CN115819263A - Organic zinc-selenium chelate, functional fertilizer, and preparation method and application thereof - Google Patents
Organic zinc-selenium chelate, functional fertilizer, and preparation method and application thereof Download PDFInfo
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- CN115819263A CN115819263A CN202211563825.5A CN202211563825A CN115819263A CN 115819263 A CN115819263 A CN 115819263A CN 202211563825 A CN202211563825 A CN 202211563825A CN 115819263 A CN115819263 A CN 115819263A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000003337 fertilizer Substances 0.000 title claims description 51
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 title description 9
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- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 120
- 239000011669 selenium Substances 0.000 claims abstract description 120
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- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 8
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
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- -1 selenium ions Chemical class 0.000 description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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Abstract
The invention provides a preparation method of an organic zinc chelate, which comprises the following steps: providing a glycine solution with the mass concentration of 5-10%; mixing glycine solution and zinc salt, and adjusting the pH value to 4-8; then heating at 60-100 ℃ for 30-150min to obtain a chelation reaction solution, wherein the molar ratio of glycine to zinc salt is 1-4; and (4) evaporating and concentrating the chelating reaction solution to obtain a concentrated solution of the organic zinc chelate. The invention also provides a preparation method of the organic selenium chelate, which comprises the following steps: providing a glycine solution with the mass concentration of 4-8%; mixing glycine solution and selenium salt, and adjusting pH to 6-8; then heating the mixture for 60-120min at 40-80 ℃ to obtain a chelation reaction solution, wherein the molar ratio of glycine to selenium salt is 2-4; and (3) evaporating and concentrating the chelation reaction solution to obtain a concentrated solution of the organic selenium chelate.
Description
Technical Field
The invention relates to the technical field of zinc-selenium-containing functional fertilizers, and in particular relates to an organic zinc-selenium chelate, a functional fertilizer, and preparation methods and applications thereof.
Background
Zinc (Zinc) and Selenium (Selenium) are necessary nutrient elements for the growth and development of a human body, zinc-rich and Selenium-rich agricultural products are produced by utilizing Zinc-rich and Selenium-rich soil, the method is an important way for utilizing Zinc and Selenium resources, a Zinc-Selenium-containing fertilizer is applied in the crop planting process, the content of Zinc and Selenium in edible parts can be improved through plant accumulation and transformation, and the method is the most economic, effective and safe method for supplementing Zinc and Selenium to the human body.
At present, most of trace element fertilizers applied in China are water-soluble inorganic salts, and because the absorption and utilization of trace elements by plants are greatly reduced due to the antagonistic action among elements, the trace elements are easily fixed in soil, are not easily dissolved in water and are easily decomposed, and are easily subjected to chemical reaction when being mixed with other solid or liquid fertilizers for application, the current trace element fertilizers cannot be well absorbed and utilized by the plants, so that the fertilizer efficiency of the fertilizers can be reduced.
In view of the above, there is a need to provide an organic zinc selenium chelate, a functional fertilizer, and a preparation method and an application thereof, so as to solve or at least alleviate the technical defect that the inorganic trace element fertilizer cannot be well absorbed and utilized by plants.
Disclosure of Invention
The invention mainly aims to provide an organic zinc-selenium chelate, a functional fertilizer, a preparation method and application thereof, and aims to solve the technical problem that the inorganic trace element fertilizer cannot be well absorbed and utilized by plants.
In order to achieve the above object, the present invention provides a method for preparing an organozinc chelate, comprising the steps of:
s1, providing a glycine solution, wherein the mass concentration of the glycine solution is 5-10%;
s2, mixing the glycine solution and a zinc salt to obtain a first mixed solution, and adjusting the pH value of the first mixed solution to 4-8; then heating the first mixed solution at 60-100 ℃ for 30-150min to obtain a chelation reaction solution;
in the first mixed solution, the molar ratio of the glycine to the zinc salt is 1-4;
and S3, carrying out evaporation concentration treatment on the chelation reaction liquid to obtain a concentrated solution of the organic zinc chelate.
Further, the method also comprises the following steps:
s4, adding absolute ethyl alcohol into the concentrated solution of the organic zinc chelate to obtain a second mixed solution; standing the second mixed solution at the temperature of 2-8 ℃ for 10-14h to obtain a first treatment solution;
s5, carrying out solid-liquid separation on the first treatment liquid to obtain a solid product; and then, carrying out vacuum freeze drying on the solid product to obtain powder of the organic zinc chelate.
