A photochemical synthesis process for the preparation of solid hydrogen peroxide compounds

Abstract

The photochemical synthesis method for preparing the solid hydrogen peroxide compound comprises the following steps: (1) loading a benzyl compound and a salt, an acid or urea into a reactor and introducing oxygen or air to form a reaction system, irradiating the reaction system with a light source containing ultraviolet light, controlling the reaction temperature to be between room temperature and 60 DEG C, and allowing the reaction to proceed for at least 10 minutes; and (2) crystallizing, separating and drying the liquid system containing the hydrogen peroxide compound to obtain the solid hydrogen peroxide compound. The present application provides a new technical solution for preparing the solid hydrogen peroxide compound. The method is simple and safe, and overcomes the defects of the reaction mechanism of the photocatalyst system.

Description

Technical Field

[0001] This invention belongs to the field of solid hydrogen peroxide compound preparation technology, and particularly relates to a method for photochemical synthesis of solid hydrogen peroxide compounds. Background Technology

[0002] Solid hydrogen peroxide compounds include peroxyacids, peroxyates, and hydrogen peroxide adducts. Hydrogen peroxide adducts are chelates formed by the addition of hydrogen peroxide molecules to one or more other molecules. They possess most of the functions and properties of hydrogen peroxide and are therefore also called solid hydrogen peroxide. Compared to liquid hydrogen peroxide, it has advantages such as ease of transportation, storage, and use, and can replace liquid hydrogen peroxide in traditional applications such as bleaching, textiles, and medicine.

[0003] In existing technologies, the preparation of solid hydrogen peroxide compounds requires the use of high-concentration hydrogen peroxide. For example, there are two production processes for peracetic acid: acetic acid oxidation and acetic anhydride oxidation. The acetic acid oxidation process involves oxidizing acetic acid in the presence of hydrogen peroxide, and the reaction can be either batch or continuous. The acetic anhydride oxidation process involves intensively mixing acetic anhydride and hydrogen peroxide separately in a micromixer, and then feeding them into a microchannel reactor for reaction. Pure peroxymonosulfuric acid is prepared by reacting solid sulfur trioxide with anhydrous hydrogen peroxide, and pernitric acid is prepared by reacting N₂O₅ with H₂O₂. Sodium percarbonate in peroxide salts is typically produced by reacting hydrogen peroxide with sodium carbonate. In some variations of what is generally referred to as the "wet process," this method involves generating an aqueous solution of sodium carbonate, mixing it with an aqueous solution of hydrogen peroxide, and adjusting the reaction conditions, including the concentrations of sodium carbonate and hydrogen peroxide and a selected temperature, to allow sodium percarbonate to crystallize from the solution. The solid sodium percarbonate product is usually separated from the solution by filtration or centrifugation and may undergo further surface treatment, granulation, or drying. The production of urea peroxide, a hydrogen peroxide adduct, commonly employs a wet process involving the reaction of hydrogen peroxide and urea. Theoretically, a 1:1 molar ratio of hydrogen peroxide to urea is sufficient to produce solid urea peroxide. However, the production process is limited by the solubility of both substances and the highly unstable and easily decomposed nature of hydrogen peroxide. Even under light-proof, dry, and sealed conditions, high-concentration hydrogen peroxide can decompose in the presence of a certain amount of air, and this decomposition reaction is highly explosive. Therefore, the preparation of solid hydrogen peroxide compounds using hydrogen peroxide as a raw material poses significant potential safety hazards. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a photochemical synthesis method for preparing solid hydrogen peroxide compounds, so as to simplify the process, reduce energy consumption and cost, and improve safety.

[0005] The photochemical synthesis method for preparing solid hydrogen peroxide compounds described in this invention comprises the following steps:

[0006] (1) Benzyl compounds and salts, acids or urea are loaded into a reactor and oxygen or air is introduced to form a reaction system. The reaction system is irradiated with a light source containing ultraviolet light. The reaction temperature is controlled at room temperature to 60°C and the reaction time is at least 10 min. After the reaction time is reached, a liquid system containing hydrogen peroxide is obtained.

[0007] (2) Crystallize, separate and dry the liquid system containing hydrogen peroxide to obtain solid hydrogen peroxide.

