Ferrous glycinate as well as preparation method and application thereof

Abstract

The invention provides ferrous glycinate and a preparation method and application thereof, and relates to the field of feed additives, the chemical formula of the ferrous glycinate is C2H11FeNO9S, the ferrous glycinate has a first coordinated iron structure and / or a second coordinated iron structure, the first coordinated iron structure is a hexa-coordinated octahedral configuration formed by coordination of tetramolecular water, bimolecular glycine carboxyl oxygen atoms and divalent iron, and the second coordinated iron structure is a hexa-coordinated octahedral configuration formed by coordination of bimolecular water, bimolecular sulfate radicals and bimolecular glycine carboxyl oxygen atoms and divalent iron. Ferrous glycinate and sulfate radicals participate in coordination, free sulfate radicals and free ferrous ions do not exist, that is, ferrous glycinate contains complex iron, and the absorption rate of animals on amino acid ferrous sub-complex iron is far higher than that of inorganic salt ferrous sulfate, so that the ferrous glycinate added into the feed can improve the feed utilization rate. And the bioavailability of animals is higher.

Description

Technical Field

[0001] The present application relates to the field of feed additives, and in particular to ferrous glycine and its preparation method and application. Background Art

[0002] Ferrous glycinate is an amino acid chelated iron with a stable molecular structure. Iron ions form a specific chelate with glycine, resulting in increased solubility. On the one hand, ferrous glycinate has beneficial effects on the physical, chemical, immune, and microbial barriers of the animal's intestines. It can improve the integrity of intestinal structure, promote the repair and regeneration of the intestinal mucosa, enhance the intestinal barrier function, and reduce the invasion of pathogens and harmful substances into the intestine. On the other hand, ferrous glycinate can promote the growth and reproduction of beneficial bacteria and inhibit the growth of harmful bacteria, thereby regulating the balance of intestinal flora, improving the intestinal microecological environment of animals, and enhancing their digestion and absorption capacity and immunity.

[0003] The relevant ferrous glycinate contains inorganic ferrous sulfate, but animals have a low absorption rate for inorganic ferrous sulfate. Therefore, the bioavailability of the relevant ferrous glycinate is low. Summary of the Invention

[0004] In order to overcome the deficiencies in the prior art, the present application provides a ferrous glycinate and a preparation method and application thereof, aiming to solve the problem of low bioavailability of the related ferrous glycinate.

[0005] To achieve the above objectives, the technical solutions adopted in this application are as follows: The embodiment of the present application provides a ferrous glycine, the chemical formula of the ferrous glycine is C2H 11 FeNO9S, and the ferrous glycine has a first coordinated iron structure and / or a second coordinated iron structure, the first coordinated iron structure is a six-coordinated octahedral configuration formed by the coordination of four molecules of water, two molecules of glycine carboxyl oxygen atoms and divalent iron, and the second coordinated iron structure is a six-coordinated octahedral configuration formed by the coordination of two molecules of water, two molecules of sulfate and two molecules of glycine carboxyl oxygen atoms and divalent iron.

[0006] In one embodiment, the ferrous glycinate has a preset ferrous content ω1, and ω1 is ≥19.8%.

[0007] In one embodiment, the ferrous glycinate has a preset glycine content ω2, and ω2 is ≥ 26.6%.

[0008] In one embodiment, the unit cell parameters of the ferrous glycinate are: a=9.0391 (3) Å, b=10.5527 (3) Å, c=10.3852 (3) Å, and α=90.00°, β=112.8740 (10)°, γ=90.00°, and the unit cell volume is 912.71 (5) Å 3 .

[0009] The embodiments of the present application also provide a method for preparing the above-mentioned ferrous glycinate, comprising: obtaining a glycine solution and ferrous sulfate, mixing them, and drying them after the reaction is completed to obtain ferrous glycinate crystals.

[0010] In one embodiment, after the reaction is completed and before the drying process is performed, a filtration process is performed at a preset temperature θ, and 50°C≤θ≤80°C.

[0011] In one embodiment, the process of obtaining the ferrous glycinate is as follows: take glycine with a mass of m1, place it in deionized water with a mass of m2, and dissolve it in a water bath at 80°C~90°C, the mass of the ferrous sulfate is m3g, and satisfies 1≤(m1+m3) / m2≤4.

[0012] In one embodiment, the molar ratio of the glycine to the ferrous sulfate is 1:1, and the ferrous sulfate is ferrous sulfate pentahydrate and / or ferrous sulfate heptahydrate.