The invention also provides an organic zinc chelate prepared by adopting the preparation method of the organic zinc chelate.
The invention also provides a preparation method of the organic selenium chelate, which comprises the following steps:
s10, providing a glycine solution, wherein the mass concentration of the glycine solution is 4-8%;
s20, mixing the glycine solution and selenium salt to obtain a third mixed solution, and adjusting the pH value of the third mixed solution to 6-8; then, heating the third mixed solution at 40-80 ℃ for 60-120min to obtain a chelation reaction solution;
in the third mixed solution, the molar ratio of the glycine to the selenium salt is 2-4:1
And S30, carrying out evaporation concentration treatment on the chelation reaction liquid to obtain a concentrated solution of the organic selenium chelate.
Further, the method also comprises the following steps:
s40, adding absolute ethyl alcohol into the concentrated solution of the organic selenium chelate to obtain a fourth mixed solution; standing the fourth mixed solution for 10-14h at the temperature of 2-8 ℃ to obtain a second treatment solution;
s50, carrying out solid-liquid separation on the second treatment solution to obtain a solid product; and then, carrying out vacuum freeze drying on the solid product to obtain powder of the organic selenium chelate.
The invention also provides an organic selenium chelate, which is prepared by adopting the preparation method of the organic selenium chelate.
The invention also provides a functional fertilizer, which comprises the organic zinc chelate and/or the organic selenium chelate.
The invention also provides application of the functional fertilizer in improving the zinc and/or selenium content of tea.
The invention also provides a method for improving the zinc and selenium content of tea, which comprises the following steps: diluting the concentrated solution of the organic zinc chelate and/or the concentrated solution of the organic selenium chelate, and applying the diluted concentrated solution of the organic zinc chelate and/or the diluted concentrated solution of the organic selenium chelate to the leaves of tea trees;
the preparation method of the organic zinc chelate comprises the following steps of preparing an organic zinc chelate by using a preparation method of the organic zinc chelate, and preparing an organic selenium chelate by using a preparation method of the organic selenium chelate;
and/or the presence of a gas in the gas,
adding water to the powder of the organic zinc chelate and/or the powder of the organic selenium chelate and applying the mixture to the root of the tea tree;
the organic zinc chelate powder is prepared by the preparation method of the organic zinc chelate, and the organic selenium chelate powder is prepared by the preparation method of the organic selenium chelate.
Furthermore, the dilution multiple of the concentrated solution is 500-1000 times.
Compared with the prior art, the invention has the following advantages:
according to the invention, glycine is used as a chelating agent, the chelating agent is prepared into a chelating solution after chelating sodium selenite and zinc sulfate heptahydrate by glycine under the conditions of specific pH and the like, the obtained chelating solution is concentrated to obtain a concentrated solution which can be used as a liquid fertilizer, and the concentrated solution can be directly sprayed on the surface of a plant after being diluted; and the concentrated solution is subjected to absolute ethyl alcohol treatment and freeze drying treatment to obtain solid powder of zinc glycine chelate and selenium glycine chelate, so that the solid powder can be applied to soil as a solid fertilizer.
After the two forms of fertilizers are applied to crops, the content of zinc and selenium in edible parts of the plants can be improved, the effectiveness of the zinc and selenium in soil can be enhanced, and the PH and organic matters of the soil can be improved; meanwhile, the glycine serving as a chelating agent has higher chelating capacity and better biodegradability and is a better substitute of EDTA (ethylene diamine tetraacetic acid), so that the chelating rate of zinc and selenium can be better chelated, the absorption of plants to the zinc and selenium is increased, and the effective utilization rate of the zinc and selenium is ensured.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is an infrared spectrum of zinc glycine chelate in example 3, selenium glycine chelate in example 6, and glycine.
The implementation, functional features and advantages of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Technical solutions between the embodiments of the present invention may be combined with each other, but it must be based on the realization of those skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The invention utilizes the glycine to chelate trace elements of zinc and selenium, and greatly improves the utilization rate of inorganic elements. It is understood that most of trace element fertilizers applied in China are water-soluble inorganic salts, and the absorption and utilization of trace elements by plants are greatly reduced due to the antagonistic action among elements. Compared with inorganic trace element fertilizers, the chelated trace element fertilizer is not easy to be fixed in soil, is easy to dissolve in water and not decomposed, can be well absorbed and utilized by plants, can be mixed with other solid or liquid fertilizers for application without chemical reaction, and does not reduce the fertilizer efficiency of any fertilizer.
