CN1164566C - Preparation of ferrous glycinate chelate by metathesis method - Google Patents
Preparation of ferrous glycinate chelate by metathesis method Download PDFInfo
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- CN1164566C CN1164566C CNB02122935XA CN02122935A CN1164566C CN 1164566 C CN1164566 C CN 1164566C CN B02122935X A CNB02122935X A CN B02122935XA CN 02122935 A CN02122935 A CN 02122935A CN 1164566 C CN1164566 C CN 1164566C
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Abstract
The present invention provides a method for preparing ferrous glycinate chelate through four double-decomposition reaction paths of calcium glycinate chelate and ferrous sulfate or ferrous glycine sulfate chelate and the hydroxide or oxide of calcium in a water medium. In the process of reaction, a stabilizing agent or a reducing agent substituting iron powder is added in. Thus, total iron content is 10 to 27%, and ferrous content is 5 to 25% in the prepared product; the product basically contains little interfering sulfate radical anions. The method has the advantages of commercial scale production, easy separation of reaction products, simple operation technology, very low cost, stable product quality, etc.
Description
The invention relates to a preparation method of ferrous glycinate chelate.
It is well known in the art that iron is an essential component of mammalian blood and must be maintained in an amount sufficient to ensure proper growth and function of the human or animal body. If the iron content in blood is insufficient, diseases such as iron deficiency anemia can be caused. Iron deficiency and anemia are the most common nutritional deficiencies in humans, especially in developing countries where cereals or legumes are the daily diet. In animals, such as newborn piglets, iron deficiency anemia is common, and piglets gain four times their body weight three weeks after birth, making it difficult to take sufficient amounts of iron from the sow's milk. Therefore, the ferrous glycinate chelate is an iron-supplementing nutrition enhancer and a medical agent for mammals including human beings. The iron-containing glycine chelate has good effect in preventing and treating iron-deficiency anemia of human.
Iron glycine chelates are the following:
1. ferrous glycinate chelate (English name: Ferrous glycinate, or Ferrous bisglycinate chelate);
2. iron glycinate chelate (British name: Ferric trisglycinate chelate);
3. ferrous glycinate sulfate chelate complexes, two of which are:
3-1 English name: ferrous 1-glyceride hydrochloride chemical
3-2 English name: ferrous 2-glyceride hydrochloride chemical
4. Ferrous glycine hydrochloride chelates, two of which are:
4-1 English name: ferroos 2-glycolate hydrochloride chemical
4-2 English name: ferroous 8-glycolate hydrochloride chemical
Iron glycinate chelate is prepared by reacting 3 moles of glycine with 1 mole of iron powder at 50 ℃ for 24 hours (U.S. Pat. No. 4,830,716 (1989)); the iron glycinate chelate can also be prepared from 3 moles of glycine and 1 mole of ferric chloride (FeCl)3·3H2O) reaction solution, and a precipitate obtained by adding 3 moles of NaOH (U.S. Pat. No. 5,516,925 (1996)). The iron glycinate chelate is trivalent iron, so that the iron glycinate chelate has poor absorption effect and is not suitable for human to serve as an iron enhancer.
Ferrous glycinate sulfate chelate "3-1" is obtained by reacting 1 mole of glycine with 1 mole of ferrous sulfate (U.S. Pat. No. 2,957,806(1960)), and studies have shown that it is no more advantageous than ferrous sulfate.
Ferrous glycinate sulfate chelate "3-2" is prepared by reacting 2 moles of glycine (containing citric acid) with 1 mole of ferrous sulfate (U.S. Pat. No. 5,504,055 (1996); U.S. Pat. No. 6,147,815 (2001)). Due to the large amount of sulfate anions present in the compound, the product is limited to non-human animal and plant applications.
The "4-1" and "4-2" compounds in ferrous glycinate chelate are obtained by reacting 2 moles of glycine with 1 mole of ferrous chloride and reacting 8 moles of glycine with 1 mole of ferrous chloride (U.S. Pat. No. 4,183,947 (1980)). The compound "4-1" is only applicable to non-human animals and crops because of the presence of a large amount of chloride anions, as well as ferrous glycinate sulfate chelate "3-2". However, the compound "4-2" is recommended by the inventors of this patent as a human.
Ferrous glycinate chelate is essentially free of physiologically interfering anions (such as chloride, sulfate or nitrate), is a highly stable chelate that can be added to most food products and is evaluated for safety as described in foodchem. toxicol, 1999, 37(7) 723-731. Ferrous glycinate chelate is best absorbed in human body, 4.7 times of ferrous sulfate and 3 times of ferrous glycinate chelate.