[0008] The above-described photochemical synthesis method for preparing solid hydrogen peroxide compounds uses a salt that is a sulfate, carbonate, phosphate, borate, or acetate, which is either solid or a saturated solution at the reaction temperature (including saturated aqueous solutions of sulfates, carbonates, phosphates, borates, or acetates, and ethanolic solutions of sulfates, carbonates, phosphates, borates, or acetates); the acid is liquid anhydrous acetic acid, a saturated aqueous solution of acetic acid at the reaction temperature, a saturated ethanolic solution of phosphoric anhydride at the reaction temperature, a saturated acidic aqueous solution of nitrite at the reaction temperature, or a saturated acidic aqueous solution of sulfate at the reaction temperature; the urea is solid urea or a saturated urea solution at the reaction temperature (including saturated aqueous solutions of urea and saturated ethanolic solutions of urea); when sulfates, carbonates, When phosphates, borates, or acetates are solid, and urea is solid urea, the mass-to-volume ratio of the phosphates to benzyl compounds (which are liquid) is 0.3–0.5:1, with mass units in g and volume units in mL, or mass units in kg and volume units in L. When sulfates, carbonates, phosphates, borates, or acetates are saturated solutions at the reaction temperature, and the acid is liquid anhydrous acetic acid, a saturated aqueous solution of acetic acid at the reaction temperature, a saturated ethanol solution of phosphoric anhydride at the reaction temperature, a saturated acidic aqueous solution of nitrite at the reaction temperature, or a saturated acidic aqueous solution of sulfate at the reaction temperature, and urea is a saturated urea solution at the reaction temperature, the volume ratio of the urea to benzyl compounds (which are liquid) is 0.5–2:1.

[0009] In the above-described photochemical synthesis method for preparing solid hydrogen peroxide compounds, the benzyl compounds are benzyl alcohol compounds, benzyl ether compounds, benzyl acid compounds, benzyl amine compounds, benzyl aldehyde compounds, benzyl alkane compounds, or benzyl ketone compounds.

[0010] The benzyl alcohol compound is preferably dimethylbenzylmethanol, 2-phenylethanol, 3-phenyl-1-propanol, or benzyl alcohol; the benzyl ether compound is preferably benzyl methyl ether, dibenzyl ether, or isochloromethane; the benzyl acid compound is preferably benzoic acid or 1,4-phenylenediacetic acid; the benzyl amine compound is preferably N,N-dimethylbenzylamine or 1,2,3,4-tetrahydroisoquinoline; the benzyl aldehyde compound is preferably benzaldehyde or phenylacetaldehyde; the benzyl alkane compound is preferably diphenylmethane or p-xylene; and the benzyl ketone compound is preferably 2-indanone or methoxyphenylacetone.

[0011] In the above method, the light source containing ultraviolet light is an artificial light source or natural light; the preferred artificial light source is a xenon lamp (λ = 300-1000nm) or a high-pressure mercury lamp (λ = 254-365nm).

[0012] In the above method, the air can be compressed air or natural air, with compressed air being preferred.

[0013] Compared with the prior art, the method described in this invention has the following beneficial technical effects:

[0014] (1) The method of the present invention loads benzyl compounds and salts, acids or urea into a reactor and introduces oxygen or air to form a reaction system. Under the irradiation of a light source containing ultraviolet light, a reaction occurs to generate hydrogen peroxide compounds. After crystallization, separation and drying, solid hydrogen peroxide compounds are obtained, providing a new technical solution for the preparation of solid hydrogen peroxide compounds.

[0015] (2) The photochemical synthesis method described in this invention uses benzyl compounds and salt, acid or urea and oxygen or air to form a reaction system, which overcomes the reaction mechanism defects of the photocatalyst system, that is, avoids the separation problem of catalyst and sacrificial agent, as well as the problems of low reaction efficiency and self-decomposition of product solid hydrogen peroxide.

[0016] (3) The raw materials of the method described in this invention are easy to obtain, the process is simple and safe, and the equipment is conventional, thus facilitating the small-scale or large-scale production of solid hydrogen peroxide compounds. Attached Figure Description

[0017] Figure 1 This is a schematic diagram of the reaction apparatus used in the embodiment. In the diagram, 1—artificial light source, 2—quartz glass cover, 3—reactor, 4—air inlet, 5—air outlet, 6—cooler, 7—water inlet, 8—water outlet, and 9—stirrer.

