Preparation method of magnesium phytate crystal material
Through the sol-gel crystallization method under low temperature environment, the problem of difficult to prepare stable magnesium phytate crystals in the existing technology is solved, high-quality preparation of magnesium phytate crystals is achieved, and its application potential in high-end fields is expanded.
Patent Information
- Application Number
- CN202411592462.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-08
- Publication Date
- 2025-02-21
AI Technical Summary
The prior art is difficult to effectively prepare pure magnesium phytate crystal materials, resulting in instability in physical and chemical properties, limiting its application potential in high-end fields.
Sol-gel crystallization method is used in low-temperature environment, by mixing sodium phytate with magnesium source, adjusting the pH value, and conducting a low-temperature reaction, gradually converting into a gel and finally forming regular magnesium phytate crystals.
The magnesium phytate crystal materials with good crystallinity and purity were successfully prepared, which enhanced its application potential in biomedical, food, anti-corrosion and other fields.
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Figure CN119490525A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the field of fine chemicals and relates to a method for preparing magnesium phytate crystal material by sol-gel crystallization under a low-temperature environment. Background Art
[0002] Phytic acid is a natural organic phosphorus compound extracted from plants. It has environmentally friendly properties such as non-toxicity and biodegradability. Phytic acid almost never exists in free form in plants, but in the form of phytates. Phytates are compounds formed by the combination of phytic acid and metal ions such as calcium, magnesium, zinc, and sodium. Among them, magnesium phytate is a specific salt compound formed by phytic acid and magnesium ions. Through specific chemical reactions or biotransformation processes, the cations in phytates can be replaced by magnesium ions to produce magnesium phytate.
[0003] At present, the main preparation method of magnesium phytate is direct precipitation, but this method can only produce amorphous magnesium phytate products. Researchers mixed phytic acid or phytate solution with magnesium salt (such as magnesium chloride, magnesium nitrate, etc.) solution in a certain proportion, and allowed the two to react directly to form a precipitate under appropriate temperature and pH conditions. The magnesium phytate product was obtained by filtering, washing, drying and other steps. The results showed that magnesium phytate, as a bio-based phosphorus flame retardant, exhibited significant flame retardant properties. At the same time, some researchers prepared magnesium phytate by direct precipitation and modified it on the electrode as a cathode hydrogen evolution material. It was found that magnesium phytate, as a catalyst, can effectively improve the electrocatalytic hydrogen evolution performance. In J. Mater. Chem. A, 2017, 5, 12943, researchers reported for the first time a MOFs crystalline material based on hexaphosphate ligands, by adding hexahydrate zinc nitrate and phytic acid to a mixed solvent of water-methanol-dimethylformamide, and then adding nitric acid to obtain a clear solution. The solvent evaporated for 1 week at room temperature, and finally obtained colorless zinc phytate crystals with a yield of 68%. Although this innovative achievement provides inspiration for the preparation of magnesium phytate crystals, this method is complex to operate and has high costs, making it difficult to achieve large-scale production and wide application.
[0004] There are many studies on the application of magnesium phytate, involving multiple fields such as electrocatalytic hydrogen evolution, metal surface treatment, and flame retardant materials. These studies reveal the unique performance and potential value of magnesium phytate in different application scenarios. However, there are few studies on the preparation of magnesium phytate, and no pure magnesium phytate crystal material has been found so far. Magnesium phytate in an amorphous state lacks a clear crystal structure and its molecular arrangement is relatively disordered, which may lead to greater instability in its physical and chemical properties. Only by preparing magnesium phytate crystals can the application potential of magnesium phytate in more high-end fields be explored. Especially in the fields of medicine, corrosion protection, food, etc., magnesium phytate crystals are conducive to studying the biological metabolic process of magnesium phytate and the corrosion protection mechanism of phytate on magnesium alloys. In view of this, research on the preparation method of magnesium phytate crystals is particularly urgent. Summary of the invention
[0005] The technical problem to be solved by the present invention is to provide a simple and low-energy consumption method for preparing magnesium phytate crystal material.
[0006] The technical solution of the present invention is to prepare magnesium phytate crystal material by sol-gel crystallization under a low temperature environment, comprising the following steps:
[0007] Step 1, preparation of sol: First, sodium phytate and a magnesium source (magnesium chloride, magnesium sulfate, magnesium citrate, magnesium carbonate, magnesium nitrate, magnesium acetate) are respectively prepared into aqueous solutions of a certain concentration, the two are mixed at a certain temperature, the pH value is adjusted to 7-14, and a white sol is obtained after stirring evenly.
