A method for synthesizing xylaric acid salt with high efficiency and low cost
Through the oxidation reaction of Fe-supported catalyst and hydrogen peroxide, the existing xylodonate synthesis problems are solved, efficient and low-cost production is achieved, and the catalyst can be recycled, which is safe and environmentally friendly.
Patent Information
- Application Number
- CN202411780868.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-05
- Publication Date
- 2025-04-01
AI Technical Summary
The existing xylodonate synthesis methods have high costs, environmental pollution and catalyst non-recyclable problems, making it difficult to achieve efficient and low-cost production.
The catalyst supported by Fe is used to synthesize xylose diates through hydrogen peroxide oxidation reaction to achieve a green, environmentally friendly, safe and efficient production process, and the catalyst can be recycled multiple times.
It realizes efficient and low-cost xylodiate synthesis, high product conversion rate, reusable catalysts, reduce production costs, and safe and environmentally friendly processes.
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Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of xylaric acid salt synthesis, and in particular relates to a method for synthesizing xylaric acid salt with high efficiency and low cost. Background Art
[0002] Xylose diacid is a derivative of xylose oxidized, and its main component is disodium xylose. The preparation methods of xylose diacid mainly include chemical method and biological method. Chemical method includes iodine oxidation method, electrolytic oxidation method and metal catalysis method. The commonly used iodine catalytic synthesis is to oxidize xylose with iodine in a strong alkaline environment with methanol as solvent, protect the hydroxyl group from oxidation, and only oxidize the aldehyde group to the carboxyl group to obtain xylose diacid, and then add concentrated acid to obtain xylose acid crystals. Metal catalytic synthesis: Use a catalyst containing 5% palladium to catalyze the substrate conversion, adjust the pH value to 10.0 with NaOH to react, and generate xylose diacid. The oxidation rate of xylose is low, but a higher conversion rate can be achieved by increasing the temperature and reaction time. The biological method mainly uses enzyme catalysis and cell catalysis. The enzyme catalysis method usually uses gluconate oxidase and xylose dehydrogenase, which requires the participation of NAD+ coenzyme, but the product concentration and conversion rate are low. The cell catalysis method uses oxidative gluconobacter, etc., and the reaction is efficient and specific.
[0003] Xylose is widely used in many fields. It is not only an important metabolite of vitamin C, but also plays a vital role in regulating the effective circulation and metabolism of vitamin C in the body. It is also a new generation of plant growth regulator and an essential additive for acidic environments in aquaculture. In addition, it can be used as a cement water reducer, dispersant and retarder, concrete binder, plasticizer, textile bleaching agent, glass cleaning agent, metal ion chelator, metallurgical rust remover and food acidifier. In addition, stable isotope-labeled xylose can also be used as an internal standard for chromatographic analysis. Summary of the invention
[0004] The purpose of the present invention is to provide a method for synthesizing xylaric acid salt with high efficiency and low cost. The method adopts Fe loaded on a porous carrier as an efficient catalyst to obtain xylaric acid salt by oxidation with hydrogen peroxide. The method is green and environmentally friendly, has a high safety factor, is highly operable, and the catalyst can be recycled for multiple times, thereby reducing the production cost.
[0005] To achieve the above object, the technical solution adopted by the present invention is:
[0006] A method for synthesizing xylaric acid salt with high efficiency and low cost is disclosed. The method comprises the following steps: uniformly mixing gluconate, deionized water and a catalyst, and heating the mixture to 50-70° C.; adding hydrogen peroxide at a certain drop rate controlled by a peristaltic pump, reacting the mixture under certain temperature and pH conditions, keeping the mixture warm for a period of time after the drop addition is completed, and filtering the mixture to obtain a xylaric acid salt solution.
[0007] Furthermore, the gluconate is one of sodium gluconate, potassium gluconate and calcium gluconate.
[0008] Furthermore, the mass ratio of the gluconate to deionized water is 1:0.7-2.0, preferably 1:0.7-1.3.
[0009] Furthermore, the molar ratio of the gluconate to the catalyst is 1:0.03-0.08.
[0010] Furthermore, the catalyst is a Fe / Fe3C nanoparticle-supported porous nitrogen-doped carbon-based oxygen reduction catalyst.
[0011] Furthermore, the preparation method of the catalyst is:
[0012] Step (1): Dissolve 5 g of melamine and 5 mL of formaldehyde in 50 mL of deionized water, place in a 60°C water bath and stir for 30 min to mix evenly, then add 1 g of SiO2, 0.7 g of ferric acetylacetonate and 2 mL of glacial acetic acid, continue stirring at this temperature for 1 h, then stir at room temperature overnight, and obtain the material by centrifugation and drying:
[0013] Step (2): the material of the above step (1) is transferred to a nickel boat and placed in a tube furnace. In an inert gas atmosphere, the temperature is first increased from room temperature to 300° C. over 55 min and maintained for 60 min, then increased to 800° C. at a heating rate of 5° C. / min and maintained for 120 min, and then naturally cooled to room temperature to obtain the material;
[0014] Step (3): The material of the above step (2) is transferred to a 20wt% hydrofluoric acid solution, soaked for 24 hours, washed with high-purity water until neutral, and then placed in an oven at 80°C for 12 hours to obtain a Fe / Fe3C nanoparticle-loaded porous nitrogen-doped carbon-based oxygen reduction catalyst.
[0015] Furthermore, the dripping rate of the hydrogen peroxide solution is 0.1-0.6 L / min.
[0016] Furthermore, the reaction temperature is 50-70° C., and the insulation time is 0.5-3.0 h.