At present, most of trace element chelated fertilizers take EDTA or EDDHA and the like as chelating agents, are limited by technical effects, and the cost of the produced trace element chelated fertilizer is higher due to the price of the raw materials of the EDTA.
The organic zinc-selenium functional fertilizer is mainly glycine chelate formed by chelating glycine and zinc-selenium serving as raw materials, and can provide technical support for zinc-rich and selenium-rich plants. In addition, the glycine can stimulate the growth of crops, enhance the stress resistance of the plants and effectively enhance the absorption of the crops to nitrogen elements.
Based on the method, the zinc and selenium content in the crops is effectively increased, the crop quality is improved, and a foundation is laid for obtaining high-efficiency and high-quality zinc-rich and selenium-rich crops.
The invention provides a preparation method of an organic zinc chelate (glycine chelated zinc), which comprises the following steps:
s1, providing a glycine solution, wherein the mass concentration of the glycine solution is 5-10%.
S2, mixing the glycine solution and a zinc salt to obtain a first mixed solution, and adjusting the pH value of the first mixed solution to 4-8; then heating the first mixed solution in a sealed way at the temperature of 60-100 ℃ for 30-150min to obtain a chelation reaction solution; the molar ratio of the glycine to the zinc salt is 1-4.
And S3, carrying out evaporation concentration treatment on the chelation reaction liquid to obtain a concentrated solution of the organic zinc chelate, wherein the concentrated solution of the organic zinc chelate can be used as a liquid zinc fertilizer.
In order to obtain the solid zinc fertilizer, the preparation method of the organic zinc chelate can further comprise the following steps:
s4, adding absolute ethyl alcohol (the addition amount of the absolute ethyl alcohol can be 9 times of that of the concentrated solution) into the concentrated solution of the organic zinc chelate to obtain a second mixed solution; and standing the second mixed solution for 10-14h at the temperature of 2-8 ℃ to obtain a first treatment solution.
S5, carrying out solid-liquid separation on the first treatment liquid to obtain a solid product; and then, freeze-drying the solid product to obtain the powder of the organic zinc chelate.
The preparation method of the organic zinc chelate can be summarized as follows:
adding glycine into a reaction kettle, adding water to dissolve the glycine to prepare a solution, adding weighed zinc sulfate heptahydrate, adjusting the pH value, heating, reacting at a constant temperature to obtain a chelating reaction solution, and concentrating the chelating reaction solution to 2/3 of the volume of the chelating reaction solution in a rotary evaporator to obtain a chelating concentrated solution, namely the glycine chelated zinc liquid fertilizer.
And (3) after the glycine chelated zinc concentrated solution is obtained, adding absolute ethyl alcohol for precipitation, performing centrifugal separation, and drying in a freeze dryer to obtain the glycine chelated zinc solid fertilizer.
The invention also provides an organic zinc chelate based on the preparation method of the organic zinc chelate, and the organic zinc chelate is prepared by adopting the preparation method of the organic zinc chelate according to any embodiment.
The invention also provides a preparation method of the organic selenium chelate (glycine chelated selenium), which comprises the following steps:
and S10, providing a glycine solution, wherein the mass concentration of the glycine solution is 4-8%.
S20, mixing the glycine solution and selenium salt to obtain a third mixed solution, and adjusting the pH value of the third mixed solution to 6-8; then, hermetically heating the third mixed solution at 40-80 ℃ for 60-120min to obtain a chelation reaction solution; the molar ratio of the glycine to the selenium salt is 2-4:1.
and S30, carrying out evaporation concentration treatment on the chelation reaction liquid to obtain a concentrated solution of the organic selenium chelate. The concentrated solution of the organic selenium chelate can be used as liquid selenium fertilizer.
In order to obtain the solid selenium fertilizer, the preparation method of the organic selenium chelate can further comprise the following steps:
s40, adding absolute ethyl alcohol (the addition amount of the absolute ethyl alcohol can be 9 times of that of the concentrated solution) into the concentrated solution of the organic selenium chelate to obtain a fourth mixed solution; and standing the fourth mixed solution for 10-14h at the temperature of 2-8 ℃ to obtain a second treatment solution.