[0008] Step 2, sol-gel crystallization: The sol obtained in step (1) is reacted at low temperature. As the reaction time increases, the upper opaque white sol gradually drops, and a clear liquid is obtained at the top. After the reaction is completed, the sol becomes completely clear, and a large number of regular, transparent crystals are generated at the bottom. In this process, the sol ages and gradually transforms into a gel, and remains in a gel state for a period of time, and then transforms into a macroscopic crystal without any environmental stimulation. The transformation process is divided into two steps: (1) After the initial crystal is formed, the surrounding gel factor molecules gradually gather towards it; (2) As the concentration of the gel factor decreases, the aggregated fibers gradually dissociate into a solution, so that more molecules gather into the crystal.
[0009] Step 3, washing and drying: The magnesium phytate crystals obtained in step 2 are washed with distilled water for 3 to 4 times, and dried to obtain regular, opaque magnesium phytate crystals.
[0010] Preferably, sodium phytate is used as the main raw material, magnesium chloride hexahydrate is used as the magnesium source, and the molar ratio of sodium phytate to the magnesium source is 1:1.
[0011] Preferably, the initial concentration of sodium phytate and magnesium source is 0.1 mol / l.
[0012] Preferably, during the experimental operation, sodium phytate is dripped into the magnesium source and the injection is completed within 1 hour.
[0013] Preferably, the mixed solution is adjusted to pH = 11.8
[0014] Preferably, the starting materials are mixed at room temperature, stirred until the mixture is uniform, and then reacted at low temperature.
[0015] Preferably, the low temperature reaction time is 4-6 hours.
[0016] Preferably, the low temperature reaction temperature is 5°C.
[0017] The beneficial effects achieved by the present invention are as follows: the present invention successfully prepares magnesium phytate crystal materials. In previous studies, although magnesium phytate has shown wide application potential in many fields, the preparation of magnesium phytate crystals has always been a difficult problem to overcome. This study achieves the stable synthesis of magnesium phytate crystals through an innovative preparation method, and also expands a new direction for the application of phytic acid and its derivatives.
[0018] The innovation of the present invention is that the sol-gel crystallization method used in this study is a method carried out under mild conditions, which is simple and low-cost. Sodium phytate and magnesium chloride hexahydrate are used as raw materials to form a gel through a chelation reaction, and the gel spontaneously transforms into crystals at 5°C. When the reaction time is 2h, some crystals are observed at the bottom of the gel, and a thin layer of transparent solution appears on the upper part of the gel. As time goes on, the gel further shrinks, the solution becomes more and more, and the crystals become larger and larger. The final crystalline material is prepared after drying and washing. Magnesium phytate crystals, as a new type of composite material, combine the excellent properties of magnesium and the special functions of phytic acid, such as biocompatibility and biodegradability. It provides new material options for specific application fields (such as biomedicine, food, antiseptic, etc.). BRIEF DESCRIPTION OF THE DRAWINGS
[0020] Figure 1 This is an optical microscope image of the magnesium phytate crystals prepared in Example 2.
[0021] Figure 2 is the X-ray diffraction pattern of the magnesium phytate crystals prepared in Example 2,
[0022] Figure 3 This is the infrared spectrum of the magnesium phytate crystals prepared in Example 2.
[0023] Figure 4 This is the Raman spectrum of the magnesium phytate crystals prepared in Example 2.
[0024] Figure 5 This is a flow chart of preparing magnesium phytate crystals by sol-gel-crystallization in Example 2. DETAILED DESCRIPTION
[0025] The technical solution of the present invention is further described below through embodiments.
[0026] Example 1
[0027] Use 0.1mol / l sodium phytate solution and 0.05mol / l magnesium chloride solution as starting materials, and the volume ratio of sodium phytate to magnesium source is 1:1. At room temperature, add 20L sodium phytate solution to magnesium chloride solution, inject it within 1h, place it in the reactor and stir for 1min until the mixed solution is uniform. Control the pH value to 12.08. Place the reactor at 5℃ for low-temperature reaction to generate a large number of regular transparent particles. After filtering and washing the particles three times with distilled water, dry them at 80℃ for 12h to obtain white powder.
[0028] Example 2
[0029] Use 0.1mol / l sodium phytate solution and 0.1mol / l magnesium chloride solution as starting materials, and the volume ratio of sodium phytate to magnesium source is 1:1. At room temperature, add 20L sodium phytate solution to magnesium chloride solution, and inject it within 1 hour. Place it in the reactor and stir for 1 minute until the mixed solution is uniform. Control the pH value to 11.80. Place the reactor at 5℃ and react at low temperature to generate a large number of regular transparent particles. After filtering and washing the particles three times with distilled water, dry them at 80℃ for 12 hours to obtain white powder.
