Organic complex and method for preparing the same, water-soluble fertilizer
By utilizing organic complex technology, which involves the formation of covalent bonds between yeast metabolites and magnesium ions, the problems of high leaching rates and environmental pollution associated with traditional magnesium fertilizers have been solved, achieving efficient utilization of magnesium fertilizers and promoting crop growth.
Patent Information
- Application Number
- CN202610448524.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-04-07
- Publication Date
- 2026-07-10
AI Technical Summary
Traditional water-soluble magnesium fertilizers are easily leached, resulting in low magnesium fertilizer utilization. Furthermore, existing magnesium fertilizer preparation processes pose risks of high energy consumption and environmental pollution, making it difficult to effectively release magnesium nutrients in different soil types.
Organic complexes are used to form covalent bonds between organic compounds in yeast metabolites and magnesium ions, making them less susceptible to leaching. These complexes are combined with the granular structure of yeast metabolites to improve the absorption and utilization efficiency of magnesium, and aerobic fermentation is used to reduce production costs.
It improves the efficiency of plant absorption and utilization of magnesium, reduces the leaching rate of magnesium fertilizer, reduces dependence on soil, and the organic complex is degradable, reducing the risk of environmental pollution and promoting crop growth and yield.
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Figure CN122355762A_ABST
Abstract
Description
Technical Field
[0001] This application relates to the field of fertilizer technology, specifically to an organic complex and its preparation method, and a water-soluble fertilizer. Background Technology
[0002] Magnesium plays an indispensable role as an essential nutrient element in crop growth. As the central atom of chlorophyll molecules, it is the central coordinating ion of the carboline rings of chlorophyll a and chlorophyll b, directly participating in the capture and conversion of light energy in photosynthesis. Magnesium deficiency leads to chloroplast structural damage, reduced grana, and thylakoid membrane damage, resulting in interveinal yellowing of older leaves, decreased photosynthetic efficiency, inhibited carbohydrate synthesis, and impaired protein synthesis. Consequently, it reduces crop grain yield, affects fruit expansion in fruits and vegetables, and significantly reduces fruit sugar content, coloring, and maturity. In addition, magnesium is an activator of more than 300 enzymes, regulating glycolysis, the tricarboxylic acid cycle, ATPase activity, DNA polymerase function, and fatty acid synthesis. It also stabilizes cell wall pectin structure, enhancing plant resistance to stress.
[0003] However, magnesium is easily leached from soil, mainly because it exists as a divalent cation (Mg). 2+ Its large hydration radius and low charge density result in low electrostatic adsorption capacity of soil colloids. Therefore, it is easily lost through water leaching in the soil.
[0004] Traditional water-soluble magnesium fertilizers are typically applied in the form of inorganic salts such as magnesium sulfate. Due to the large hydrated ionic radius of magnesium ions, their low adhesion to soil, and high mobility within the soil, they are easily leached. This results in a high leaching rate and low plant uptake, leading to waste. While some research has explored ways to improve magnesium fertilizer utilization efficiency, such as the patent (CN111099934A) which describes how mixing magnesium with dolomite powder effectively reduces magnesium leaching or runoff loss, these fertilizers are poorly water-soluble and require specific soil conditions, only suitable for acidic soils where magnesium can be released. There is also a patent with publication number CN114163279A that uses magnesite as raw material to prepare magnesium fertilizer. Although it reduces energy consumption through short-process technology and hydration exothermic reaction, reduces production costs by replacing chemical raw materials with natural minerals, simplifying the process and recycling raw materials, and achieves slow release of magnesium ions and easy absorption by crops by using composite magnesium salt components and water-dispersible granule formulations, there are still high-energy-consuming links in magnesite calcination and ultrafine grinding. In addition, the use of mixed acid, the nitrate ions contained in magnesium nitrate and the mining and calcination of magnesite still pose potential environmental risks of local pollution, eutrophication of water bodies and ecological damage. Summary of the Invention
[0005] Based on this, this application provides an organic complex that can reduce magnesium fertilizer leaching and is easily degradable, as well as its preparation method and a water-soluble fertilizer.
[0006] This application provides an organic complex comprising a central metal ion and an organic ligand, wherein the organic ligand comprises yeast metabolites; the yeast metabolites comprise one or more of fulvic acid, humic acid, succinic acid, acetic acid, free amino acids, hydrolyzed amino acids, and proteins; and the central metal ion comprises magnesium ions.
[0007] This application also provides a method for preparing the organic complex as described above, comprising the following steps:
[0008] The raw materials for the organic complex are mixed and heated to 60°C~95°C to carry out a complexation reaction to prepare the organic complex.
[0009] The raw materials include yeast metabolites and magnesium salts; the yeast metabolites include one or more of fulvic acid, humic acid, succinic acid, acetic acid, free amino acids, hydrolyzed amino acids, and proteins. All of the above organic compounds are biodegradable in soil.