S50, carrying out solid-liquid separation on the second treatment solution to obtain a solid product; and then, freeze-drying the solid product to obtain the powder of the organic selenium chelate.
The preparation method of the organic selenium chelate can be summarized as follows:
adding glycine into a reaction kettle, adding water to dissolve the glycine to prepare a solution, adding weighed sodium selenite, adjusting the pH value, heating, reacting at a constant temperature to obtain a chelation reaction solution, and concentrating the chelation solution to 2/3 of the original volume in a rotary evaporator to obtain chelation, thus obtaining the liquid fertilizer of glycine chelated selenium.
And (3) continuously adding absolute ethyl alcohol after obtaining the glycine selenium chelate concentrated solution, centrifugally separating, and drying in a freeze dryer to obtain the glycine selenium chelate solid fertilizer.
Based on the preparation method of the organic selenium chelate, the invention also provides the organic selenium chelate, which is prepared by adopting the preparation method of the organic selenium chelate according to any embodiment.
Based on the organic zinc chelate and the organic selenium chelate, the invention also provides a functional fertilizer which comprises or is the organic zinc chelate and/or the organic selenium chelate.
The organic zinc chelate and the organic selenium chelate have strong chelation on zinc and selenium and can be used as liquid fertilizer and solid fertilizer, and the invention also provides application of the functional fertilizer in improving the zinc and/or selenium content of tea.
Illustratively, the present invention provides a method for increasing the zinc and selenium content of tea, comprising: diluting the concentrated solution of the organic zinc chelate and/or the concentrated solution of the organic selenium chelate, and applying the diluted concentrated solution to the leaves of the tea trees; the dilution factor may be 500-1000 times.
The preparation method of the organic zinc chelate (concentrated solution) is adopted to prepare the concentrated solution of the organic zinc chelate, and the preparation method of the organic selenium chelate (concentrated solution) is adopted to prepare the concentrated solution of the organic zinc chelate.
And/or the presence of a gas in the gas,
and adding water to the powder of the organic zinc chelate and/or the powder of the organic selenium chelate, and applying the mixture to the root of the tea tree.
Wherein the powder of the organic zinc chelate is prepared by the method for preparing the organic zinc chelate (powder) as described in any one of the above, and the powder of the organic selenium chelate is prepared by the method for preparing the organic selenium chelate (powder) as described in any one of the above.
In a specific application process, only the organic zinc chelate can be applied, and only the organic selenium chelate can be applied; when both are to be applied, they may be applied at intervals (i.e. they are applied separately to the soil or foliage at different times) to avoid adverse effects of both in the soil or plant growth system; of course, when both are applied simultaneously, both can be applied together, and although both have partial inhibition effect in the whole system, the present invention still has a significance in comparison with the prior art.
It is noted that when the pH is adjusted<6, i.e. pH under acidic conditions, H + Will compete with metal ions for electron donating groups, which is not favorable for the generation of glycine chelate salt; when pH is changed>9, under the higher alkaline condition, hydroxyl and electron donating groups compete for metal ions to generate precipitates, and the product yield efficiency is reduced.
However, in the invention, when the pH is 4, the zinc glycinate chelate still has a large chelating rate, which shows that the selection of the pH in the invention does not depend on the mechanism completely, and an unexpected technical effect is achieved.
Furthermore, it was unexpected that the chelating rate of selenium glycine chelate could be increased by maintaining the pH at 6 to 8 when selenium glycine chelate (nonmetallic element) is prepared, whereas the chelating rate of selenium glycine chelate could be suppressed at pH 4.
It should also be noted that, during the product concentration process, anhydrous ethanol is added as a crystallization promoter, so that the yield can be improved. The vacuum freeze drying is to freeze water in the material into ice, and then the ice is sublimated at low temperature to be dried in a vacuum state, so that the drying effect is good, the appearance shape and the material structure can be effectively kept, the problem that the product is exposed in the air and has secondary reaction with oxygen can be prevented compared with the drying, the product and the water can be effectively prevented from forming crystal water, the content of the crystal water is reduced, the free water among crystals is easy to evaporate, the product drying is facilitated, the obtained product is loose and is not easy to agglomerate, the dispersibility is good, the product quality is high, and the product is easy to store.
To facilitate understanding by those skilled in the art, the following is illustrated:
in the following examples and comparative examples, the chelate ratios of zinc and selenium were measured by ICP-OES (inductively coupled plasma emission spectrometer).
