Preparation method and application of tannic acid rare earth chelate

Abstract

The invention discloses a preparation method and application of a tannic acid rare earth chelate, and the preparation method comprises the following steps: (1) placing tannic acid and a lanthanide rare earth compound or a cerium rare earth compound in a reaction solvent, heating and dissolving, and then carrying out heat treatment; and (2) filtering and collecting solid precipitates in the material obtained in the step (1), washing with pure water, and carrying out vacuum drying to obtain the product. The tannic acid rare earth chelate prepared by the invention is innovatively applied to the field of livestock and poultry breeding, has remarkable advantages and effects, not only improves the production efficiency and the economic benefit, but also improves the animal health condition and the product quality, and plays a positive role in promoting the sustainable development of the breeding industry.

Description

Technical Field

[0001] The present invention belongs to the technical field of rare earth material synthesis and feed additive development, and specifically relates to a preparation method and application of rare earth tannate chelate. Background Art

[0002] Currently, due to their unique physical and chemical properties, rare earth elements are gradually showing their roles in promoting growth and improving feed conversion rate in the livestock industry. There are abundant types of rare earth elements, and their unique physical and chemical properties, such as excellent optical, electrical, magnetic, and catalytic properties, endow them with broad application potential in multiple fields. In the livestock industry, rare earth elements play roles in promoting growth and improving feed conversion rate by participating in various physiological processes in animals, such as promoting bone development, enhancing immunity, and improving digestion and absorption functions. This not only helps improve the production performance of animals, but also reduces feed costs and improves breeding efficiency, providing a new way for the sustainable development of the livestock industry.

[0003] In the livestock industry, a lot of research results have also been achieved in the application of rare earths, providing strong support for promoting the development of the livestock industry. However, despite certain progress, there are still significant bottlenecks in the existing technologies.

[0004] In terms of inorganic rare earth additives, although lanthanum nitrate, cerium chloride, etc. have low costs, their high adsorption properties lead to poor uniformity when mixed with feed (solubility <5 g / L), and excessive intake is likely to cause metabolic burdens on the kidneys and livers of animals. Although organic rare earths (such as rare earth amino acids and rare earth vitamin C) improve bioavailability through coordination structures, their synthesis processes are complex (requiring multiple-step purification), and the rare earth amino acids disclosed in CN1105819A are easily decomposed by microorganisms in the intestine (ineffectiveness rate >80%), and long-acting release cannot be achieved. Although carrier-type rare earth additives (such as the cation exchange resin-supported type in CN1911071A) improve stability, limited by the biocompatibility of the carrier material, their actual absorption efficiency is still less than 40%, and poor palatability may lead to a decrease in feed intake.

[0005] As a natural polyphenol compound, the antioxidant property (ORAC value ≥30,000 μmol TE / g) and antibacterial activity (MIC against Escherichia coli as low as 0.1 mg / mL) of tannic acid have been confirmed in the feed field, but existing patents such as CN114468138A and CN1823613A have not effectively integrated the synergistic effect of tannic acid and rare earths. For example, although CN109258962A introduces organic rare earth to improve eggshell strength, due to the problem of the structural stability of the complex not being solved (dissociation rate >60% at pH >7), its practical application is limited.

[0006] In addition, the prior art has the problem of poor dose adaptability. CN110169497A regulates the intestinal function of livestock and poultry by gadolinium chloride, but the recommended addition amount range fluctuates by up to 25%-300% (depending on the differences in animal breeds), and it is easy to cause toxicity risks due to operation errors. At the same time, although the rare earth-hypercithiol composite process proposed by CN109221681A simplifies the production process, the mechanical mixing of rare earth and carrier is difficult to achieve molecular-level binding, and the release is uncontrollable during actual feeding (the in vitro dissolution deviation is ±30%). Summary of the Invention

[0007] The purpose of the present invention is to overcome the defects of the prior art and provide a preparation method and application of tannic acid rare earth chelate.

[0008] Another purpose of the present invention is to provide the application of the tannic acid rare earth chelate prepared by the above preparation method.

[0009] The technical solution of the present invention is as follows:

[0010] A preparation method of tannic acid rare earth chelate, comprising the following steps:

[0011] (1) Placing tannic acid and lanthanide rare earth compound or cerium series rare earth compound in a reaction solvent, heating and dissolving, and then performing heat treatment; the heat treatment is specifically: heating to 120°C within 30 minutes, keeping warm for 24 hours, and then cooling to 30°C for 24 hours; or specifically: refluxing at 60°C for 1 hour;

[0012] (2) Filtering and collecting the solid precipitate in the material obtained in step (1), washing with pure water, and then performing vacuum drying to obtain the product.