[0018] Figure 2 The graph shows the change in concentration of ammonium persulfate prepared in Example 1 over reaction time. Detailed Implementation

[0019] The photochemical synthesis method for producing H2O2 using benzyl compounds as a hydrogen source, as described in this invention, will be further illustrated below with reference to the accompanying drawings and examples. Obviously, the described examples are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without inventive effort are within the scope of protection of this invention.

[0020] In the following embodiments, except for Embodiments 3 and 4, all other embodiments use Figure 1 The reaction apparatus shown includes an artificial light source 1, a quartz glass cover 2, a reactor 3, a condenser 6, and a stirrer 9. The stirrer 9 is a pedestal-type stirrer, mainly composed of a hollow base, a motor installed inside the base, and a stirring paddle connected to the motor's output shaft. The reactor 3 is a glass cylinder closed at the bottom and open at the top, with an air inlet 4 and an air outlet 5 respectively provided on its left and right side walls. The reactor 3 is placed on the top surface of the stirrer 9's base, and the stirring paddle of the stirrer 9 is located inside the reactor 3. The contact point between the stirring paddle and the bottom wall of the reactor 3 is sealed with sealant. The condenser 6 is used to control the reaction temperature of the reaction system. It is a jacketed structure and is arranged around the outer wall of the reactor 3. The condenser 6 has a water inlet 7 and a water outlet 8 respectively provided on its left and right side walls. The quartz glass cover 2 is matched with the reactor 3 and is used to cover the upper part of the reactor 3. The artificial light source 1 is fixed above the reactor 3. In use, the inlet 7 and outlet 8 of the cooler 6 are connected to the outlet and inlet of the constant temperature water bath device respectively through pipe fittings, and the inlet 4 of the reactor 3 is connected to the oxygen source through pipe fittings.

[0021] The benzyl compounds, salts, acids, and urea in the following examples were of analytical grade and purchased commercially.

[0022] Example 1

[0023] In this embodiment, dimethylbenzyl methanol and a saturated aqueous solution of ammonium sulfate at 20°C are used as raw materials, oxygen is used as the oxygen source, and a xenon lamp is used as the light source containing ultraviolet light. Figure 1 The reaction apparatus shown follows the steps below:

[0024] (1) 5 mL of dimethylbenzyl methanol and 5 mL of ammonium sulfate saturated aqueous solution were added to reactor 3 and mixed thoroughly. Then, oxygen was introduced into the reactor at a flow rate of 10 mL / min to form a reaction system. The xenon lamp was 300 W with a light power density of 560 mW / cm². 2 Under the irradiation and stirring of the xenon lamp, the reaction was carried out at 20°C for 1 hour. During the entire reaction process, oxygen was kept in the air and the gas outlet 5 set on the side wall of the reactor 3 was kept open. After the reaction time was reached, a liquid system containing (NH4)2S2O8 was obtained.

[0025] The concentration of (NH4)2S2O8 in the liquid system containing (NH4)2S2O8 obtained after 1 hour of reaction was tested according to the method described in national standard GB / T23940-2021. The test results are shown in [Figure 1]. Figure 2 The concentration of (NH4)2S2O8 was 19.43 mM.

[0026] (2) Repeat step (1) and react for 2 hours; the concentration of (NH4)2S2O8 in the liquid system containing (NH4)2S2O8 obtained after 2 hours of reaction is tested using the method described in national standard GB / T23940-2021. The test results are shown in […]. Figure 2 The concentration of (NH4)2S2O8 was 36.47 mM.

[0027] (3) Repeat step (1) and react for 3 hours; the concentration of (NH4)2S2O8 in the liquid system containing (NH4)2S2O8 obtained after 3 hours of reaction is tested using the method described in national standard GB / T23940-2021. The test results are shown in […]. Figure 2 The concentration of (NH4)2S2O8 was 55.86 mM.

[0028] (4) Repeat step (1) and react for 4 hours; the concentration of (NH4)2S2O8 in the liquid system containing (NH4)2S2O8 obtained after 4 hours of reaction is tested using the method described in national standard GB / T23940-2021. The test results are shown in […]. Figure 2 The concentration of (NH4)2S2O8 was 72.42 mM, and the yield was 24.48%.