Chelate rate (%) = content of chelated trace elements/total amount of trace elements × 100%
1. Preparation of glycine chelated zinc (organic zinc chelate)
Example 1
50g of glycine was dissolved in a reaction vessel containing 1L of water to prepare a 5% glycine solution.
Mixing zinc sulfate heptahydrate into a reaction kettle, and controlling the molar ratio of glycine to zinc sulfate heptahydrate to be 4:1, obtaining a mixed solution, and adjusting the pH =6 of the mixed solution; sealing and heating the reaction kettle to 80 ℃, and reacting at constant temperature for 120min to obtain a chelation reaction solution; and (3) concentrating the chelating solution to 2/3 of the original volume in a rotary evaporator to obtain a concentrated solution of the glycine chelated zinc (glycine chelated zinc liquid fertilizer).
Adding 9 times volume of absolute ethyl alcohol into the obtained zinc glycinate concentrated solution, standing for 12 hours in an environment at 4 ℃, centrifugally separating the obtained precipitate, and drying for 36 hours at-60 ℃ in a vacuum freeze dryer to obtain zinc glycinate powder (zinc glycinate solid fertilizer).
Example 2
In this example, the amount of glycine added was 50g, the concentration of glycine solution was 5%, the pH of the mixed solution was 8, and the molar ratio of glycine to zinc sulfate heptahydrate was 1:1, the heating temperature in the reaction kettle is 100 ℃, the constant temperature reaction time is 150min, and other conditions are consistent with those of the example 1.
Example 3
In this example, the amount of glycine added was 100g, the concentration of the glycine solution was 10%, the pH of the mixed solution was 6, and the molar ratio of glycine to zinc sulfate heptahydrate was 4:1, the heating temperature in the reaction kettle is 100 ℃, the constant temperature reaction time is 30min, and other conditions are consistent with those of the embodiment 1.
Example 4
In this example, the amount of glycine added was 100g, the concentration of the glycine solution was 10%, the pH of the mixed solution was 6, and the molar ratio of glycine to zinc sulfate heptahydrate was 2:1, the heating temperature in the reaction kettle is 80 ℃, the constant temperature reaction time is 150min, and other conditions are consistent with those of the embodiment 1.
Example 5
In this example, the amount of glycine added was 100g, the concentration of the glycine solution was 10%, the pH of the mixed solution was 4, and the molar ratio of glycine to zinc sulfate heptahydrate was 2:1, the heating temperature in the reaction kettle is 80 ℃, the constant temperature reaction time is 150min, and other conditions are consistent with those of the embodiment 1.
Analytical example 1
The chelating ratio of the zinc glycine chelate powder in examples 1 to 7 is shown in the following table:
| group of | Chelating ratio/% |
| Example 1 | 84.21 |
| Example 2 | 80.20 |
| Example 3 | 94.70 |
| Example 4 | 82.89 |
| Example 5 | 92.30 |
2. Preparation of glycine chelated selenium (organic selenium chelate)
Example 6
40g of glycine was dissolved in a reaction vessel containing 1L of water to prepare a 4% glycine solution.
Mixing sodium selenite into the reaction kettle, and controlling the molar ratio of glycine to sodium selenite to be 2:1, obtaining a mixed solution, and adjusting the pH of the mixed solution to be =6; heating the reaction kettle to 40 ℃ in a closed manner, and reacting for 60min at constant temperature to obtain a chelation reaction liquid; and (3) concentrating the chelating solution to 2/3 of the original volume in a rotary evaporator to obtain a concentrated solution of glycine chelated selenium (glycine chelated selenium liquid fertilizer).
Adding 9 times volume of absolute ethyl alcohol into the obtained concentrated solution of the glycine chelated selenium, standing the obtained precipitate in an environment at 4 ℃ for 12 hours, centrifugally separating the obtained precipitate, and drying the precipitate in a vacuum freeze dryer at-60 ℃ for 36 hours to obtain powder of the glycine chelated selenium (the glycine chelated selenium solid fertilizer).
Example 7
In this example, the addition amount of glycine is 40g, the concentration of the glycine solution is 4%, the pH of the mixed solution is 8, and the molar ratio of glycine to sodium selenite is 4:1, the heating temperature in the reaction kettle is 60 ℃, the constant temperature reaction is carried out for 80min, and other conditions are kept consistent with those in the example 6.