[0013] In a preferred embodiment of the present invention, the mass ratio of tannic acid to lanthanide rare earth compound or cerium series rare earth compound is 1-1.5:1-1.5.

[0014] In a preferred embodiment of the present invention, the reaction solvent is selected from pure water, tetrahydrofuran, acetone and DMF.

[0015] In a preferred embodiment of the present invention, the temperature of the vacuum drying is 50-110°C, and the time is 3-10 hours.

[0016] In a preferred embodiment of the present invention, the lanthanide rare earth compound is selected from lanthanum chloride and lanthanum nitrate, and the cerium series rare earth compound is selected from cerium chloride and cerium nitrate.

[0017] Use of the tannic acid rare earth chelate prepared by the above preparation method in the preparation of feed additives.

[0018] A feed additive, the active ingredient of which comprises the tannic acid rare earth chelate prepared by the above preparation method.

[0019] Use of the above feed additive in the preparation of poultry feed compositions.

[0020] A poultry feed composition, characterized in that its raw materials include the above feed additive.

[0021] The beneficial effects of the present invention are:

[0022] 1. The present invention promotes the growth rate and weight gain rate: The tannic acid rare earth chelate prepared by the present invention has a significant promoting effect on the growth rate and weight gain rate of livestock and poultry, can accelerate the growth of livestock and poultry, make their weight increase more significantly in the same time, and improve the breeding production efficiency.

[0023] 2. The present invention improves the feed conversion rate: Using the tannic acid rare earth chelate prepared by the present invention can effectively improve the feed conversion rate, enable animals to utilize the nutritional components in the feed more efficiently, reduce feed waste, and thus enhance the breeding benefit and economic benefit.

[0024] 3. The present invention enhances the disease resistance and survival rate: By applying the tannic acid rare earth chelate prepared by the present invention, the disease resistance and survival rate of livestock and poultry are significantly improved, the disease incidence and mortality rate in the breeding process are reduced, losses are decreased, and the stability and sustainability of breeding are enhanced.

[0025] 4. The present invention improves the quality of animal products: The tannic acid rare earth chelate prepared by the present invention can not only promote the growth of animals, but also improve the quality of animal products, such as enhancing the tenderness of meat, increasing the thickness and strength of eggshells, etc., making livestock and poultry products more competitive in the market and increasing the added value.

[0026] 5. The present invention promotes the sustainable development of the breeding industry: The innovative application of the tannic acid rare earth chelate prepared by the present invention in the field of livestock and poultry breeding has significant advantages and effects. It not only improves the production efficiency and economic benefit, but also improves the animal health status and product quality, and plays a positive role in promoting the sustainable development of the breeding industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 It is the infrared spectrum of the rare earth tannic acid in the present invention. It can be seen from this infrared spectrum that the wave numbers (cm -1 ) of tannic acid with a purity of 96% are 3293s, 1701s, 1608s, 1534m, 1440m, 1355w, 1306s, 1175s, 1081w, 1011m, 869w, 754w; the wave numbers (cm -1) are 3212w, 1701s, 1608m, 1530w, 1444w, 1314s, 1191s, 1089w, 1024m, 865w, 759w; The wave numbers (cm -1 ) of the cerium tannate-based rare earth chelates prepared in Examples 6 to 10 are 3343m, 1573s, 1423w, 1403m, 1351s, 1201w, 1050w, 777s, 597w, 542w.

[0028] Figure 2 shows the surface morphology of the lanthanum tannate-based rare earth chelates prepared in Examples 1 to 5 of the present invention.

[0029] Figure 3 is the powder X-ray diffraction analysis pattern of the rare earth tannate chelate in the present invention, and the formula is 2dsinθ = nλ. As can be seen from the figure: the 2θ (0–50) diffraction peaks of the lanthanum tannate-based rare earth chelates prepared in Examples 1 to 5 are 10.7, 11.4, 11.7, 13.22, 13.5, 15.8, 16.8, 17.8, 19.9, 20.6, 22.8, 23.1, 23.4, 26.9, 28.2, 32.9, 33.9, 34.3, 35.9, 39.1, 40.5, 41.1, 41.9, 45.1, 45.8, 46.5, and the error range is 2θ = ±0.25. The unit cell parameters with the highest symmetry are a = 8.9, b = 10.7, c = 6.6, α = 78.8, β = 102.2, γ = 92.1, and the error range is and 0.5 degrees, and the space group is P-1; the 2θ (0–50) diffraction peaks of the cerium tannate-based rare earth chelates prepared in Examples 6 to 10 show a disordered crystal form.