[0010] In one embodiment, the yeast metabolite comprises fulvic acid, humic acid, succinic acid, acetic acid, free amino acids, hydrolyzed amino acids, and proteins in a mass ratio of (35~45): (1~5): (0.5~2): (0.5~2): (1~5): (5~15): (15~25).
[0011] In one embodiment, the magnesium salt includes one or more of magnesium sulfate, magnesium nitrate, and magnesium chloride.
[0012] In one embodiment, the yeast metabolite includes the filtrate from one or more fermentation raw materials selected from molasses, hydrolyzed sugar, beet, barley, and corn after aerobic fermentation.
[0013] In one embodiment, the temperature for aerobic fermentation is 25°C to 30°C.
[0014] In one embodiment, the pH value of aerobic fermentation is 5.0 to 6.5.
[0015] In one embodiment, the raw materials include the yeast metabolites and the magnesium salt in a mass ratio of (35~50):(50~65).
[0016] In one embodiment, the coordination reaction takes 1.5 to 2.5 hours.
[0017] Furthermore, this application also provides a water-soluble fertilizer, including the organic complex as described above or the organic complex prepared by the preparation method described above.
[0018] The organic complex provided in this application utilizes organic compounds from yeast metabolites as ligands. Through a coordination reaction, magnesium ions are used as the central ion. The magnesium ions provide empty orbitals to form shared electron pairs, i.e., covalent bonds, with electron pairs provided by organic compounds in yeast metabolites such as fulvic acid and amino acid derivatives. This forms new amide bonds or O and N of the amino group and Mg. 2+ The organic complexes formed by coordination are less susceptible to leaching than free magnesium ions, thus improving the efficiency of magnesium absorption and utilization by plants. They are not limited by soil pH and both the organic complexes and their residues can be degraded in the environment. Attached Figure Description
[0019] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.
[0020] Figure 1 The images show the full UV spectrum (200-1000 nm) of the organic complex, yeast metabolite, and magnesium sulfate obtained in Example 1 of this application.
[0021] Figure 2 The images show the local ultraviolet (300-400 nm) spectra of the organic complex, yeast metabolite, and magnesium sulfate obtained in Example 1 of this application.
[0022] Figure 3 The images show the infrared spectra of the organic complex, yeast metabolite, and magnesium sulfate obtained in Example 1 of this application.
[0023] Figure 4 The images show partial infrared spectra of the organic complex, yeast metabolite, and magnesium sulfate obtained in Example 1 of this application.
[0024] Figure 5 The X-ray photoelectron spectroscopy spectra of the organic complex, yeast metabolite, and magnesium sulfate prepared in Example 1 of this application are shown.
[0025] Figure 6 The images show actual plant specimens from control group 1, control group 2, and experimental group 1, respectively.
[0026] Figure 7 Bar charts showing leaf area for control group 1, control group 2, and experimental group 1, respectively.
[0027] Figure 8 The images show actual plant rhizomes from control group 1, control group 2, and experimental group 1, respectively.
[0028] Figure 9 Bar charts showing stem diameter and fresh stem weight of plant rhizomes using control group 1, control group 2, and experimental group 1 respectively.
[0029] Figure 10 Bar charts showing the fresh weight of the aboveground parts of plants using control group 1, control group 2, and experimental group 1, respectively.
[0030] Figure 11 Bar charts showing the content of soluble sugars and soluble proteins in plants using control group 1, control group 2, and experimental group 1, respectively.
[0031] Figure 12 Bar chart showing vegetable yields using water-soluble inorganic magnesium fertilizer and magnesium fertilizer containing the organic compound of this application, respectively.
[0032] Figure 13 The bar chart shows the magnesium accumulation of the magnesium fertilizer using water-soluble inorganic magnesium fertilizer and the magnesium fertilizer containing the organic complex of this application, respectively. Detailed Implementation
[0033] To facilitate understanding of this application, a more complete description will be provided below with reference to the accompanying drawings. Preferred embodiments of this application are shown in the drawings. However, this application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of this application.
[0034] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
[0035] As used herein, the term "and / or" encompasses any one of two or more of the related listed items, as well as any and all combinations of the related listed items. These arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. For example, "A and / or B" includes three parallel options: A, B, and "a combination of A and B".
[0036] In this document, unless otherwise stated, "one or more" means any one of the listed items or any combination of the listed items. Similarly, "one or more" and other instances of "one or more" are to be understood in the same way unless otherwise stated.
[0037] In this document, terms such as "further," "even further," "especially," "for example," "like," "example," and "exemplary" are used for descriptive purposes to indicate a connection in the coverage of different technical solutions presented earlier and later. However, they should not be construed as limitations on the preceding technical solution or on the scope of protection of this document. Unless otherwise specified, in this document, A (e.g., B) indicates that B is a non-limiting example of A, and it can be understood that A is not limited to B.
[0038] In this document, "optionally," "optionally," and "optional" mean that something is optional, that is, it is selected from either "present" or "absent." If multiple "options" appear in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "option" is independent. In this application, descriptions such as "optionally contains" and "optionally includes" indicate "contains or does not contain." "Optional component X" indicates whether component X exists or does not exist, or whether component X is contained or not.