Example 8
In this example, the addition amount of glycine is 80g, the concentration of the glycine solution is 8%, the pH of the mixed solution is 8, and the molar ratio of glycine to sodium selenite is 4:1, the heating temperature in the reaction kettle is 80 ℃, the reaction is carried out for 80min at constant temperature, and other conditions are kept consistent with those in the example 6.
Comparative example 1
In the comparative example, the amount of glycine added was 80g, the concentration of glycine solution was 8%, the pH of the mixed solution was 4, and the molar ratio of glycine to sodium selenite was 4:1, the heating temperature in the reaction kettle is 80 ℃, the reaction is carried out for 80min at constant temperature, and other conditions are kept consistent with those in the example 6.
Analytical example 2
The chelating ratio of the glycine chelated selenium powder in examples 5-8 is shown in the following table:
| group of | Chelating ratio/% |
| Example 6 | 50.94 |
| Example 7 | 48.32 |
| Example 8 | 45.79 |
| Comparative example 1 | 38.32 |
3. Structural analysis of glycine chelated zinc and glycine chelated selenium
Example 9
The glycine chelated zinc powder in the embodiment 3 and the glycine chelated selenium powder in the embodiment 6 are subjected to substance structure analysis, specifically, a KBr tabletting method is adopted for tabletting, and the measurement is carried out for 400-4000 cm -1 Infrared spectrum of (1). The infrared spectrum structural analysis of the glycine chelated zinc and the glycine chelated selenium is shown in figure 1, wherein the glycine chelated zinc, the glycine chelated selenium and the glycine are sequentially arranged from top to bottom in the figure.
As shown in FIG. 1, after the ligand forms a chelate with zinc and selenium ions, some main absorption peaks of the chelate are obviously shifted and the relative strength is changed compared with the chelate ligand, thereby confirming that the zinc ions and the selenium ions are coordinated with glycine.
The peak of hydroxyl group association is reduced because it is greatly influenced by other groups after the coordination reaction, and is 3100cm -1 The left and right peaks are red shifted; 1408cm -1 The absorption peak of (a) is ascribed to the-CH-group. Glycine is 2000cm -1 Left and right-NH 3 + The characteristic peak disappears completely in the infrared spectrum of the chelate. 3326cm -1 And 3262cm -1 The absorption peak of the stretching vibration characteristic of the N-H bond appears. At 1599cm -1 And 1392cm -1 The absorption peaks appeared are respectively the stretching vibration of COO-, and are respectively shifted to a lower wave number and a higher wave number than the ligandKinetic indicates that COO-participates in coordination with monodentate coordination, and a chelate ring exists in the molecule. At 543cm -1 And 456cm -1 There are stretching vibration peaks of R-N, respectively, which further illustrate the formation of chelates. 3400cm -1 A broad absorption peak appears nearby, indicating the presence of water molecules in the chelate. Since only one oxygen atom of the carboxylate ion is involved in the coordination, the water molecule is likely to form a hydrogen bond between the two chelate molecules. The change of characteristic absorption peak shows that the chelate formed by the reaction of glycine with zinc and selenium ions is a new compound different from parent molecule, and the carbonyl and imino in peptide bond, and the carboxyl in side chain or terminal group are the main reaction sites participating in the chelation of zinc and selenium ions in glycine molecule. The formation of new species was confirmed by infrared spectroscopy.
4. Application of glycine chelated zinc and glycine chelated selenium in improvement of zinc and selenium content in tea
Example 10
1. Test materials:
the variety of the tested tea tree is 'Fuding Dabai', and the age of the tea tree is annual.
The experiment was performed in a pot culture using a zinc source from example 3 and a selenium source from example 6.
The concentrations of zinc and selenium in the embodiment are obtained by multiplying the addition of zinc or selenium in the corresponding embodiment by the chelation rate of the zinc or selenium in the corresponding embodiment and then converting the obtained product; namely: the concentrations of zinc and selenium in this example are post-chelated zinc and selenium concentrations.
Test site:
the tea institute of Guizhou university artificial climate room. The conditions are set to be under the environment of temperature (22 +/-2) DEG C, illumination time length of 12h/d, illumination intensity of 8000lx and humidity of 65%.
2. And (3) experimental design:
a total of 8 treatments were tested, divided into two forms, soil fertilization and foliar fertilization.
