-soluble salts thereof, formulations thereof, and pharmaceutical uses thereof |
| US11865099B2 (en) | 2015-07-17 | 2024-01-09 | Laboratori Baldacci S.P.A. | Product based on iron bis-glycinate chelate and alginic acid and/or water-soluble salts thereof, formulations thereof, and pharmaceutical uses thereof |
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| WO2017054084A1 (en) * | 2015-10-01 | 2017-04-06 | The Governing Council Of The University Of Toronto | Iron-fortified tea preparations |
| CN105309776B (en) * | 2015-11-05 | 2018-11-30 | 湛江市博泰生物化工科技实业有限公司 | A kind of method that discarded shrimp head water phase adds hydrogen to prepare ferrous amino acid chelate |
| CN107821942A (en) * | 2017-11-24 | 2018-03-23 | 淮南市春风粮油食品有限公司 | A kind of processing method of the function intensified flour of amino acid chelated iron |
| CN109081786A (en) * | 2018-10-15 | 2018-12-25 | 禄丰天宝磷化工有限公司 | A kind of preparation method of amino acid ferrous chelate compound |
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| CN110041213A (en) * | 2019-04-11 | 2019-07-23 | 中国农业科学院兰州畜牧与兽药研究所 | A kind of preparation method of glutamate chelate iron |
| CN110128307B (en) * | 2019-06-12 | 2021-06-29 | 天宝动物营养科技股份有限公司 | Preparation method of stable ferrous amino acid complex |
| CN111718272B (en) * | 2020-07-14 | 2023-09-19 | 安徽华恒生物科技股份有限公司 | Preparation method and application of alanine metal chelate |
| CN112174844B (en) * | 2020-09-30 | 2023-09-19 | 安徽华恒生物科技股份有限公司 | Preparation method and application of ferrous alanine chelate |
| CN115918885B (en) * | 2022-12-08 | 2024-02-27 | 益盐堂（应城）健康盐制盐有限公司 | Anti-caking edible salt and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11213505B2 (en) * | 2015-07-17 | 2022-01-04 | Laboratori Baldacci S.P.A. | Product based on iron bis-glycinate chelate and alginic acid and/or water-soluble salts thereof, formulations thereof, and pharmaceutical uses thereof |
| US11865099B2 (en) | 2015-07-17 | 2024-01-09 | Laboratori Baldacci S.P.A. | Product based on iron bis-glycinate chelate and alginic acid and/or water-soluble salts thereof, formulations thereof, and pharmaceutical uses thereof |
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