[0017] Furthermore, the molar ratio of the gluconate to H2O2 is 1:2.0-5.0.
[0018] Furthermore, the pH is adjusted by using a sodium hydroxide solution with a mass fraction of 20%-50%, and the pH value of the solution is adjusted to 8-12.
[0019] The reaction principle of the present invention is:
[0020]
[0021] After the synthesis method of the present invention is completed, the catalyst obtained by filtering can be washed and dried, and then recycled.
[0022] Compared with the prior art, the present invention has the following beneficial effects:
[0023] 1. The present invention adopts gluconate as raw material and hydrogen peroxide as oxidant, which is safe, non-toxic, green and environmentally friendly.
[0024] 2. The preparation process of this method is stable and easy to control, the operation is simple, the catalytic activity of the catalyst is high, it can be recycled and reused, and the conversion rate of the product is still high. DETAILED DESCRIPTION
[0025] The technical solutions and effects of the present invention are further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited thereto.
[0026] Example 1
[0027] The present invention provides a method for synthesizing xylaric acid salt with high efficiency and low cost, comprising the following steps:
[0028] (1) Add 21.814 g of sodium gluconate and 0.003 mol of catalyst into 20 mL of deionized water and mix for later use;
[0029] (2) Raise the temperature to 65°C and begin to drip 61.836 g of 27.5 wt % hydrogen peroxide solution. Stir mechanically and use 32 wt % sodium hydroxide solution to control the pH to 11.4-11.8. After the dripping is completed, keep warm for 2.0 h, i.e. the reaction is completed. Discharge the material and filter to obtain the sodium xylarate solution.
[0030] According to liquid phase determination, the conversion rate of sodium gluconate reaches 92%, and the conversion rate of sodium xylarate can reach 75%.
[0031] Example 2
[0032] The present invention provides a method for synthesizing xylaric acid salt with high efficiency and low cost, comprising the following steps:
[0033] (1) Add 23.425 g potassium gluconate and 0.003 mol of catalyst into 20 mL of deionized water and mix for later use;
[0034] (2) Raise the temperature to 65°C and begin to drip 61.836 g of 27.5 wt% hydrogen peroxide solution. Stir mechanically and use 32 wt% sodium hydroxide solution to control the pH value to 11.4-11.8. After the dripping is completed, keep warm for 2.0 h, i.e. the reaction is completed. Discharge the material and filter to obtain potassium xylate solution.
[0035] According to liquid phase determination, the conversion rate of potassium gluconate reaches 92%, and the conversion rate of potassium xylate can reach 75%.
[0036] Example 3
[0037] The present invention provides a method for synthesizing xylaric acid salt with high efficiency and low cost, comprising the following steps:
[0038] (1) Add 21.814 g of sodium gluconate and 0.003 mol of the catalyst that was reused for the seventh time into 20 mL of deionized water and mix them for later use;
[0039] (2) Raise the temperature to 65°C and begin to drip 61.836 g of 27.5 wt% hydrogen peroxide solution. Stir mechanically and use 32 wt% sodium hydroxide solution to control the pH value to 11.4-11.8. After the dripping is completed, keep warm for 2.0 h, i.e. the reaction is completed. Discharge the material and filter to obtain the sodium xylarate solution.
[0040] The specific test results of the catalyst catalytic oxidation from the first cycle to the tenth cycle are shown in Table 1.
[0041] Table 1 Test results
[0042]
[0043] It can be seen from Table 1 that the conversion rates of sodium gluconate and sodium xylarate can still be maintained after the catalyst is reused 10 times.
[0044] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.
Claims
1. A method for synthesizing xylaric acid salt with high efficiency and low cost, characterized in that: The method comprises the following steps: uniformly mixing gluconate, deionized water and a catalyst, and heating the mixture to 50-70°C; adding hydrogen peroxide at a certain drop rate controlled by a peristaltic pump, reacting the mixture under certain temperature and pH conditions, keeping the mixture warm for a period of time after the addition is completed, and filtering the mixture to obtain a xylate solution.
2. The method for synthesizing xylaric acid salt with high efficiency and low cost according to claim 1, characterized in that: The gluconate is one of sodium gluconate, potassium gluconate and calcium gluconate.
3. The method for synthesizing xylaric acid salt with high efficiency and low cost according to claim 1, characterized in that: The mass ratio of the gluconate to deionized water is 1:0.7-2.0, preferably 1:0.7-1.
3.
4. The method for synthesizing xylaric acid salt with high efficiency and low cost according to claim 1, characterized in that: The molar ratio of the gluconate to the catalyst is 1:0.03-0.
08.
5. The method for synthesizing xylaric acid salt with high efficiency and low cost according to claim 1, characterized in that: The catalyst is a Fe / Fe3C nanoparticle-loaded porous nitrogen-doped carbon-based oxygen reduction catalyst.
6. The method for synthesizing xylaric acid salt with high efficiency and low cost according to claim 1, characterized in that: The dropping rate of the hydrogen peroxide solution is 0.1-0.6 L / min.
7. The method for synthesizing xylaric acid salt with high efficiency and low cost according to claim 1, characterized in that: The reaction temperature is 50-70° C., and the insulation time is 0.5-3.0 h.
8. The method for synthesizing xylaric acid salt with high efficiency and low cost according to claim 1, characterized in that: The molar ratio of the gluconate to H2O2 is 1:2.0-5.
0.
9. The method for synthesizing xylaric acid salt with high efficiency and low cost according to claim 1, characterized in that: The pH is adjusted by using a sodium hydroxide solution with a mass fraction of 20%-50%, and the pH value of the solution is adjusted to 8-12.