The preparation of ferrous glycine chelate by Albion corporation in the United states is obtained by reacting glycine with or without citric acid with the elemental iron or ferrous carbonate or ferrous hydroxide, oxide (U.S. Pat. No. 4,830,716 (1989)). Neither of these methods is ideal. The reaction between glycine and iron element is as long as 24 hr, and is mainly used for preparing ferric glycine chelate, i.e. under the protection of nitrogen or carbon dioxide, the ferrous content of the obtained product is only half of total iron content. And glycine reacts with ferrous carbonate or ferrous hydroxide, even if citric acid participates in the promotion reaction, after the reaction is finished, a considerable amount of colloidal substances with fine particles and difficult dissolution exist, the filtering operation is very difficult, the total iron content of the obtained product is not high, and the ferrous content is only about two thirds of the total iron content.
Anionically-free amino acid metal chelates can be successfully prepared electrolytically (U.S. Pat. No. 4,599,152(1986)), but this process is quite expensive and particularly time-consuming.
Another ferrous glycine chelate has been proposed in the U.S. Albion company funded bioassay Unit publication by slowly adding glycine to a solution of iron and reducing it to the ferrous state, but a detailed preparation is not disclosed (Bovell-Benjamin, AC.et al., am. Clin. Nutr., 2000, 711563-9).
The invention adopts a double decomposition method to prepare the glycine ferrous chelate, can be prepared by four ways, has simple and easy method and very low cost, and the total iron content and the ferrous iron content and other properties of the obtained product are consistent with those of a Ferrochel product of Albion company.
Route 1: the water is used as medium, calcium glycinate is used as raw material, and is subjected to double decomposition reaction with ferrous sulfate to generate calcium sulfate which is difficult to dissolve in water and ferrous glycinate chelate with excellent water solubility, and the calcium sulfate and the ferrous glycinate chelate are easily separated by filtration. Their reaction formula is as follows:
in the above metathesis reaction, calcium glycinate: ferrous sulfate in the molar ratio of 1.0-2.0 to 1.0 at 20-100 deg.c for 0.5-5.0 hr. During the metathesis reaction, 5-50% of a stabilizer is added, corresponding to the amount of glycine. After the reaction is finished, filtering out calcium sulfate precipitate, washing, removing water from ferrous glycinate chelate filtrate with excellent water solubility and washing liquor, drying to obtain solid, and pulverizing to obtain black brown ferrous glycinate chelate powder, wherein the total iron content in the product is 10-27%, the ferrous content is 5-25%, and the sulfate anion in the product is few.
The stabilizer added in the metathesis reaction can be citric acid, ascorbic acid, tartaric acid, fumaric acid, malic acid, lactic acid, malonic acid, succinic acid, aspartic acid, glutamic acid, picolinic acid, acetic acid, carbonic acid, and their mixture.
Route 2: using water as medium, using glycine as initial raw material, firstly making it react with calcium hydroxide or calcium oxide to produce calcium glycinate aqueous solution, then makingit undergo the process of double decomposition reaction with ferrous sulfate. Their reaction formula is as follows:
in the above reaction, glycine, calcium hydroxide and ferrous sulfate are (mole ratio) 2.0-4.0: 1.0-2.0: 1.0, reaction temperature is 20-100 deg.C, reaction time is 0.5-5.0 hr, and in the double decomposition reaction, 5-50% of the above-mentioned stabilizing agent is added. The post-treatment process of the prepared ferrous glycinate chelate solution and calcium sulfate precipitate is the same as that in the way 1, and the total iron content and the ferrous content in the product are also in the range described in the way 1.
Route 3: the water is used as medium, ferrous glycinate sulfate chelate is used as raw material, and double decomposition is carried out with calcium hydroxide or calcium oxide. The reaction formula is as follows:
in the double decomposition reaction, the mol ratio of glycine ferrous sulfate chelate to calcium hydroxide is 1.0: 1.0-2.0, the reaction temperature is 20-100 ℃, the reaction time is 0.5-5.0 hours, and in the double decomposition reaction, 5-50% of the stabilizing agent corresponding to the dosage of glycine is added. After the reaction is finished, the total iron content and the ferrous content in the obtained product are also in the range of the way 1 after filtration, washing and drying.