[0013] In one embodiment, the reaction temperature of the glycine solution and the ferrous sulfate is 50° C. to 90° C., and the reaction time of the glycine solution and the ferrous sulfate is 10 min to 40 min.

[0014] An embodiment of the present application also provides an application of the above-mentioned ferrous glycine, wherein the ferrous glycine is used as an additive in animal feed, and the animal feed includes laying hen feed, and the addition amount per ton of feed is 60ppm to 100ppm based on the iron content in the ferrous glycine.

[0015] Compared with the prior art, the present invention has the following advantages: The ferrous glycine provided by the present application has a first coordinated iron structure of a hexacoordinated octahedral configuration formed by the coordination of four molecules of water, two molecules of glycine carboxyl oxygen atoms and divalent iron, and a second coordinated iron structure of a hexacoordinated octahedral configuration formed by the coordination of two molecules of water, two molecules of sulfate and two molecules of glycine carboxyl oxygen atoms and divalent iron. On the one hand, sulfate participates in the coordination, and there are no free sulfate and free ferrous ions, that is, the ferrous glycine does not contain inorganic ferrous sulfate, but is pure organic iron in the form of amino acid ferrous. Because the absorption rate of animals for organic amino acid ferrous is much greater than the absorption rate of inorganic ferrous sulfate, the ferrous glycine provided by the present application is added to feed, and the animal's bioavailability is higher. On the other hand, the ferrous glycine contains less crystalline water content, which is convenient for storage, transportation and use. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following is a brief introduction to the drawings required for use in the embodiments. It should be understood that the following drawings only show certain embodiments of the present application and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other relevant drawings can be obtained based on these drawings without creative work.

[0017] Figure 1 The spatial structure diagram of ferrous glycine is shown; Figure 2 Shown is a schematic flow diagram of a method for preparing ferrous glycine; Figure 3 A comparison of the simulated and detected spectra of ferrous glycinate is shown. DETAILED DESCRIPTION

[0018] The following describes in detail embodiments of the present application. Examples of the embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present application and are not to be construed as limiting the present application.

[0019] In the description of the present application, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", "clockwise", "counterclockwise", "axial", "radial", "circumferential" and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as a limitation on the present application.

[0020] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of the technical features being referred to. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of the features. Throughout the description of this application, "plurality" means two or more, unless otherwise specifically defined.

[0021] In this application, unless otherwise expressly specified or limited, terms such as "mounted," "connected," "connect," and "fixed" should be understood in a broad sense. For example, they may refer to fixed connections, detachable connections, or integration; mechanical connections or electrical connections; direct connections or indirect connections through an intermediate medium; and internal connections between two components or interactions between two components. Those skilled in the art will understand the specific meanings of these terms in this application based on specific circumstances.

[0022] In this application, unless otherwise expressly specified or limited, when a first feature is "above" or "below" a second feature, it may mean that the first and second features are in direct contact, or the first and second features are in indirect contact through an intermediate medium. Furthermore, when a first feature is "above," "above," or "above" a second feature, it may mean that the first feature is directly above or diagonally above the second feature, or simply means that the first feature is at a higher level than the second feature. When a first feature is "below," "below," or "below" a second feature, it may mean that the first feature is directly below or diagonally below the second feature, or simply means that the first feature is at a lower level than the second feature.

[0023] Example 1 The present invention provides a ferrous glycine salt, wherein the chemical formula of the ferrous glycine salt is C2H 11 FeNO9S, and the ferrous glycinate has a first coordination iron structure and a second coordination iron structure. Figure 1 The first coordinated iron structure is a hexacoordinated octahedral configuration formed by the coordination of four molecules of water and two molecules of glycine carboxyl oxygen atoms with divalent iron. The second coordinated iron structure is a hexacoordinated octahedral configuration formed by the coordination of two molecules of water, two molecules of sulfate, and two molecules of glycine carboxyl oxygen atoms with divalent iron.

[0024] In other embodiments, the ferrous glycinate has the first coordinated iron structure or the second coordinated iron structure.

[0025] In some embodiments, the ferrous glycinate has a predetermined ferrous content ω1, and ω1 is ≥19.8%. The ferrous glycinate has a predetermined glycine content ω2, and ω2 is ≥26.6%.

[0026] Furthermore, ω1 = 19.87% and ω2 = 26.69%.

[0027] Existing ferrous glycinate, such as [Fe(C2H5NO2)2SO4·4H2O]·[FeSO4·6H2O], has a structural formula containing one molecule of complexed ferrous glycinate and one molecule of ferrous sulfate hexahydrate, i.e., organic and inorganic ferrous forms coexist, and the sulfate group exists in a free form and does not participate in coordination. In addition, its ferrous content is 17.61%, and its glycine content is 23.65%, i.e., the active ingredient content is relatively low. Moreover, it contains 10 crystal waters, and is prone to problems such as water loss, hardening, and discoloration during use, which has a significant impact on processes such as warehousing, transportation, and mixing.