[0039] In this document, the terms "first aspect," "second aspect," "third aspect," and "fourth aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," "third," and "fourth" serve only as a non-exhaustive enumeration and should be understood as not constituting a closed limitation on quantity.
[0040] In this article, the technical features described in an open-ended manner include both closed technical solutions composed of the listed features and open technical solutions that include the listed features.
[0041] In this document, when referring to numerical intervals (i.e., numerical ranges), unless otherwise specified, the distribution of selectable values within a numerical interval is considered continuous, and includes the two endpoints (i.e., the minimum and maximum values) of the numerical interval, as well as every value between these two endpoints. Unless otherwise specified, when a numerical interval refers only to integers within that interval, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints, which is equivalent to directly listing every integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be merged. In other words, unless otherwise specified, the numerical ranges disclosed herein should be understood to include any and all subranges included therein. The "numerical value" in this numerical interval can be any quantitative value, such as a number, percentage, ratio, etc. The term "numerical interval" can be broadly included to include percentage intervals, ratio intervals, proportion intervals, and other numerical interval types.
[0042] Soluble sugars refer to a class of low-molecular-weight carbohydrates in plants that can dissolve in water and the cytoplasm. They mainly include monosaccharides (such as glucose and fructose) and disaccharides (such as sucrose and trehalose). They are not only direct substrates for energy metabolism and carbon skeleton supply, but also play crucial roles in osmotic regulation, signal transduction, and stress response. Their content and dynamic changes are important indicators for measuring plant carbon assimilation, transport and distribution, and physiological state. Soluble proteins refer to a class of proteins that can dissolve in the cytoplasm and aqueous environments such as vacuoles under specific mild, non-denaturing extraction conditions (usually neutral or near-neutral buffer solutions). They mainly include enzymes involved in metabolism, signal transduction components, molecular chaperones, stress-resistant proteins, and some structural proteins. Their content and composition are key physiological indicators for measuring cellular metabolic activity, growth and development status, and stress response capacity, and are often used to assess plant nitrogen nutrition levels and overall physiological health.
[0043] In this document, the terms "room temperature" or "normal temperature" generally refer to 4°C to 35°C, for example, 20°C ± 5°C. In some embodiments of this document, "room temperature" or "normal temperature" refers to 10°C to 30°C. In some embodiments of this document, "room temperature" or "normal temperature" refers to 20°C to 30°C.
[0044] In this document, for methods involving multiple steps, unless otherwise explicitly stated herein, there is no strict order constraint on the execution of these steps; they may be executed in any order other than those described. Moreover, any step may include multiple sub-steps or multiple stages, which are not necessarily completed at the same time, but may be executed at different times, and their execution order is not necessarily sequential, but may be executed in turn, alternately, or simultaneously with other steps or parts of the sub-steps or stages of other steps.
[0045] This application provides an organic complex comprising a central metal ion and an organic ligand, wherein the organic ligand comprises yeast metabolites; the yeast metabolites comprise one or more of fulvic acid, humic acid, succinic acid, acetic acid, free amino acids, hydrolyzed amino acids, and proteins; and the central metal ion comprises magnesium ions.
[0046] Understandably, the central metal ion and organic ligand in the organic complex formed above can, but are not limited to, combine according to the following structural formula.
[0047]
[0048] .
[0049] The organic complex provided in this application utilizes organic compounds from yeast metabolites as ligands. Through a coordination reaction, magnesium ions are used as the central ion. The magnesium ions provide empty orbitals to form shared electron pairs, i.e., coordinate bonds, with electron pairs provided by organic compounds in yeast metabolites such as fulvic acid and amino acid derivatives. This forms new amide bonds or O and N of the amino group and Mg. 2+ Coordination forms organic complexes, which are less susceptible to leaching than free magnesium ions, thus improving the efficiency of magnesium absorption and utilization by plants.
[0050] In a specific example, yeast metabolites include fulvic acid, humic acid, yeast polysaccharides, amino acids, peptides, organic acids, phenols and pyrazines, and some metabolic intermediates (such as enzymes and coenzymes). Understandably, yeast metabolites are byproducts of aerobic fermentation of raw materials such as molasses (a byproduct of the sugar industry), followed by yeast extraction. These yeast metabolites are rich in small-molecule organic acids such as fulvic acid and amino acid derivatives. These organic substances can bind with soil particles to form aggregates, reduce nutrient leaching, stimulate root growth, increase root hair density, and promote healthy and rapid plant growth.
[0051] In a specific example, magnesium salts include one or more of magnesium sulfate, magnesium nitrate, and magnesium chloride. Magnesium sulfate is preferred, used to replenish magnesium and sulfur in the soil. Magnesium is a core component of chlorophyll and directly participates in photosynthesis. Magnesium sulfate is highly water-soluble, allowing for rapid replenishment of magnesium and improved chlorophyll synthesis. Sulfur is a constituent element of amino acids and proteins and participates in the construction of plant enzyme systems. Therefore, magnesium sulfate, as a magnesium fertilizer, is used to address crop growth retardation caused by magnesium and sulfur deficiencies, and can enhance crop resistance to stress and disease, thereby increasing crop yield and quality.