The soil fertilization group is used after a powdery product (solid fertilizer) is added with water, and comprises the following concrete steps:
CK (T1): no fertilizer was applied and only an equal amount of water was applied.
Zinc (T2) applied alone: the zinc concentration was 2g/L and the application was 500ml per pot for a total of 3 tea plants per pot, about 15Kg of soil per pot.
Selenium (T3) administered alone: selenium concentration is 200mg/L, application amount is 500 ml/pot, each pot has 3 tea trees, and each pot has 15Kg of soil.
Zinc and selenium co-administration (T4): the zinc concentration is 2g/L, the selenium concentration is 200mg/L, the zinc and the selenium are prepared in the same water body together, the application amount is 500 ml/pot, 3 tea trees are applied in each pot, and each pot is about 15Kg of soil.
When the soil is fertilized, the chelated solution is uniformly dripped at a position 15cm away from the rhizome and 10cm deep. Potted tea plants were randomly arranged. Picking 1 time (sampling tea) in 1 month for 3 times.
The foliar fertilization group is used after diluting a concentrated solution (liquid fertilizer) and comprises the following specific steps:
CK (T5): no fertilizer was applied and only an equal amount of water was applied.
Zinc (T6) applied alone: the zinc concentration is 500mg/L, the application amount is 200 ml/pot, and 3 tea trees are applied in each pot.
Selenium (T7) administered alone: the selenium concentration is 60mg/L, the application amount is 200 ml/pot, and each pot has 3 tea trees.
Zinc and selenium mixed administration (T8): the zinc concentration is 500mg/L, the selenium concentration is 60mg/L, the zinc and the selenium are prepared in the same water body together, the application amount is 200 ml/pot, and 3 tea trees are applied in each pot.
When the foliage is sprayed, the soil in the basin is covered by a preservative film to prevent the solution from entering the soil, and when the foliage is sprayed, the solution firstly flows from top to bottom, and then flows to the front of the foliage until water drops on the foliage drip. After 10 days, the tea leaves are sampled, and the tea leaves are picked once every 10 days for 3 times.
3. After sampling, washing off dust on leaf surfaces and residual zinc and selenium by using pure water, putting the leaf surfaces and the residual zinc and selenium into a refrigerator at the temperature of minus 40 ℃ for refrigeration, and waiting for detection.
Tea detection results:
zinc content (mg/Kg) of soil fertilizer application -1 ) The data are as follows:
| T1 | T2 | T3 | T4 | |
| 30 days | 19.85 | 31.85 | 5.94 | 13.34 |
| 60 days | 22.68 | 77.74 | 18.70 | 28.30 |
| 90 days | 24.26 | 53.57 | 20.39 | 41.41 |
Selenium content (mg/Kg) for soil fertilization 1 ) The data are as follows:
| T1 | T2 | T3 | T4 | |
| 30 days | 0.142 | 0.098 | 1.52 | 0.39 |
| 60 days | 0.192 | 0.136 | 2.16 | 1.39 |
| 90 days | 0.200 | 0.030 | 2.29 | 1.10 |
Zinc content (mg/Kg) of foliar fertilizer 1 ) The data are as follows:
| T5 | T6 | T7 | T8 | |
| 10 days | 10.33 | 62.18 | 32.24 | 46.63 |
| 20 days | 13.18 | 42.25 | 23.96 | 58.50 |
| 30 days | 19.89 | 47.26 | 25.31 | 32.64 |
Selenium content (mg/Kg) for foliar fertilization 1 ) The data are as follows:
| T5 | T6 | T7 | T8 | |
| 10 days | 0.15 | 0.25 | 5.35 | 3.28 |
| 20 days | 0.19 | 0.47 | 6.18 | 5.85 |
| 30 days | 0.28 | 0.34 | 4.77 | 4.23 |
The test results show that the zinc and selenium content in the tea can be obviously improved, and the germination and growth of tea tree buds are promoted.
The absorption efficiency of applying glycine chelated zinc and glycine chelated selenium in the soil is high, the selenium content reaches a selenium-rich state only in 30 days, the zinc content reaches zinc-rich state in 60 days due to comprehensive influence of soil factors, and the zinc content still keeps a stable state in 90 days.
Zinc glycine chelate and selenium glycine chelate are applied to leaf surfaces, and the zinc-rich state and the selenium-rich state are always maintained in 10 to 30 days, so that the foundation is laid for zinc-rich and selenium-rich agricultural products.