[0028] As for the ferrous glycine provided by the present application, on the one hand, sulfate ions participate in the coordination, and there are no free sulfate ions and free ferrous ions, that is, the ferrous glycine does not contain inorganic ferrous sulfate, but is pure organic iron in the form of amino acid ferrous. Because the absorption rate of animals for organic ferrous amino acid is much higher than that for inorganic ferrous sulfate, therefore, when the ferrous glycine provided by the present application is added to feed, the animal's bioavailability is higher. On the other hand, the ferrous content in the ferrous glycine is 19.87%, and the glycine content is 23.69%, that is, compared with the existing [Fe(C2H5NO2)2SO4·4H2O]·[FeSO4·6H2O], the ferrous glycine provided by the present application has a higher ferrous content, that is, a higher content of effective ingredients, which can further improve the animal's bioavailability. In addition, the ferrous glycinate provided in the present application has a low content of crystalline water, a more stable structure at higher temperatures (60°C~100°C), is less prone to water loss, discoloration, and hardening, and is easy to store, transport, and use.

[0029] It can be understood that the iron in the ferrous glycinate is pure organic iron. Compared with inorganic iron or semi-organic iron and semi-inorganic iron, the ferrous glycinate in the form of pure organic iron is added to the feed as a feed additive, and has higher bioavailability. In addition, the ferrous glycinate has a high ferrous content, which can improve the problem of excessive addition of the ferrous glycinate during actual use.

[0030] In some embodiments, the unit cell parameters of the ferrous glycinate are: a=9.0391 (3) Å, b=10.5527 (3) Å, c=10.3852 (3) Å, and α=90.00°, β=112.8740 (10)°, γ=90.00°, and the unit cell volume is 912.71 (5) Å 3 .

[0031] It should be noted that the molecular weight of the ferrous glycinate is 281.03, the ferrous glycinate is a monoclinic crystal, and the space group of the ferrous glycinate is P2(1) / n.

[0032] Example 2 See also Figure 2 The present application also provides a method for preparing the ferrous glycine in the first embodiment, the method comprising the following steps: S100: Obtain glycine and deionized water, and dissolve the glycine in the deionized water under a water bath condition at a first preset temperature θ1 to prepare a glycine solution; S200: obtaining ferrous sulfate and mixing the ferrous sulfate with a glycine solution to prepare a reaction solution; S300: reacting the reaction solution in a water bath at a second preset temperature θ2, and allowing the reaction solution to stand after the reaction is completed; S400: filtering the reaction liquid after standing at a third preset temperature θ3 to obtain a filter cake, and drying the filter cake to obtain ferrous glycinate crystals.

[0033] In some embodiments, the mass of the glycine in S100 is m1, the mass of the deionized water in S100 is m2, and the mass of the ferrous sulfate in S200 is m3, and 1≤(m1+m3) / m2≤4 is satisfied.

[0034] It is understandable that in the preparation process of the ferrous glycinate, the solid-liquid ratio of the reaction raw materials is 1:1~4:1.

[0035] In some embodiments, the ferrous sulfate in S200 is ferrous sulfate pentahydrate or ferrous sulfate heptahydrate.

[0036] In other embodiments, the ferrous sulfate in S200 is ferrous sulfate pentahydrate and ferrous sulfate heptahydrate.

[0037] In some embodiments, θ2=θ1, and 80°C≤θ1≤90°C.

[0038] Furthermore, θ1=80°C.

[0039] In some embodiments, the reaction solution in S200 needs to react in a water bath at 80° C. for a first preset time t1, and 10 min≤t1≤40 min.

[0040] Furthermore, t=30 min, and the temperature of the reaction solution dropped to 60° C. after the reaction for 30 min.

[0041] In some embodiments, the glycine and the ferrous sulfate in the reaction solution in S300 react at a molar ratio of 1:1.

[0042] It should be noted that the reaction equation of the reaction solution in S300 is: C2H5NO2+FeSO4·7H2O→C2H 11 FeNO9S+4H2O.

[0043] In some embodiments, the reaction solution in S300 needs to be left to stand for a second preset time t2 after the reaction is completed, and t2 ≥ 2h.

[0044] In some embodiments, 50°C ≤ θ3 ≤ 80°C.

[0045] Furthermore, θ3=60°C.