[0029] from Figure 2 It can be seen that as the reaction time increases, the concentration of (NH4)2S2O8 in the resulting liquid system containing (NH4)2S2O8 increases;

[0030] (5) The liquid system containing (NH4)2S2O8 obtained by reacting in step (4) for 4 hours was allowed to stand and spontaneously crystallize at room temperature. Then, it was filtered and the solid phase obtained by filtration was centrifuged to remove water. Then it was dried at 80℃ for 300 min to obtain solid (NH4)2S2O8 with a mass of 0.276 g.

[0031] The obtained solid (NH4)2S2O8 was analyzed using the method described in the national standard GB / T26519.1-2021. The mass fraction of (NH4)2S2O8 was greater than 98.5%, the mass fraction of active O was greater than 6.91%, and the mass fraction of moisture was less than 0.15%, which is a superior product and meets the national standard.

[0032] Example 2

[0033] In this embodiment, 2-phenylethanol and solid sodium bisulfate are used as raw materials, oxygen is used as the oxygen source, and a xenon lamp is used as the light source containing ultraviolet light. Figure 1 The reaction apparatus shown follows the steps below:

[0034] (1) 5 mL of 2-phenylethanol and 2 g of solid sodium bisulfate were loaded into reactor 3. Then, oxygen was introduced into the reactor at a flow rate of 10 mL / min to form a reaction system. The xenon lamp was 300 W with a light power density of 560 mW / cm². 2 Under the irradiation and stirring of the xenon lamp, the reaction was carried out at 30°C for 4 hours. During the entire reaction process, oxygen was kept in the air and the gas outlet 5 set on the side wall of the reactor 3 was kept open. After the reaction time was reached, a liquid system containing Na2S2O8 was obtained.

[0035] The concentration of Na2S2O8 in the liquid system containing Na2S2O8 obtained after 4 hours of reaction was tested using the method described in national standard GB / T23940-2021. The concentration of Na2S2O8 in the liquid system was 40.22 mM, and the yield was approximately 14.29%.

[0036] (2) The liquid system containing Na2S2O8 obtained in step (1) was allowed to stand and spontaneously crystallize at room temperature. Then it was filtered and the solid phase obtained by filtration was centrifuged to remove water. Then it was dried at 80℃ for 300 min to obtain solid Na2S2O8 with a mass of 0.153 g.

[0037] The obtained solid Na2S2O8 was analyzed using the method described in the national standard GB / T26519.1-2021. The mass fraction of Na2S2O8 was greater than 99%, the mass fraction of active O was greater than 6.65%, and the mass fraction of moisture was less than 0.1%, which is a superior product and meets the industry standard.

[0038] Example 3

[0039] In this embodiment, N,N-dimethylbenzylamine and a saturated aqueous solution of sodium sulfate at 30°C are used as raw materials, natural air is used as the oxygen source, and natural light is used as the light source containing ultraviolet light. The steps are as follows:

[0040] (1) 5 mL of N,N-dimethylbenzylamine and 5 mL of sodium sulfate saturated aqueous solution were placed into a shallow pool photoreactor exposed to air and mixed evenly. The mixture was reacted for 4 h under natural light and stirring (reaction temperature about 30 °C). After the reaction time was reached, a liquid system containing Na2SO4·H2O·0.5H2O2 adduct was obtained.

[0041] (2) The liquid system containing Na2SO4·H2O·0.5H2O2 adduct obtained in step (1) is cooled to 15°C under stirring to crystallize, and then filtered under reduced pressure. The filter cake obtained is dried at 140°C for 150 min. The white powdery crystals obtained are solid Na2SO4·H2O·0.5H2O2 adduct with a mass of 0.065 g.

[0042] (3) According to the reference "Li Benbin, Zhao Hongkun, Liu Guoji. Preparation and characterization of sodium sulfate hydrogen peroxide adduct [J]. Journal of Zhengzhou University (Engineering Science), 2004, (02): 20-22+35.)", the solid Na2SO4·H2O·0.5H2O2 adduct was analyzed. The operation was as follows: 0.005g of Na2SO4·H2O·0.5H2O2 was dissolved, and the sodium sulfate content was titrated with standard barium chloride solution using alizarin red as an indicator. The mass fraction of sodium sulfate in the adduct was 62.7%. Based on the mass fraction of sodium sulfate in the solid Na2SO4·H2O·0.5H2O2 adduct, the concentration of Na2SO4·H2O·0.5H2O2 adduct in the liquid system containing Na2SO4·H2O·0.5H2O2 obtained after 4h of reaction was calculated to be 13.17mM, and the yield was about 5.82%.