[0052] This application also provides a method for preparing an organic complex, comprising the following steps:
[0053] The raw materials for the mixed organic complex are heated to 60℃~95℃ to carry out a complexation reaction to prepare the organic complex.
[0054] The raw materials include yeast metabolites and magnesium salts; the yeast metabolites include fulvic acid, humic acid, succinic acid, acetic acid, free amino acids, hydrolyzed amino acids, and proteins.
[0055] In one specific example, yeast metabolites include fulvic acid, humic acid, succinic acid, acetic acid, free amino acids, hydrolyzed amino acids, and proteins in a mass ratio of (35~45): (1~5): (0.5~2): (0.5~2): (1~5): (5~15): (15~25).
[0056] In one specific example, yeast metabolites include the filtrate from one or more fermentation feedstocks selected from molasses, hydrolyzed sugar, beets, barley, and corn after aerobic fermentation.
[0057] In a specific example, the preparation method of yeast metabolites includes the following steps: using molasses, hydrolyzed sugar, barley, and corn as main raw materials, yeast strains are cultured for fermentation through aerobic fermentation; fermentation conditions are controlled at a temperature of 25℃~30℃ (the optimal growth temperature for yeast); the pH value is adjusted and maintained between 5.0 and 6.5; and sufficient oxygen is ensured to promote yeast metabolism. Yeast separation: After fermentation, the yeast cells are separated from the fermentation broth by centrifugation or filtration, retaining the liquid portion containing metabolites (i.e., low-concentration yeast metabolites). The low-concentration yeast metabolites are concentrated through multi-effect evaporation to form a yeast metabolite concentrate with a dry matter content of approximately 40%~60%, which is the yeast metabolite. This application fully utilizes yeast metabolites as one of the raw materials for organic complexes. No additional processing is required; only concentration and mixing with magnesium salts are needed to obtain the organic complexes of this application, significantly reducing processing costs.
[0058] Specifically, the temperature for aerobic fermentation can be, but is not limited to, 25℃, 26℃, 27℃, 28℃, 29℃, or 30℃. The pH value for aerobic fermentation can be, but is not limited to, 5, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6, 6.1, 6.2, 6.3, 6.4, or 6.5.
[0059] In a specific example, the raw materials include yeast metabolites and magnesium salts in a mass ratio of (35~50):(50~65). The raw materials also include a solvent, with the mass ratio of yeast metabolites, magnesium salts, and inorganic solvent being (35~50):(50~65):(25~55). Furthermore, the inorganic solvent can be, but is not limited to, water. By utilizing the relationship between the solubility saturation of magnesium salts, such as magnesium sulfate, in water and the dissolution temperature, the magnesium salts are fully dissolved and react with the yeast metabolites to form organic complexes, thus maximizing the degree of complexation between organic matter and magnesium.
[0060] In a specific example, the coordination reaction time is 1.5 hours to 2.5 hours. The coordination reaction time can be, but is not limited to, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours, 2 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, or 2.5 hours.
[0061] In a specific example, the temperature of the complexation reaction is 60℃~85℃. Specifically, the temperature of the complexation reaction can be, but is not limited to, 60℃, 65℃, 70℃, 75℃, 80℃, or 85℃. Using the heat released during the dissolution of anhydrous magnesium sulfate to control the temperature of the complexation reaction allows the process to be completed with almost no external heat input, thereby achieving the goal of energy saving, consumption reduction, and cost reduction in the production process of magnesium fertilizer containing organic complexes.
[0062] Furthermore, this application also provides a water-soluble fertilizer, including the organic complex as described above or the organic complex prepared by the preparation method described above.
[0063] Furthermore, this application provides the application of the above-mentioned organic complex or the organic complex prepared by the above-mentioned method or the water-soluble fertilizer as described above in plant growth.
[0064] The following detailed embodiments illustrate this application in more detail. It should also be understood that the following embodiments are only for further explanation of this application and should not be construed as limiting the scope of protection of this application. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of this application fall within the scope of protection of this application. The specific process parameters, etc., in the following embodiments are merely examples within a suitable range; that is, those skilled in the art can make appropriate selections within the range based on the description herein, and are not necessarily limited to the specific values in the embodiments below.
[0065] The yeast metabolites used in the embodiments of this application are fermented by aerobic fermentation of yeast strains using molasses as the main raw material. The specific composition of the yeast metabolites is shown in Table 1 below.
[0066] Table 1
[0067]
[0068]
[0069]
[0070] Understandably, the yeast metabolites mentioned above include fulvic acid, humic acid, succinic acid, acetic acid, free amino acids, hydrolyzed amino acids, and proteins in a mass ratio of 41.94 : 2.59 : 0.99 : 0.80 : 2.53 : 10.8 : 20.9. The protein specifically refers to number 43 in the table.