[0030] The powder obtained in Example 2 was placed under a microscope for observation. Figure 1 As shown, the morphology of magnesium phytate is regular and is a spindle structure. Magnesium phytate was subjected to X-ray diffraction test, and its X-ray diffraction pattern is Figure 2 ,Depend on Figure 2 It can be seen that magnesium phytate has a high degree of crystallinity.
[0031] Figure 3 This is the infrared spectrum of the magnesium phytate crystals prepared in Example 2.
[0032] Figure 4 This is the Raman spectrum of the magnesium phytate crystals prepared in Example 2.
[0033] Example 3
[0034] Use 0.1mol / l sodium phytate solution and 0.2mol / l magnesium chloride solution as starting materials, and the volume ratio of sodium phytate to magnesium source is 1:1. At room temperature, add 20L sodium phytate solution to magnesium chloride solution, and inject it within 1 hour. Place it in the reactor and stir for 1 minute until the mixed solution is uniform. Control the pH value to 11.57. Place the reactor at 5℃ and react at low temperature to generate a large number of regular transparent particles. After filtering and washing the particles three times with distilled water, dry them at 80℃ for 12 hours to obtain white powder.
[0035] Example 4
[0036] Use 0.1mol / l sodium phytate solution and 0.4mol / l magnesium chloride solution as starting materials, and the volume ratio of sodium phytate to magnesium source is 1:1. At room temperature, add 20L sodium phytate solution to magnesium chloride solution, and inject it within 1 hour. Place it in the reactor and stir for 1 minute until the mixed solution is uniform. Control the pH value to 9.8. Place the reactor at 5℃ and react at low temperature to generate a large number of regular transparent particles. After filtering and washing the particles three times with distilled water, dry them at 80℃ for 12 hours to obtain white powder.
[0037] Example 5
[0038] Use 0.1mol / l sodium phytate solution and 0.6mol / l magnesium chloride solution as starting materials, and the volume ratio of sodium phytate to magnesium source is 1:1. At room temperature, add 20L sodium phytate solution to magnesium chloride solution, inject it within 1h, place it in the reactor and stir for 1min until the mixed solution is uniform. Control the pH value to be 8.5 respectively. Place the reactor at 5℃ for low temperature reaction to generate a large number of regular transparent particles. After filtering and washing the particles with distilled water three times, dry them at 80℃ for 12h to obtain white powder.
[0039] Example 6
[0040] Use 0.1mol / l sodium phytate solution and 0.1mol / l magnesium chloride solution as starting materials, the volume ratio of sodium phytate to magnesium source is 1:1, P:Mg=6:1. At room temperature, add 20L sodium phytate solution to magnesium chloride solution, inject it within 1h, place it in the reactor and stir for 1min until the mixed solution is uniform. Control the pH value to 11.80. Place the reactor at 25℃ to react and generate a large number of regular transparent particles. After filtering and washing the particles three times with distilled water, dry them at 80℃ for 12h to obtain white powder.
[0041] Example 7
[0042] A mixture of 0.1 mol / l sodium phytate solution and 0.1 mol / l magnesium chloride solution was used as the starting material, and the volume ratio of sodium phytate to magnesium source was 1:1, that is, P:Mg=6:1. At room temperature, 20L of sodium phytate solution was added to the magnesium chloride solution, and the injection was completed within 1 hour. The pH was adjusted to 11.8, and the mixture was placed in the reactor and stirred for 1 hour, and a large amount of white precipitate was directly generated. After the reactor was placed at 5°C for low-temperature reaction, there was no obvious change. The white precipitate was filtered and washed three times with distilled water, and then dried at 60°C for 12 hours to obtain a white powder.
[0043] Embodiment 8-11
[0044] The pH values in Examples 8-11 were 7, 8, 9, and 10, respectively, and the other reaction conditions were the same as those in Example 7.
[0045] Example 12
[0046] A mixture of 0.1 mol / l sodium phytate solution and 0.1 mol / l magnesium chloride solution was used as the starting material, and the volume ratio of sodium phytate to magnesium source was 1:1, that is, P:Mg=6:1. At room temperature, 20L of sodium phytate solution was added to the magnesium chloride solution, and the injection was completed within 1 hour. The pH was adjusted to 11.8, and the mixture was placed in the reactor and stirred for 1 hour, and a large amount of white precipitate was directly generated. After the reactor was placed at 5°C for low-temperature reaction, there was no obvious change. The white precipitate was filtered and washed three times with distilled water, and then dried at 80°C for 12 hours to obtain a white powder.