Route 4: the water is used as medium, glycine is used as initial raw material, firstly, it reacts with ferrous sulfate to produce ferrous glycine sulfate chelate aqueous solution, then it is undergone the process of double decomposition reactionwith calcium hydroxide or calcium oxide. Their reaction formula is as follows:
in the double decomposition reaction, the mol ratio of glycine, ferrous sulfate and calcium hydroxide is 2.0-4.0: 1.0-2.0, the reaction temperature is 20-100 ℃, the reaction time is 0.5-5.0 hours, and in the double decomposition reaction, 5-50% of the stabilizing agent corresponding to the dosage of glycine is added. After the reaction is finished, the total iron and ferrous content in the product of the glycine ferrous chelate obtained by filtering, washing and drying can also reach the range of the way 1.
In the above-mentioned 4 routes of double decomposition reaction, iron powder reducing agent can be added, and can be partially substituted for the above-mentioned stabilizing agent, and its addition quantity is 5-50% of glycine.
The invention uses the four ways to prepare the ferrous glycinate chelate by a double decomposition method and has the advantages of high ferrous content, less interference anions, easy separation of reaction products, simple operation process, low cost, mild reaction conditions and stable product quality.
Detailed Description
Example 1
9.4g of calcium glycinate, 1.5g of ascorbic acid and 25ml of distilled water are put into a 0.5 liter reaction bottle with magnetic stirring, stirred and heated to 35 ℃ to be completely dissolved, the pH value is about 10, then the mixture is put into a cold water bath to be stirred, 13.9g of ferrous sulfate with 7 crystal water and 25ml of distilled water are poured into a beaker to be continuously stirred and heated to 35 ℃ to be completely dissolved, the pH value is about 3, the latter is poured into the reaction bottle to quickly separate out dark green precipitate, then the mixture is continuously stirred for 0.5 hour, the liquid temperature is 18 to 20 ℃, then the mixture is filtered, filter cake is washed by distilled water, the filter cake is beige calcium sulfate, and 5.4g of filter cake is obtained after drying. Adding 2.0g citric acid monohydrate into the filtrate, stirring to dissolve, pouring into a tray, dehydrating and drying at 105-108 ℃ to obtain 15.0g dark brown product, and grinding into powder.
1g of the product was dissolved in water at pH 7.6, clear without precipitation and determined as total Fe: 19.56% of Fe++：18.21％。
Example 2
250ml of water and 18.7 g of calcium hydroxide are added into a 0.5 l reaction flask with magnetic stirring, the mixture is heated to 50 ℃ under stirring to form a white suspension, 37.5 g of glycine is added to form a semitransparent liquid, the semitransparent liquid is reacted at 80 ℃ for 1 hour, the temperature is reduced to 70 ℃, and 8g of ascorbic acid is added. Finally, 70 g of ferrous sulfate with 7 crystal waters and 125ml of water are added, the mixture is heated to 60 ℃ water solution, the mixture is stirred and reacted for 0.5 hour at 50-60 ℃, the temperature is reduced to room temperature, the mixture is filtered, the calcium sulfate filter cake is washed by water, 11.0 g of citric acid is added into the washing filtrate, the mixture is stirred and dissolved, and the mixture is dried at the temperature lower than 110 ℃, so that 71.7 g of dark green product is obtained. pH of 1% aqueous solution 8.2, total Fe: 18.57% of Fe++：18.16％。
If 11 g of fumaric acid were used instead of citric acid, 74 g of the product were obtained, the pH of the 1% aqueous solution was 7.3, and the total Fe: 19.60% of Fe++：18.16％。
If 6 grams of fumaric acid plus 6 grams of citric acid were used instead of 11 grams of citric acid, 74 grams of product would be obtained. pH of 1% aqueous solution 7.4, total Fe: 19.98% of Fe++：18.20％。
If 14.2 g of calcium oxide reacts with water to generate calcium hydroxide, the reaction is carried out to obtain 79 g of product. pH of 1% aqueous solution 7.4, total Fe: 20.32% of Fe++：18.90％。
Example 3
Adding 5g calcium hydroxide and 50ml water into a 0.5L reaction bottle with magnetic stirring, heating to 50 deg.C under stirring, adding 21g ferrous glycinate sulfate chelate, aqueous solution containing small amount of citric acid and 50ml water, precipitating large amount of blue precipitate, red ferric iron on the inner wall of the bottle, adding 1.5gVc to make the red disappear, reacting at 50-60 deg.C under stirring for 0.5 hr, cooling to room temperature, filtering, washing the filter cake with 15ml waterThe filter cake was then dried to give 11.7g of calcium sulfate as a yellow-brown product. The washed filtrate of 128ml is dried at the temperature of less than 110 ℃ to obtain 15g of the product. pH of 1% aqueous solution 7.8, total Fe: 18.64% of Fe++：17.16％。