[0071] Example 1
[0072] This embodiment provides an organic complex comprising 42.86 parts of yeast metabolite (on a dry matter basis), 57.14 parts of anhydrous magnesium sulfate, and 44.44 parts of water.
[0073] The process of concentrating and evaporating the by-product metabolites involves concentrating the yeast metabolites to a 50% concentrate. The concentrate is then introduced into a settling tank to allow it to cool naturally to 60°C. It is then transferred to a reaction vessel, where powdered magnesium sulfate is gradually added while simultaneously stirring thoroughly. By controlling the rate of magnesium sulfate addition, the temperature of the mixed slurry is controlled and maintained between 72°C and 75°C using the exothermic reaction of magnesium sulfate during the reaction. This ensures that the magnesium sulfate dissolves as completely as possible within this temperature range. If the temperature is too high, an appropriate amount of water is added to maintain the temperature between 72°C and 75°C; if the temperature is too low, an appropriate amount of magnesium sulfate is added to maintain the temperature between 72°C and 75°C. The reaction is carried out for 2 hours. After the reaction is complete, the mixture is first transferred to a buffer tank, and then from the buffer tank to a centrifugal spray system. In the centrifugal spray system, the mixture undergoes centrifugal atomization, drying, cooling, and dehumidification processes to form a dry organic complex.
[0074] The organic complex of Example 1 was characterized, and the results of component analysis are shown in Table 2 below.
[0075] Table 2
[0076]
[0077] Example 2
[0078] The difference between this embodiment and Embodiment 1 lies in the proportion of raw materials. The raw materials provided in this embodiment include 46.17 parts of yeast metabolites, 53.83 parts of anhydrous magnesium sulfate, and 33.19 parts of water.
[0079] Detection and analysis were performed using a UV-vis (Ultraviolet-Visible Spectroscopy) spectrophotometer, within the detection wavelength range of 300-400 nm, such as... Figure 1 The image shows the full spectrum (200-1000 nm) of the organic complex, yeast metabolite, and magnesium sulfate obtained in Example 1 of this application. Figure 2The image shows partial spectra (300-400 nm) of the organic complex, yeast metabolite, and magnesium sulfate obtained in the embodiments of this application. The scanning range is 200.0-1000.0 nm, the scanning step size is 1.0 nm, and the scanning filter is 49. Information related to the above characteristic peaks is summarized in Table 3 below. In the organic complexes obtained in this application, the outer electrons of the functional groups (unsaturated hydrocarbons and heterocyclic compounds) / metal complexes undergo transitions from the ground state to the excited state after receiving ultraviolet radiation of a specific wavelength. The transitions mainly involve two energy levels: n→π. * And π → π*.
[0080] Table 3
[0081]
[0082] The UV-vis spectra of coordination compounds often show a redshifted absorption band in the ligand field in the visible light region, usually due to the transition metal from d→d * The absorption at 350-370 nm in the organic complex prepared in this application is a result of the red shift in the absorption of yeast metabolites. However, Mg is not a transition metal, and coordination is indirectly reflected through changes in the absorption of the ligands themselves (such as ligand deprotonation or changes in electronic structure). The red shift of the UV-vis absorption peak in the organic complex prepared in this application suggests that the ligands in the magnesium complex are transferring electrons to the Mg cation through their O or N coordination sites.
[0083] The substances involved in this application were analyzed by FT-IR (Fourier Transform Infrared Spectroscopy), such as... Figure 3 As shown:
[0084] Based on the infrared spectral characteristics, the infrared spectra of yeast metabolites, anhydrous magnesium sulfate, and the substance of this application can be divided into three regions (A1, A2, A3) for observation: A1 (wavenumber at 3400 cm⁻¹) -1 (Left and right): All three pictures are at 3400cm -1 An absorption peak appears at this location; this is a characteristic peak (i.e., a "water peak") generated by the functional group -OH of the solvent-water molecule. There is no obvious difference between the three graphs. The absorption of the amino group NH is also in this region, possibly encapsulated within the water peak. A3 (wavenumber ≤ 1000 cm⁻¹) -1 As can be seen from the infrared spectrum of magnesium sulfate, at 1100 cm⁻¹ -1 and 627cm -1A characteristic strong peak for sulfate ions was observed. Comparison shows that these two strong peaks also appeared in the infrared spectrum of the substance in this application. Because these two peaks are too strong, they mask the fine peak structure in this region, making it impossible to observe the absorption peaks in this region in the infrared spectrum of the yeast metabolite in the infrared spectrum of the substance in this application.
[0085] like Figure 4 The image shows the characteristics of region A2 in the infrared spectrum. A2 (1350 cm⁻¹) -1 ≤wavenumber≤1800cm -1 Infrared spectra of yeast metabolites at 1590 cm⁻¹ -1 and 1400cm -1 Two distinct strong peaks appear at this point. Based on the characteristic peak pattern of the infrared spectrum and the presence of fulvic acid and various amino acid derivatives in yeast metabolites, the double peaks here can be identified as characteristic peaks of carboxylate (R-COO-), amide bond (-CO-NH-), and amino group (NH2).