[0047] Examples 13-16
[0048] The pH values in Examples 13-16 were 7, 8, 9, and 10, respectively, and the other reaction conditions were the same as those in Example 12.
[0049] Embodiment 17
[0050] A mixture of 0.1 mol / l sodium phytate solution and 0.1 mol / l magnesium chloride solution was used as the starting material, and the volume ratio of sodium phytate to magnesium source was 1:1, that is, P:Mg=6:1. At room temperature, 20L of sodium phytate solution was added to the magnesium chloride solution, and the injection was completed within 1 hour. The pH was adjusted to 11.8, and the mixture was placed in a reactor and stirred for 1 hour, and a large amount of white precipitate was directly generated. After the reactor was placed at 5°C for low-temperature reaction, there was no obvious change. The white precipitate was filtered and washed three times with distilled water, and then dried at 100°C for 12 hours to obtain a white powder.
[0051] Examples 18-21
[0052] The pH values in Examples 18-21 were 7, 8, 9, and 10, respectively, and the other reaction conditions were the same as those in Example 17.
[0053] Embodiment 22
[0054] Use 0.1mol / l sodium phytate solution and 0.2-0.6mol / l magnesium chloride solution as starting materials, with a volume ratio of sodium phytate to magnesium source of 1:1. At 60°C, add 20L of sodium phytate solution to magnesium chloride solutions of different concentrations, and complete the injection within 1 hour. Adjust the pH to 7, 8, 9, 10, and place in a reactor and heat and stir at 60°C for 1 hour to allow the mixture to react fully. Place the reactor at 5°C for low-temperature reaction.
[0055] Embodiment 23-24
[0056] The reaction temperatures in Examples 23-24 were 80°C and 100°C, respectively, and the other reaction conditions were the same as in Example 22.
[0057] Embodiment 25
[0058] Use 0.1mol / l sodium phytate solution and 0.1mol / l magnesium chloride solution as starting materials, the volume ratio of sodium phytate to magnesium source is 2:3, that is, P:Mg=4:1. At 80℃, add 20L sodium phytate solution to magnesium chloride solution, and inject it within 1 hour. Adjust pH=11.8, place it in a reactor and heat and stir at 80℃ for 1 hour to make the mixed solution fully react. Place the reactor at 5℃ for low temperature reaction for 4 days to generate a large number of regular transparent particles. The particles are filtered and washed three times with distilled water and dried at 80℃ for 12 hours to obtain white powder.
[0059] Embodiment 26
[0060] Use 0.1mol / l sodium phytate solution and 0.1mol / l magnesium chloride solution as starting materials, the volume ratio of sodium phytate to magnesium source is 1:3, that is, P:Mg=2:1. At 80℃, add 20L sodium phytate solution to magnesium chloride solution, inject it within 1h, adjust pH=11.8, place it in a reactor and heat and stir at 80℃ for 1h to make the mixed solution fully react. Place the reactor at 5℃ for low temperature reaction for 4d to generate a large number of regular transparent particles. The particles are filtered and washed three times with distilled water and dried at 80℃ for 12h to obtain white powder.
[0061] Embodiment 27
[0062] Use 0.1mol / l sodium phytate solution and 0.1mol / l magnesium chloride solution as starting materials, the volume ratio of sodium phytate to magnesium source is 1:6, that is, P:Mg=1:1. At 80℃, add 20L sodium phytate solution to magnesium chloride solution, and inject it within 1h. Adjust pH=11.8, place it in a reactor and heat and stir at 80℃ for 1h to make the mixed solution fully react. Place the reactor at 5℃ for low temperature reaction for 4d to generate a large number of regular transparent particles. The particles are filtered and washed three times with distilled water and dried at 80℃ for 12h to obtain white powder.
[0063] In order to more comprehensively demonstrate the innovation and technical effects of the present invention in the field of material synthesis, a comparative example is provided below to compare and analyze the technical solution of the present invention with the prior art. By comparison, it is intended to clarify the significant advantages of the present invention in solving specific technical problems, improving material performance or optimizing synthesis processes.