[0046] It should be noted that filtering the reaction solution at 60° C. is beneficial to the stability of ferrous ions and can reduce the possibility of ferrous ions being oxidized to ferric ions, thereby ensuring the ferrous content in the ferrous glycine.

[0047] In some embodiments, the drying temperature of the filter cake in S400 is 50°C to 100°C.

[0048] In some embodiments, the ferrous glycinate crystals in S400 are crystalline solids with good fluidity and are not prone to agglomeration.

[0049] It is understood that the preparation method of the ferrous glycine is as follows: glycine, deionized water and ferrous sulfate heptahydrate are obtained, and glycine is dissolved in deionized water under 80°C water bath conditions to obtain a glycine solution, ferrous sulfate heptahydrate is mixed with the glycine solution to obtain a reaction solution, and the reaction solution is reacted under 80°C water bath conditions for 30 minutes, the reaction solution is cooled to 60°C, allowed to stand for crystallization for 2 hours, and filtered at 60°C to obtain a filter cake, and the filter cake is dried at 50°C~100°C to obtain ferrous glycine crystals.

[0050] In order to better illustrate the effect of the preparation method of the ferrous glycinate involved in this embodiment on improving the effective content of the prepared ferrous glycinate, the following example verification experiment was conducted: Experimental Group 1: 8 g of glycine was dissolved in 30 mL of deionized water in an 80°C water bath. 30 g of ferrous sulfate heptahydrate was then added and the mixture was allowed to react in an 80°C water bath for 30 min. After standing for 2 h to crystallize, the mixture was filtered at 50°C to obtain a filter cake, which was then dried at 70°C to obtain the first crystal.

[0051] Experimental Group 2: 8 g of glycine was dissolved in 30 mL of deionized water in an 80°C water bath. 30 g of ferrous sulfate heptahydrate was then added and the mixture was allowed to react in an 80°C water bath for 30 min. After standing for 2 h to crystallize, the mixture was filtered at 60°C to obtain a filter cake, which was then dried at 70°C to obtain a second crystal.

[0052] Experimental Group 3: 8 g of glycine was dissolved in 30 mL of deionized water in an 80°C water bath. 30 g of ferrous sulfate heptahydrate was then added and the mixture was allowed to react in an 80°C water bath for 30 min. After standing for 2 h to crystallize, the mixture was filtered at 65°C to obtain a filter cake, which was then dried at 70°C to obtain the third crystal.

[0053] Experimental Group 4: 8 g of glycine was dissolved in 30 mL of deionized water in an 80°C water bath. 30 g of ferrous sulfate heptahydrate was then added and the mixture was allowed to react in an 80°C water bath for 30 min. After standing for 2 h to crystallize, the mixture was filtered at 70°C to obtain a filter cake, which was then dried at 70°C to obtain the fourth crystal.

[0054] Experimental Group 5: 8 g of glycine was dissolved in 30 mL of deionized water in an 80°C water bath. 30 g of ferrous sulfate heptahydrate was then added and the mixture was allowed to react in an 80°C water bath for 30 min. After standing for 2 h to crystallize, the mixture was filtered at room temperature of 25°C to obtain a filter cake, which was then dried at 70°C to obtain the fifth crystal.

[0055] Experimental Group 6: 9 g of glycine was dissolved in 500 mL of deionized water, heated to 68°C, 23 g of ferrous nitrate was added and stirred, and the reaction was carried out for 0.8 h. The mixture was then cooled to 25°C, filtered to obtain a filter cake, and dried at 70°C to obtain the sixth crystal.

[0056] The contents of the first, second, third, fourth, fifth, and sixth crystals were measured, respectively, to obtain a comparative table of ferric iron content, ferrous iron content, glycine content, and free glycine content, as shown in Table 1.

[0057] It should be noted that the difference between Example 1, Example 2, Example 3, Example 4 and Example 5 lies in the different filtration temperatures, and Example 6 is an existing method for preparing ferrous glycinate.

[0058] Table 1 Comparison of various content determinations

[0059] It should be noted that the ferric iron content and ferrous iron content of the first, second, third, and fourth crystals were determined by redox titration, the glycine content of the first, second, third, fourth, fifth, and sixth crystals was determined by Kjeldahl nitrogen determination, and the free glycine content of the first, second, third, fourth, fifth, and sixth crystals was determined by the national standard method (GB / T 21996-2008). The specific testing procedures for each content are not described here one by one.