[0030] Figure 4 shows the results of the field experiment of Example 17 of the present invention. Specific Embodiments

[0031] The technical solutions of the present invention will be further described and illustrated below through specific embodiments in conjunction with the accompanying drawings.

[0032] Example 1

[0033] (1) In a reaction kettle, 1.5 g (purity 96%) of tannic acid and 1.5 g of lanthanum chloride were placed in 20 mL of pure water and heated to dissolve. The temperature was raised to 120 °C within 30 min, kept warm for 24 h, and then cooled to 30 °C within 24 h.

[0034] (2) The solid precipitate in the material obtained in step (1) was collected by filtration, washed with 500 mL of pure water, and vacuum dried at 110 °C for 10 h to finally obtain the lanthanum tannate-based rare earth chelate.

[0035] Example 2

[0036] (1) In a reaction kettle, 1.5 g (purity 96%) of tannic acid and 1.5 g of lanthanum chloride were placed in 20 mL of tetrahydrofuran and heated to dissolve. The temperature was raised to 120 °C within 30 min, kept warm for 24 h, and then cooled for 24 h to 30 °C.

[0037] (2) The solid precipitate in the material obtained in step (1) was collected by filtration, washed with 500 mL of pure water, and vacuum dried at 110 °C for 10 h to finally obtain a lanthanide rare earth chelate of tannic acid.

[0038] Example 3

[0039] (1) In a reaction kettle, 1.5 g (purity 96%) of tannic acid and 1.5 g of lanthanum chloride were placed in 20 mL of acetone and heated to dissolve. The temperature was raised to 120 °C within 30 min, kept warm for 24 h, and then cooled for 24 h to 30 °C.

[0040] (2) The solid precipitate in the material obtained in step (1) was collected by filtration, washed with 500 mL of pure water, and vacuum dried at 110 °C for 10 h to finally obtain a lanthanide rare earth chelate of tannic acid.

[0041] Example 4

[0042] (1) In a reaction kettle, 1.5 g (purity 96%) of tannic acid and 1.5 g of lanthanum nitrate were placed in 20 mL of DMF and heated to dissolve. The temperature was raised to 120 °C within 30 min, kept warm for 24 h, and then cooled for 24 h to 30 °C.

[0043] (2) The solid precipitate in the material obtained in step (1) was collected by filtration, washed with 500 mL of pure water, and vacuum dried at 110 °C for 10 h to finally obtain a lanthanide rare earth chelate of tannic acid.

[0044] Example 5

[0045] (1) In a reaction kettle, 1.5 g (purity 96%) of tannic acid and 1.5 g of lanthanum nitrate were placed in 20 mL of absolute ethanol and heated to dissolve. The temperature was raised to 120 °C within 30 min, kept warm for 24 h, and then cooled for 24 h to 30 °C.

[0046] (2) The solid precipitate in the material obtained in step (1) was collected by filtration, washed with 500 mL of pure water, and vacuum dried at 110 °C for 10 h to finally obtain a lanthanide rare earth chelate of tannic acid.

[0047] The lanthanide rare earth chelates of tannic acid prepared in the above Examples 1 to 5 are as Figures 1 to 3 shown, being [La7(tanninsacid)]14- Elemental analysis data, theoretical values: C, 17.71; H, 1.12; O, 39.13; La, 34.98; actual values: C, 18.01; H, 1.57; O, 40.05; La, 34.33. The test source of La is ICPAES.

[0048] Example 6

[0049] (1) In a reaction kettle, 1.5 g (purity 96%) of tannic acid and 1.5 g of cerium chloride were placed in 20 mL of pure water and heated to dissolve. The temperature was raised to 120 °C within 30 min, held for 24 h, and then cooled to 30 °C over 24 h.

[0050] (2) The solid precipitate in the material obtained in step (1) was collected by filtration, washed with 500 mL of pure water, and vacuum dried at 110 °C for 10 h to finally obtain a rare earth chelate of tannic acid cerium system.

[0051] Example 7

[0052] (1) In a reaction kettle, 1.5 g (purity 96%) of tannic acid and 1.5 g of cerium chloride were placed in 20 mL of absolute ethanol and heated to dissolve. The temperature was raised to 120 °C within 30 min, held for 24 h, and then cooled to 30 °C over 24 h.

[0053] (2) The solid precipitate in the material obtained in step (1) was collected by filtration, washed with 500 mL of pure water, and vacuum dried at 110 °C for 10 h to finally obtain a rare earth chelate of tannic acid cerium system.