[0043] According to the reference in step (3), 0.005g of Na2SO4·H2O·0.5H2O2 was dissolved, and the hydrogen peroxide content was determined by the cerium sulfate method (Wang Ruibin. Research on accurate determination method of hydrogen peroxide content [J]. Chemical Engineer, 2005, 18(12):62-64.). The mass fraction of hydrogen peroxide in the adduct was 36.9%; the water content was calculated by the difference method, and the mass fraction of water was 0.19%.

[0044] The active oxygen content was calculated according to the literature "Huang Ganqiang. Preparation of peroxyacid and determination of its active oxygen content [J]. China Pulp & Paper, 1997, (00): 44-47.)", and the mass fraction of active oxygen in the adduct was found to be 6.34%.

[0045] Example 4

[0046] In this embodiment, N,N-dimethylbenzylamine and a saturated aqueous solution of sodium sulfate and sodium chloride at 20°C are used as raw materials. The mass ratio of sodium sulfate to sodium chloride in the saturated aqueous solution is 1:1. Natural air is used as the oxygen source, and natural light is used as the light source containing ultraviolet light. The steps are as follows:

[0047] (1) 5 mL of N,N-dimethylbenzylamine and 5 mL of sodium sulfate and sodium chloride saturated aqueous solution were put into a shallow pool photoreactor exposed to air and mixed evenly. The mixture was reacted for 4 h under natural light and stirring (reaction temperature about 20 °C). After the reaction time was reached, a liquid system containing 4Na2SO4·2H2O2·NaCl adduct was obtained.

[0048] (2) Cool the liquid system containing the 4Na2SO4·2H2O2·NaCl adduct obtained in step (1) to 15°C to crystallize it, then filter it and centrifuge the obtained solid phase to remove water, and then dry it at 80°C for 300 min to obtain the solid 4Na2SO4·2H2O2·NaCl adduct with a mass of 0.059 g.

[0049] (3) The determination of sodium sulfate content, hydrogen peroxide content, and moisture content in the solid 4Na2SO4·2H2O2·NaCl adduct was performed according to Example 3. The mass fraction of sodium sulfate in the adduct was 37.72%, the mass fraction of hydrogen peroxide was 24.6%, and the moisture content was less than 0.18%, meeting the requirements of the product standard. The determination of active oxygen was the same as in Example 3, and the mass fraction of active oxygen in the adduct was 4.36%. Based on the mass fraction of sodium sulfate in the solid 4Na2SO4·2H2O2·NaCl adduct, the concentration of the 4Na2SO4·2H2O2·NaCl adduct in the liquid system containing the 4Na2SO4·2H2O2·NaCl adduct obtained after 4 hours of reaction was calculated to be 12.25 mM, and the yield was approximately 5.03%.

[0050] Example 5

[0051] In this embodiment, 1,2,3,4-tetrahydroisoquinoline and solid sodium metaborate are used as raw materials, compressed air is used as the oxygen source, and a xenon lamp is used as the light source containing ultraviolet light. Figure 1 The reaction apparatus shown follows the steps below:

[0052] (1) 5 mL of 1,2,3,4-tetrahydroisoquinoline and 2 g of sodium metaborate were loaded into reactor 3. Then, compressed air was introduced into the reactor at a flow rate of 5 mL / min to form a reaction system. The xenon lamp was 300 W with a light power density of 560 mW / cm². 2 Under the irradiation and stirring of the xenon lamp, the reaction was carried out at 20°C for 4 hours. During the entire reaction process, compressed air was kept in the air and the air outlet 5 set on the side wall of the reactor 3 was kept open. After the reaction time was reached, a liquid system containing sodium perborate was obtained.

[0053] The sodium perborate concentration in the liquid system containing sodium perborate obtained after 4 hours of reaction was tested using the method described in industry standard HG / T 2518-2008. The concentration of sodium perborate in the liquid system was 169.38 mM, and the yield was approximately 40.62%.

[0054] (2) The liquid system containing sodium perborate obtained in step (1) was allowed to stand at 20°C to allow it to crystallize spontaneously. Then, it was filtered and the solid phase obtained by filtration was centrifuged to remove water. Then, it was dried at 40°C for 300 min to obtain solid sodium perborate with a mass of 0.458 g.