Example 4
Adding 125ml of water into a 0.5 liter reaction bottle with magnetic stirring, boiling for 0.5 hour, cooling slightly, adding 35g of ferrous sulfate containing 7 crystal water and 18.8g of glycine, stirring and heating to be transparent, stirring and reacting for 0.5 hour at 80 ℃, adding 3g of ascorbic acid, then adding an aqueous suspension prepared by 9.7g of calcium hydroxide by 100ml of water, precipitating, stirring and reacting for 0.5 hour at 60-70 ℃, coolingto room temperature, filtering, washing a filter cake to be green and blue by using a small amount of water, and drying to be brick red to obtain 20.2g of calcium sulfate. 285ml of the washing filtrate was dissolved by adding 4g of citric acid with stirring, and dried at<110 ℃ to obtain 34.7g of a.1% aqueous solution having a pH of 7.8, and the total Fe was measured: 19.85% of Fe++：18.86％。
If 7.0g of calcium oxide reacts with water to form calcium hydroxide, the reaction is carried out, and 36 g of the product can be obtained. pH of 1% aqueous solution 7.5, total Fe: 20.00% of Fe++：19.14％。
Example 5
Adding 150ml of water and 56.4g of calcium glycinate into a 0.5 liter reaction bottle with magnetic stirring, heating and stirring to 40 ℃ to form a solution, adding 14g of iron powder after dissolution, stirring and heating to 70 ℃, adding an aqueous solution prepared by 83.4g of ferrous sulfate and 150ml of water which are dissolved in advance, stirring for 0.5 hour at 80-90 ℃, cooling to room temperature, filtering, washing a filter cake with 50ml of water, drying to obtain 54.2g of calcium sulfate, adding 12g of citric acid into washing liquor and filtrate, stirring to dissolve, totally 420ml, drying at the temperature lower than 110 ℃ to obtain 80g of dark brown product, and crushing to obtain powder. pH of 1% aqueous solution 7.3, total Fe: 22.49%, Fe++：14.98％。
If the reaction is carried out by adding 6g of citric acid and 6g of fumaric acid instead of 12g of citric acid, 53.6g of calcium sulfate is obtained after filtering, washing and drying. Washing, washing,And (5) drying the filtrate 410ml to obtain 82g of product. pH of 1% aqueous solution 7.3, total Fe determined: 21.89%, Fe++：15.66％。
Claims (3)
1. A method for preparing ferrous glycinate chelate, characterized in that the method comprises the following steps in an aqueous medium when a stabilizer is added:
(1) carrying out double decomposition reaction on the calcium glycinate chelate and ferrous sulfate according to the molar ratio of 1.0-2.0: 1.0;
(2) glycine and hydroxide or oxide of calcium are reacted firstly, and then the glycine and ferrous sulfate are subjected to double decomposition reaction according to the molar ratio of 2.0-4.0: 1.0-2.0: 1.0;
(3) carrying out double decomposition reaction on ferrous glycinate chelate and hydroxide or oxide of calcium according to the molar ratio of the ferrous glycinate chelate to the hydroxide or oxide of the calcium being 1.0: 1.0-2.0;
(4) glycine and ferrous sulfate react firstly, and then the glycine and the hydroxide or oxide of calcium are subjected to double decomposition reaction according to the molar ratio of the glycine to the ferrous sulfate to the hydroxide or oxide of calcium of 2.0-4.0: 1.0-2.0;
the double decomposition reaction temperature of the four ways is 20-100 ℃, the reaction time is 0.5-5.0 hours, and then ferrous glycinate chelate with total iron content of 10-27% and ferrous iron content of 5-25% can be prepared by filtering, washing, drying and crushing.
2. The method for preparing ferrous glycine chelate according to claim 1 wherein the stabilizer added in the four metathesis reactions is selected from the group consisting of citric acid, ascorbic acid, tartaric acid, fumaric acid, malic acid, lactic acid, malonic acid, succinic acid, aspartic acid, glutamic acid, picolinic acid, acetic acid, carbonic acid and mixtures thereof and is added in an amount corresponding to 5 to 50% of the amountof glycine.
3. The process for preparing ferrous glycine chelate according to claim 1 wherein in the four metathesis reactions, the stabilizer is partially replaced by iron powder reducing agent in an amount corresponding to 5-50% of the amount of glycine.
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