[0064] Comparative Example
[0065] In the synthesis reported in "Wang Wenjuan. Synthesis of magnesium phytate and study on its electrocatalytic hydrogen evolution performance [J]. Yunnan Chemical Industry, 2018, 45(07): 66-67.", the researchers used a direct precipitation method to prepare magnesium phytate complexes. 30 ml of phytic acid was placed in a 400 ml beaker and 100 ml of ultrapure water was added. MgCl2 was weighed at a molar ratio of 1:6 and added to the beaker. Under the stirring of a magnetic stirrer, 1 mol / L NaOH was slowly injected over 1 hour to adjust the pH to 6. The mixture was stirred at a constant temperature of 60 ° C and a magnetic stirrer for 0.5 hours, aged, and filtered. It was placed in a crucible, dried at room temperature overnight, and baked at 105 ° C for 1 hour. The resulting magnesium phytate was amorphous.
[0066] After many attempts and optimizations, this study successfully prepared magnesium phytate crystals. XRD results showed that the prepared crystals had clear diffraction peaks, indicating good crystallinity. Optical microscopy images further confirmed the morphology and structural characteristics of the crystals. In addition, infrared spectroscopy analysis showed that the characteristic functional groups of phytic acid were retained in magnesium phytate crystals and formed stable chemical bonds with magnesium ions.
[0067] This study successfully prepared magnesium phytate crystals with good crystallinity and purity, which provides an important foundation for subsequent scientific research and application development. This study not only demonstrates the possibility of phytic acid and metal ions forming crystal structures, but also provides new ideas and methods for the research of metal-organic framework materials. In the future, we will continue to explore the properties and functions of magnesium phytate crystals and strive to develop its application potential in biomedicine, materials science and other fields.
Claims
1. A method for preparing a magnesium phytate material, characterized in that: The following steps are involved: (1) Preparation of sol: First, sodium phytate and a magnesium source (magnesium chloride, magnesium sulfate, magnesium citrate, magnesium carbonate, magnesium nitrate, magnesium acetate) are respectively prepared into aqueous solutions of a certain concentration, the two are mixed at a certain temperature, the pH value is adjusted to 7-14, and a white sol is obtained after stirring evenly. (2) Sol-gel crystallization: The sol obtained in step (1) is reacted at low temperature. As the reaction time increases, the opaque white sol on the upper layer gradually drops, and a clear liquid is obtained at the upper part. After the reaction is completed, the sol becomes completely clear, and a large number of regular, transparent crystals are generated at the bottom. In this process, the sol is aged and gradually transformed into a gel. They remain in a gel state for a while, but then transform into macroscopic crystals without any environmental stimulation. The transformation process is divided into two steps: ① After the initial crystal is formed, the surrounding gel factor molecules gradually gather towards it; ② As the concentration of the gel factor decreases, the aggregated fibers gradually dissociate into a solution, allowing more molecules to gather into the crystal. (3) Washing and drying: The magnesium phytate crystals obtained in step (2) are washed with distilled water for 3 to 4 times, and dried to obtain regular, opaque magnesium phytate crystals.
2. The method for preparing a magnesium phytate material according to claim 1, characterized in that: The main raw material used in step (1) is sodium phytate, and the magnesium source is magnesium chloride, magnesium sulfate, magnesium citrate, magnesium carbonate, magnesium nitrate, magnesium acetate, etc.
3. The method for preparing a magnesium phytate material according to claim 1, characterized in that: When sodium phytate is mixed with a magnesium source in step (1), the specific operation is to inject sodium phytate into the magnesium source.
4. The method for preparing a magnesium phytate material according to claim 1, characterized in that: In step (1), sodium hydroxide or aqueous ammonia is used to adjust the pH value.
5. The method for preparing a magnesium phytate material according to claim 1, characterized in that: The molar ratio of sodium phytate to magnesium source used in step (1) is 1:1 to 10:
1.
6. The method for preparing a magnesium phytate material according to claim 1, characterized in that: In step (1), the mixing temperature of sodium phytate and the magnesium source is 25-120°C.
7. The method for preparing a magnesium phytate material according to claim 1, characterized in that: In step (1), the mixing and stirring time of sodium phytate and the magnesium source is 10s to 6h.
8. The method for preparing a magnesium phytate material according to claim 1, characterized in that: In step (1), the mixing stirring rate of sodium phytate and the magnesium source is 50 rpm to 5000 rpm.
9. The method for preparing a magnesium phytate material according to claim 1, characterized in that: In step (2), the reaction temperature is -5 to 25° C., and the reaction time is 2 h to 30 days.
10. The method for preparing a magnesium phytate material according to claim 1, characterized in that: The drying temperature in step (3) is 50-120°C.