[0086] The two peaks in the infrared spectrum of the substance in this application are shifted to higher wavenumbers by approximately 30 cm⁻¹. -1 Moved to 1637cm -1 and 1437cm -1 This is because coordination alters the force constant of the bond, thus changing the spectral frequency. For example, when oxygen participates in coordination with a carboxylate, the C=O peak increases. In compounds containing amide bonds (-CO-N), when oxygen participates in coordination, the C=O peak decreases; when nitrogen participates in coordination, the CN peak decreases, and the C=O peak increases. The increased peaks in the substance of this application indicate that coordination with both N and O has occurred. This is because yeast metabolites are a mixture of fulvic acid and various amino acid derivatives, and different components interact with Mg through their respective N or O. 2+ Coordination was achieved.
[0087] According to numerous literature records on the formation of coordination compounds between amino acid derivatives and metals (Synthesis and Crystal Structure of a Novel 1D Magnesium(II) Coordination Polymer Constructed by L-CysteicAcid) -- LIHai-Ye LIAOBei-LingJIANGYi-MinZHANGShu-HuaLIJun-Xia (2007.8 Chinese J.Struct.Chem.907~910), if an amino acid reacts with a metal (such as magnesium) to form a complex, the characteristic peaks of C=O and CN will shift. For example, in an amide bond (-CO-NH-) containing a carbon-oxygen double bond and an amino group, if a magnesium ion forms a metal complex with a nitrogen atom, the original electrons on the nitrogen atom will tend to move towards the magnesium ion, reducing the electron cloud density of nitrogen and thus attracting electrons from the carbon-oxygen double bond, resulting in a stronger carbon-oxygen double bond. In infrared spectra, this is reflected in the fact that carbon-oxygen double bonds can absorb infrared light at higher wavenumbers, that is, the characteristic peaks shift towards higher wavenumbers; conversely, if magnesium ions form metal complexes with the carboxyl oxygen of amino acids, it will also cause the CN bond peak of amino acids to shift towards higher wavenumbers.
[0088] Therefore, the infrared spectrum of the substance in this application shows a clear shift towards higher wavenumbers, specifically around 1600 cm⁻¹. -1 and 1400cm -1 The presence of peaks is sufficient to indicate that a new complex has been formed in the material of this application, which is composed of O or N coordinated with Mg ions.
[0089] Analysis using XPS (X-ray Photoelectron Spectroscopy): Figure 5 XPS spectra of the organic complexes, yeast metabolites, and magnesium sulfate prepared in the embodiments of this application.
[0090] As can be seen in the N1s plot, nitrogen molecules physically adsorbed on the surface of magnesium sulfate elute at 399.98 eV. Yeast metabolites mainly elute with two distinct peaks at 395.98 eV and 398.18 eV. The broad peak in the 400-404 eV region may be due to the large number of components in the metabolites, their mutual influence and complexity, which caused the broadening of the N peak. The material in this application showed two new peaks (403.18 eV and 397.18 eV) that moved to higher binding energy positions. This indicates that N in the material in this application has coordinated with magnesium ions, and there are likely two different coordination forms. It is possible that the amide nitrogen and amino nitrogen of fulvic acid and amino acid derivatives are coordinated with magnesium ions respectively.
[0091] In the O1s plot, magnesium sulfate only shows a peak at 532.28 eV, while yeast metabolites mainly show two peaks (533.13 eV and 531.08 eV). The peaks of 532.48 eV and 529.83 eV in the material of this application correspond to the peaks of magnesium sulfate and yeast metabolites, respectively. In addition, a peak of 535.13 eV that shifts to a higher binding energy position also appears, which proves that O coordinates with magnesium ions in the material of this application.
[0092] In the Mg1s diagram, magnesium ions of magnesium sulfate elute at 1304.63 eV, while yeast metabolites elute at 1307.98 eV. The peaks of 1305.33 eV and 1308.73 eV in the present application can be attributed to magnesium sulfate and yeast metabolites, respectively. In addition, a new peak appears at a low binding energy position of 1299.88 eV, which may be a new organomagnesium complex formed by the coordination reaction between magnesium ions in magnesium sulfate and substances in yeast metabolites such as fulvic acid or amino acid derivatives.
[0093] The theoretical basis for the above XPS spectrum analysis is as follows: When O or N acts as a coordinating atom and binds to a metal ion, their lone pairs of electrons transfer to the empty orbitals of the metal ion, resulting in a decrease in the electron density around O and N. This decrease in electron density leads to an increase in binding energy, which is reflected in the XPS binding energy (the interaction between the atomic nucleus and electrons) as a shift of the XPS peak towards higher binding energies. The metal ion (Mg ion in this application) accepts electrons from coordinating atoms (such as lone pairs of electrons from O or N), reducing its effective positive charge and increasing its electron density. This leads to a decrease in the binding energy of the metal ion (Mg ion in this application), manifested as a shift of its XPS peak towards lower binding energies.