[0060] Since it is difficult to ensure that the experimental conditions are completely consistent, there is a certain error in the above experimental data, but it does not affect the final experimental results. It can be seen from Table 1 that the ferrous content measured in the experimental group two is the largest, and the glycine content measured in the experimental group two is the largest. Therefore, the preparation method of the ferrous glycine in the above-mentioned experimental group two is adopted. In the prepared ferrous glycine crystals, the contained ferrous content and glycine content are the highest, that is, the active ingredient content is the highest. It can be seen that filtering the reaction solution at 60 ° C is conducive to the stability of ferrous ions, so as to ensure the high ferrous content in the prepared ferrous glycine, and the crystallization water content is small, and the subsequent drying energy consumption is low. In addition, compared to filtering under existing normal temperature conditions, the preparation method of the ferrous glycine provided by the application reduces the time required for the cooling crystallization process.

[0061] See also Figure 3 The simulated spectrum of ferrous glycine with 19% ferrous content was used as the standard spectrum. By performing X-ray powder diffraction analysis on the standard spectrum and the second crystal in experimental group 2, it was found that the peak shapes of the two were basically consistent, indicating that the crystal forms were consistent.

[0062] Example 3 The embodiment of the present application also provides an application of the ferrous glycine in the above-mentioned embodiment 1. The ferrous glycine is used as an additive in feed, and therefore has all the beneficial effects of the ferrous glycine in any of the above-mentioned embodiments 1, which will not be described in detail here.

[0063] Furthermore, the ferrous glycine is used as an additive in laying hen feed.

[0064] In some embodiments, the addition amount per ton of laying hen feed is 60 ppm to 100 ppm based on the iron content in ferrous glycine.

[0065] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present application. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine different embodiments or examples described in this specification and features of different embodiments or examples without contradiction.

[0066] Although the embodiments of the present application have been shown and described above, it can be understood that the above embodiments are exemplary and cannot be understood as limitations on the present application. Ordinary technicians in this field can change, modify, replace and modify the above embodiments within the scope of the present application.

Claims

1. A ferrous glycinate, characterized in that The chemical formula of the ferrous glycine is C2H 11 FeNO9S, and the ferrous glycine has a first coordinated iron structure and / or a second coordinated iron structure, the first coordinated iron structure is a six-coordinated octahedral configuration formed by the coordination of four molecules of water, two molecules of glycine carboxyl oxygen atoms and divalent iron, and the second coordinated iron structure is a six-coordinated octahedral configuration formed by the coordination of two molecules of water, two molecules of sulfate and two molecules of glycine carboxyl oxygen atoms and divalent iron.

2. The ferrous glycinate according to claim 1, wherein The ferrous glycinate has a preset ferrous content ω1, and ω1 is ≥19.8%.

3. Ferrous glycine according to claim 2, characterized in that, The ferrous glycinate has a preset glycine content ω2, and ω2 is ≥26.6%.

4. The ferrous glycinate according to claim 1, wherein The unit cell parameters of the ferrous glycinate are: a=9.0391(3)Å, b=10.5527(3)Å, c=10.3852(3)Å, and α=90.00°, β=112.8740(10)°, γ=90.00°, and the unit cell volume is 912.71(5)Å. 3 .

5. The method for preparing ferrous glycinate according to any one of claims 1 to 4, wherein include: A glycine solution and ferrous sulfate are obtained and mixed, and after the reaction is completed, drying is performed to obtain ferrous glycine crystals.

6. The method for preparing ferrous glycinate according to claim 5, wherein: After the reaction is completed and before the drying process is performed, filtration is required to be performed at a preset temperature θ, and 50°C ≤ θ ≤ 80°C.

7. The method for preparing ferrous glycinate according to claim 5, wherein: The specific process of obtaining the ferrous glycinate is as follows: take glycine with a mass of m1, place it in deionized water with a mass of m2, and dissolve it in a water bath at 80°C~90°C. The mass of the ferrous sulfate is m3, and it satisfies 1≤(m1+m3) / m2≤4.

8. The method for preparing ferrous glycinate according to claim 7, wherein The molar ratio of the glycine to the ferrous sulfate is 1:1, and the ferrous sulfate is ferrous sulfate pentahydrate and / or ferrous sulfate heptahydrate.

9. The method for preparing ferrous glycinate according to claim 7, wherein The reaction temperature of the glycine solution and the ferrous sulfate is 50° C. to 90° C., and the reaction time of the glycine solution and the ferrous sulfate is 10 min to 40 min.

10. A use of ferrous glycinate according to any one of claims 1 to 4, characterized in that: The ferrous glycine is used as an additive in animal feed, and the animal feed includes laying hen feed. The addition amount per ton of feed is 60ppm to 100ppm based on the iron content in the ferrous glycine.

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