From the test results, the zinc and selenium compound application has certain promotion effect on the absorption of zinc and selenium of tea trees, the mixed application of the zinc and selenium compound application in leaf surfaces and soil reaches the NY/T600-2002 standard of selenium-rich tea (0.25 mg/kg-4.0 mg/kg), and the long picking time is beneficial to the improvement of yield and economic benefit. Meanwhile, the invention has the advantages of no toxicity, no pollution, safety, environmental protection, low cost and wide application prospect.
In the above technical solutions of the present invention, the above are only preferred embodiments of the present invention, and the technical scope of the present invention is not limited thereby, and all the technical concepts of the present invention, equivalent structural changes made by using the contents of the description and the drawings of the present invention, or direct/indirect applications in other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A preparation method of an organic zinc chelate is characterized by comprising the following steps:
s1, providing a glycine solution, wherein the mass concentration of the glycine solution is 5-10%;
s2, mixing the glycine solution and a zinc salt to obtain a first mixed solution, and adjusting the pH value of the first mixed solution to 4-8; then heating the first mixed solution at 60-100 ℃ for 30-150min to obtain a chelation reaction solution;
in the first mixed solution, the molar ratio of the glycine to the zinc salt is 1-4;
and S3, carrying out evaporation concentration treatment on the chelation reaction liquid to obtain a concentrated solution of the organic zinc chelate.
2. The method of claim 1, further comprising the steps of:
s4, adding absolute ethyl alcohol into the concentrated solution of the organic zinc chelate to obtain a second mixed solution; standing the second mixed solution at the temperature of 2-8 ℃ for 10-14h to obtain a first treatment solution;
s5, carrying out solid-liquid separation on the first treatment liquid to obtain a solid product; and then, carrying out vacuum freeze drying on the solid product to obtain powder of the organic zinc chelate.
3. An organozinc chelate compound characterized by being produced by the production method according to claim 1 or 2.
4. A preparation method of organic selenium chelate is characterized by comprising the following steps:
s10, providing a glycine solution, wherein the mass concentration of the glycine solution is 4-8%;
s20, mixing the glycine solution and selenium salt to obtain a third mixed solution, and adjusting the pH value of the third mixed solution to 6-8; then, heating the third mixed solution at 40-80 ℃ for 60-120min to obtain a chelation reaction solution;
in the third mixed solution, the molar ratio of the glycine to the selenium salt is 2-4:1
And S30, carrying out evaporation concentration treatment on the chelation reaction liquid to obtain a concentrated solution of the organic selenium chelate.
5. The method of claim 4, further comprising the steps of:
s40, adding absolute ethyl alcohol into the concentrated solution of the organic selenium chelate to obtain a fourth mixed solution; standing the fourth mixed solution for 10-14h at the temperature of 2-8 ℃ to obtain a second treatment solution;
s50, carrying out solid-liquid separation on the second treatment solution to obtain a solid product; and then, carrying out vacuum freeze drying on the solid product to obtain powder of the organic selenium chelate.
6. An organic selenium chelate compound characterized by being produced by the production method as claimed in claim 4 or 5.
7. A functional fertilizer comprising the organozinc chelate compound of claim 3 and/or the organoselenium chelate compound of claim 6.
8. Use of a functional fertilizer as claimed in claim 7 for increasing the zinc and/or selenium content of tea.
9. A method for improving the zinc and selenium content of tea is characterized by comprising the following steps: diluting the concentrated solution of the organic zinc chelate and/or the concentrated solution of the organic selenium chelate, and applying the diluted concentrated solution to the leaves of the tea trees;
wherein the concentrated solution of the organic zinc chelate is prepared by the preparation method of claim 1, and the concentrated solution of the organic selenium chelate is prepared by the preparation method of claim 4;
and/or the presence of a gas in the gas,
adding water to the powder of the organic zinc chelate and/or the powder of the organic selenium chelate and applying the mixture to the root of the tea tree;
wherein the powder of the organozinc chelate complex is prepared by the preparation method as set forth in claim 2, and the powder of the organoselenium chelate complex is prepared by the preparation method as set forth in claim 5.
10. The method for increasing the zinc and selenium content in tea leaves as claimed in claim 9, wherein the dilution factor of the concentrated solution is 500-1000 times.
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