[0094] Based on the XPS test results of yeast metabolites, anhydrous magnesium sulfate, and the substances of this application, the peak elutions of their N1s, O1s, and Mg1s plots conform to the above-mentioned trends.
[0095] Based on the above UV-vis, FT-IR and XPS detection analyses, it can be clearly seen that, through this application, the organic functional groups in yeast metabolites and magnesium ions in magnesium sulfate underwent a coordination reaction, forming a new organic magnesium complex. The new substance formed in this application is an "N→Mg" or "COO→Mg" complex produced by the coordination reaction of magnesium ions with fulvic acid or amino acid derivatives.
[0096] Using the machine's built-in data processing software, the Mg1s plot of the X-ray photoelectron spectroscopy (XPS) in Example 1 above can be fitted. Figure 5The peak areas of the three peaks are as follows: the peak area corresponding to the Mg1s characteristic peak of the magnesium complex in the yeast metabolite raw material at 1305.33 eV is 1010.961; the peak area corresponding to the Mg1s characteristic peak of magnesium sulfate at 1308.73 eV is 948.013; and the peak area corresponding to the Mg1s characteristic peak of the newly generated organic magnesium complex at 1299.88 eV is 1022.982.
[0097] Based on the fact that the magnesium element in the organic compound magnesium fertilizer of this application has three forms, namely the magnesium complex contained in the raw material, magnesium sulfate and newly generated magnesium complex; it can be inferred from the peak area that the content of the above three forms of magnesium element in the organic compound magnesium fertilizer of Example 1 of this application is 33%, 33% and 34% respectively.
[0098] In Example 1 of this application, the product was commissioned to the Vegetable Research Institute of the Guangdong Academy of Agricultural Sciences for crop application trials. The experimental crop was sweet cabbage, and three treatments were set up: control group 1, control group 2, and experimental group 1.
[0099] 1) Control group 1, whose nutrient input was 180 kg / ha of nitrogen, 60 kg / ha of phosphorus, and 90 kg / ha of potassium.
[0100] 2) Control group 2, whose nutrient input was 180 kg / ha of nitrogen, 60 kg / ha of phosphorus, 90 kg / ha of potassium, 50 kg / ha of magnesium, and 10 kg of yeast metabolites used in this application (a simple mixture of magnesium sulfate and yeast metabolites).
[0101] 3) Experimental group 1, the nutrient input is 180 kg / ha of nitrogen, 60 kg / ha of phosphorus, 90 kg / ha of potassium and 50 kg / ha of magnesium (the source of magnesium nutrient here is the organic complex produced in Example 1 of this application).
[0102] Experimental results:
[0103] like Figure 6 To use actual plant images of control group 1, control group 2, and experimental group 1 respectively, and as follows: Figure 7 The bar chart shows the leaf area of control group 1, control group 2, and experimental group 1. The results indicate that magnesium promotes crop growth, and the organic complex in experimental group 1 showed a more significant promoting effect on crop growth. Furthermore, the product of this application significantly promotes leaf growth. Statistical results show that the leaf area of Chinese cabbage leaves using this product increased by 111% compared to the control group and by 21.8% compared to control group 2.
[0104] like Figure 8 The images shown are actual photos of plant rhizomes from control group 1, control group 2, and experimental group 1, respectively. Figure 9The bar charts shown depict the stem diameter and fresh weight of the rhizomes from plants grown in control group 1, control group 2, and experimental group 1, respectively. This indicates that the product of this application has a significant promoting effect on crop stem growth. Compared to control group CK, experimental group 1 showed a 47.8% increase in stem diameter and a 234.4% increase in fresh stem weight, and compared to control group 2, it showed an 8.4% increase in stem diameter and a 27.9% increase in fresh stem weight.
[0105] like Figure 10 Bar charts showing the fresh weight of aboveground parts of plants for control group 1, control group 2, and experimental group 1 are presented separately. This indicates that the product of this application has a statistically significant effect on crop growth. Under the experimental conditions, experimental group 1 showed an 88% increase in harvest yield compared to control group CK, and a 14.6% increase in harvest yield compared to control group 2.
[0106] like Figure 11 The bar charts shown depict the soluble sugar and soluble protein content in plants using control group 1, control group 2, and experimental group 1, respectively. Under the experimental conditions, the soluble sugar content per plant of crops using the product of this application increased by 117.7% and the soluble protein content per plant increased by 112.9% compared to the control; compared to control group 2, the soluble sugar content per plant of crops using the product of this application increased by 19.5% and the soluble protein content increased by 21.3%. The product of this application has a significant effect on improving crop quality.
[0107] Based on the above test results, the magnesium fertilizer of the organic compound of this application, compared with the control group CK in this experiment (which did not use magnesium fertilizer and organic materials) and the simple mixture of yeast metabolites and magnesium sulfate, can significantly promote crop growth, significantly increase yield and agricultural product quality.