[0054] Example 8

[0055] (1) In a reaction kettle, 1.5 g (purity 96%) of tannic acid and 1.5 g of cerium chloride were placed in 20 mL of tetrahydrofuran and heated to dissolve. The temperature was raised to 120 °C within 30 min, held for 24 h, and then cooled to 30 °C over 24 h.

[0056] (2) The solid precipitate in the material obtained in step (1) was collected by filtration, washed with 500 mL of pure water, and vacuum dried at 110 °C for 10 h to finally obtain a rare earth chelate of tannic acid cerium system.

[0057] Example 9

[0058] (1) In a reaction kettle, 1.5 g (purity 96%) of tannic acid and 1.5 g of cerium nitrate were placed in 20 mL of pure acetone and heated to dissolve. The temperature was raised to 120 °C within 30 min, held for 24 h, and then cooled to 30 °C over 24 h.

[0059] (2) Filter and collect the solid precipitate in the material obtained in step (1), wash it with 500 mL of pure water, and vacuum dry it at 110 °C for 10 h to finally obtain a cerium tannate-based rare earth chelate.

[0060] Example 10

[0061] (1) In a reaction kettle, place 1 g (purity 96%) of tannic acid and 1.5 g of cerium chloride in 20 mL of DMF, and heat to dissolve. Heat up to 120 °C within 30 min, keep the temperature for 24 h, and then cool down to 30 °C over 24 h.

[0062] (2) Filter and collect the solid precipitate in the material obtained in step (1), wash it with 500 mL of pure water, and vacuum dry it at 110 °C for 10 h to finally obtain a cerium tannate-based rare earth chelate.

[0063] The cerium tannate-based rare earth chelates prepared in Examples 6 to 10 above are as Figure 1 and Figure 3 shown, which is [Ce7(tannins acid)] 14- . The elemental analysis data, theoretical values: C, 25.71; H, 1.48; Ce, 27.6; actual values: C, 25.60; H, 1.22; Ce, 28.19, where the test source of Ce is ICPAES.

[0064] Example 11

[0065] In a reflux device, weigh 3.0 g of lanthanum chloride and 2.0 - 3.5 g (purity 65%) of tannic acid, place them in 30 mL of pure water, and heat and stir to dissolve. Control the temperature at 60 °C and reflux for 1 h to obtain a dark solid. After filtration, wash it three times with 50 mL of pure water, and then carry out low-temperature vacuum drying at 50 °C for 3 h to finally obtain a lanthanum tannate-based rare earth chelate.

[0066] Example 12

[0067] In a reflux device, weigh 3.0 g of lanthanum chloride and 3.5 g (purity 65%) of tannic acid, place them in 30 mL of absolute ethanol, and heat and stir to dissolve. Control the temperature at 60 °C and reflux for 1 h to obtain a dark solid. After filtration, wash it three times with 50 mL of pure water, and then carry out low-temperature vacuum drying at 50 °C for 3 h to finally obtain a lanthanum tannate-based rare earth chelate.

[0068] Example 13

[0069] In a reflux apparatus, 3.0 g of lanthanum chloride and 3.5 g of tannic acid (purity 65%) were weighed and placed in 30 mL of acetone. They were heated with stirring for dissolution. The temperature was controlled at 60 °C and refluxed for 1 h to obtain a dark solid. After filtration, it was washed three times with 50 mL of pure water and then dried under low-temperature vacuum at 50 °C for 3 h to finally obtain a lanthanum-based rare earth chelate of tannic acid.

[0070] Example 14

[0071] In a reflux apparatus, 3.0 g of lanthanum chloride and 3.5 g of tannic acid (purity 65%) were weighed and placed in 30 mL of tetrahydrofuran. They were heated with stirring for dissolution. The temperature was controlled at 60 °C and refluxed for 1 h to obtain a dark solid. After filtration, it was washed three times with 50 mL of pure water and then dried under low-temperature vacuum at 50 °C for 3 h to finally obtain a lanthanum-based rare earth chelate of tannic acid.

[0072] Example 15

[0073] In a reflux apparatus, 3.0 g of lanthanum chloride and 3.5 g of tannic acid (purity 65%) were weighed and placed in 30 mL of DMF. They were heated with stirring for dissolution. The temperature was controlled at 60 °C and refluxed for 1 h to obtain a dark solid. After filtration, it was washed three times with 50 mL of pure water and then dried under low-temperature vacuum at 50 °C for 3 h to finally obtain a lanthanum-based rare earth chelate of tannic acid.