[0108] In addition, a comparison was conducted between the organic complex of this application and magnesium sulfate with the same magnesium nutrient content. Crop trials were performed to study the magnesium nutrient absorption and utilization rates of the two different types of magnesium fertilizers. This experiment was also commissioned to the Vegetable Research Institute of the Guangdong Academy of Agricultural Sciences, and the results are as follows: Figure 12 as well as Figure 13 As shown. Figure 12 Bar charts showing vegetable yields using water-soluble inorganic magnesium fertilizer and magnesium fertilizer containing magnesium compounds (specifically, the organic complexes described in this application). Figure 13 The bar chart shows the magnesium accumulation of vegetables using water-soluble inorganic magnesium fertilizer and the magnesium fertilizer containing the magnesium complex as described in this application. It is evident that supplying the same amount of magnesium nutrients resulted in a significant difference in vegetable yield. The application of the magnesium fertilizer containing the magnesium complex increased vegetable yield by 18.3% compared to conventional water-soluble inorganic magnesium fertilizer. The cumulative absorption of magnesium nutrients by vegetables from the two different types of magnesium fertilizer also differed significantly; the accumulation of magnesium nutrients in vegetables from the magnesium fertilizer containing the magnesium complex was 14.5% higher than that from conventional water-soluble inorganic magnesium fertilizer.
[0109] The organic complex, amino acid magnesium, sugar alcohol magnesium, and EDTA magnesium provided in this application are used for uniform seedling cultivation of water spinach. Compared with amino acid magnesium, sugar alcohol magnesium, and EDTA magnesium, the organic complex provided in this application has a higher yield per acre.
[0110] This application describes a complex formed by the coordination reaction of magnesium sulfate and yeast metabolites, resulting in a magnesium-organic ligand complex with good water solubility. When this organic complex is applied to the soil as a magnesium fertilizer, the presence of the coordination structure and free magnesium... 2+ Compared to other fertilizers, it is less prone to leaching, improving the absorption and utilization efficiency of magnesium nutrients and resulting in higher fertilizer utilization efficiency. When used as fertilizer with the same magnesium nutrient, it can lead to better crop yields. Magnesium fertilizers containing organic compounds can not only solve the problem of magnesium deficiency in soil and crops in agriculture, but also promote crop growth, comprehensively improving the effectiveness of organic matter and magnesium fertilizer.
[0111] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.
[0112] The embodiments described above are merely illustrative of several implementation methods of this application, intended to facilitate a detailed understanding of the technical solutions of this application, but should not be construed as limiting the scope of protection of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the scope of protection of this application. It should be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided in this application through logical analysis, reasoning, or limited experimentation are all within the scope of protection of the appended claims. Therefore, the scope of protection of this patent application should be determined by the content of the appended claims, and the specification can be used to interpret the content of the claims.
Claims
1. An organic complex, characterized in that, It includes a central metal ion and an organic ligand, wherein the organic ligand includes yeast metabolites; the yeast metabolites include one or more of fulvic acid, humic acid, succinic acid, acetic acid, free amino acids, hydrolyzed amino acids, and proteins; and the central metal ion includes magnesium ions.
2. A method for preparing the organic complex as described in claim 1, characterized in that, Includes the following steps: The raw materials for the organic complex are mixed and heated to 60°C~95°C to carry out a complexation reaction to prepare the organic complex. The raw materials include yeast metabolites and magnesium salts; the yeast metabolites include one or more of fulvic acid, humic acid, succinic acid, acetic acid, free amino acids, hydrolyzed amino acids, and proteins.
3. The method for preparing the organic complex according to claim 2, characterized in that, The yeast metabolites include fulvic acid, humic acid, succinic acid, acetic acid, free amino acids, hydrolyzed amino acids, and proteins in a mass ratio of (35~45):(1~5):(0.5~2):(0.5~2):(1~5):(5~15):(15~25).
4. The method for preparing the organic complex according to claim 2, characterized in that, The magnesium salt includes one or more of magnesium sulfate, magnesium nitrate, and magnesium chloride.
5. The method for preparing the organic complex according to claim 2, characterized in that, The yeast metabolites include the filtrate from one or more fermentation raw materials selected from molasses, hydrolyzed sugar, beet, barley, and corn after aerobic fermentation.
6. The method for preparing the organic complex according to claim 4, characterized in that, The temperature for aerobic fermentation is 25℃~30℃.
7. The method for preparing the organic complex according to claim 4, characterized in that, The pH value for aerobic fermentation is 5.0~6.
5.
8. The method for preparing the organic complex according to any one of claims 2 to 7, characterized in that, The raw materials include the yeast metabolites and the magnesium salt in a mass ratio of (35~50):(45~65).
9. The method for preparing the organic complex according to any one of claims 2 to 7, characterized in that, The reaction time is 1.5 hours to 2.5 hours.
10. A water-soluble fertilizer, characterized in that, This includes the organic complex as described in claim 1 or the organic complex prepared by the preparation method described in any one of claims 2 to 9.
Citation Information
Patent Citations
Magnesium-containing compound fertilizer with quick-acting and slow-acting characteristics and preparation method thereof
CN111099934A
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CN114163279A