[0074] Example 16

[0075] In a reflux apparatus, 3.0 g of lanthanum chloride and 3.5 g of tannic acid (purity 65%) were weighed and placed in 30 mL of methanol. They were heated with stirring for dissolution. The temperature was controlled at 60 °C and refluxed for 1 h to obtain a dark solid. After filtration, it was washed three times with 50 mL of pure water and then dried under low-temperature vacuum at 50 °C for 3 h to finally obtain a lanthanum-based rare earth chelate of tannic acid.

[0076] The characterization data and results of the lanthanum-based rare earth chelates of tannic acid prepared in Examples 11 to 16 above are the same as those of the lanthanum-based rare earth chelates of tannic acid prepared in Examples 1 to 5 above.

[0077] Example 17

[0078] 315 one-day-old white - feather broilers were selected and randomly divided into 7 groups, with 9 replicates in each group and 5 chickens in each replicate. The experimental period was 42 days and the cage - rearing method was adopted.

[0079] Among them, the control group was fed with a basal diet; the experimental group 1 was fed with a basal diet supplemented with 100 g / t of the cerium tannate-based rare earth chelate prepared in Examples 6 to 10; the experimental group 2 was fed with a basal diet supplemented with 100 g / t of the lanthanum tannate-based rare earth chelate prepared in Examples 1 to 5 and Examples 11 to 15; the experimental group 3 was fed with a basal diet supplemented with 1000 g / t of neomycin; the experimental group 4 was fed with a basal diet supplemented with 600 g / t of a similar imported brand product. The test results are as Figure 4 shown. Compared with the control group, the average daily feed intake of the experimental group 2 decreased by 2.69%, and the average daily weight gain increased by 3.11%.

[0080] It should be added that:

[0081] The basal diet was divided into the chick stage, the growth stage, the mid-growth stage, and the late-growth stage. Specifically:

[0082] (1) In the chick stage (0 - 10 days old), the formula of its basal diet was: corn 56.3%, soybean meal 38%, calcium hydrogen phosphate 1.4%, stone powder 1%, salt 0.3%, vegetable oil 3%;

[0083] (2) In the growth stage (10 - 21 days old), the formula of its basal diet was: corn 55.2%, soybean meal 34%, vegetable meal 5%, calcium hydrogen phosphate 1.5%, stone powder 1%, salt 0.3%, vegetable oil 3%;

[0084] (3) In the mid-growth stage (21 - 35 days old), the formula of its basal diet was: corn 49%, cassava 10%, soybean meal 35%, soybean oil 6%;

[0085] (4) In the late-growth stage (> 35 days old), the formula of its basal diet was: corn 61%, soybean meal 20%, wheat 15%, fish meal 2%, vegetable oil 2%.

[0086] As described above, it is only a preferred embodiment of the present invention, and thus the scope of implementation of the present invention cannot be limited thereby. That is, equivalent changes and modifications made according to the scope of the present invention patent and the content of the specification should still fall within the scope covered by the present invention.

Claims

1. A preparation method of a rare earth chelate of tannic acid, characterized in that: It includes the following steps: (1) Put tannic acid and lanthanide rare earth compound or cerium-based rare earth compound into a reaction solvent, heat and dissolve them, and then conduct heat treatment; specifically, the heat treatment is: heat up to 120 °C within 30 min, keep warm for 24 h, and then cool down for 24 h to 30 °C; or specifically: reflux at 60 °C for 1 h; (2) Filter and collect the solid precipitate in the material obtained in step (1), wash it with pure water, and then conduct vacuum drying to obtain the product.

2. The preparation method according to claim 1, characterized in that: The mass ratio of the tannic acid to the lanthanide rare earth compound or cerium-based rare earth compound is 1-1.5:1-1.

5.

3. The preparation method according to claim 1, characterized in that: The reaction solvent is selected from pure water, tetrahydrofuran, acetone and DMF.

4. The preparation method according to claim 1, characterized in that: The temperature of the vacuum drying is 50-110 °C, and the time is 3-10 h.

5. The preparation method according to any one of claims 1 to 4, characterized in that: The lanthanide rare earth compound is selected from lanthanum chloride and lanthanum nitrate, and the cerium-based rare earth compound is selected from cerium chloride and cerium nitrate.

6. Use of the rare earth chelate of tannic acid prepared by the preparation method according to any one of claims 1 to 5 in the preparation of feed additives.

7. A feed additive, characterized in that: Its active ingredient includes the rare earth chelate of tannic acid prepared by the preparation method according to any one of claims 1 to 4.

8. Use of the feed additive according to claim 7 in the preparation of poultry feed compositions.

9. A poultry feed composition, characterized in that: It has the feed additive according to claim 7.

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