[0055] The obtained solid sodium perborate was analyzed using the method described in industry standard HG / T 2518-2008. The mass fraction of active O was greater than 15.1%, indicating that it was sodium perborate monohydrate, which meets the industry standard.

[0056] Example 6

[0057] In this embodiment, p-xylene and a saturated sodium bicarbonate ethanol solution at 20°C are used as raw materials, compressed air is used as the oxygen source, and a xenon lamp is used as the light source containing ultraviolet light. Figure 1 The reaction apparatus shown follows the steps below:

[0058] (1) Add 5 mL of p-xylene and 5 mL of sodium bicarbonate saturated ethanol solution to reactor 3 and mix thoroughly. Then, introduce compressed air into the reactor at a flow rate of 10 mL / min to form a reaction system. Use a 300W xenon lamp with a light power density of 400 mW / cm². 2 Under the irradiation and stirring of the xenon lamp, the reaction was carried out at 20°C for 4 hours. During the entire reaction process, compressed air was kept in the air and the air outlet 5 set on the side wall of the reactor 3 was kept open. After the reaction time was reached, a liquid system containing sodium percarbonate was obtained.

[0059] The sodium percarbonate concentration in the liquid system containing sodium percarbonate obtained after 4 hours of reaction was tested using the method described in industry standard HG / T 2764-2008. The concentration of sodium percarbonate in the liquid system was 43.78 mM, and the yield was approximately 14.93%.

[0060] (2) The liquid system containing sodium percarbonate obtained in step (1) was allowed to stand and evaporate and crystallize naturally at room temperature. Then it was filtered and the solid phase obtained by filtration was centrifuged and dehydrated. Then it was dried at 90°C for 300 min to obtain solid sodium percarbonate with a mass of 0.162 g.

[0061] The obtained solid sodium percarbonate was analyzed using the method described in industry standard HG / T 2764-2008. The mass fraction of active oxygen was greater than 13.5%, and the mass fraction of moisture was less than 2.0%, classifying it as a type I product, which meets industry standards.

[0062] Example 7

[0063] In this embodiment, diphenylmethane and a saturated aqueous solution of sodium bicarbonate at 40°C are used as raw materials, compressed air is used as the oxygen source, and a xenon lamp is used as the light source containing ultraviolet light. Figure 1 The reaction apparatus shown follows the steps below:

[0064] (1) Add 5 mL of diphenylmethane and 5 mL of saturated sodium bicarbonate aqueous solution to reactor 3 and mix thoroughly. Then, introduce compressed air into the reactor at a flow rate of 10 mL / min to form a reaction system. Use a 300W xenon lamp with a light power density of 560 mW / cm². 2Under the irradiation and stirring of the xenon lamp, the reaction was carried out at 40°C for 4 hours. During the entire reaction process, compressed air was kept in the air and the air outlet 5 set on the side wall of the reactor 3 was kept open. After the reaction time was reached, a liquid system containing sodium percarbonate was obtained.

[0065] The sodium percarbonate concentration in the liquid system containing sodium percarbonate obtained after 4 hours of reaction was tested using the method described in industry standard HG / T 2764-2008. The concentration of sodium percarbonate in the liquid system was 85.29 mM, and the yield was approximately 27.23%.

[0066] (2) The liquid system containing sodium percarbonate obtained in step (1) was allowed to stand and evaporate and crystallize naturally at room temperature. Then it was filtered and the solid phase obtained by filtration was centrifuged and dehydrated. Then it was dried at 90°C for 300 min to obtain solid sodium percarbonate with a mass of 0.325 g.

[0067] The obtained solid sodium percarbonate was analyzed using the method described in industry standard HG / T 2764-2008. The mass fraction of active oxygen was greater than 13.5%, and the mass fraction of moisture was less than 2.0%, classifying it as a type I product, which meets industry standards.

[0068] Example 8

[0069] In this embodiment, benzaldehyde and a saturated acidic aqueous solution of potassium nitrite at 20°C are used as raw materials, compressed air is used as the oxygen source, and a xenon lamp is used as the light source containing ultraviolet light. Figure 1 The reaction apparatus shown follows the steps below:

[0070] (1) Add 5 mL of benzaldehyde and 5 mL of saturated acidic potassium nitrite solution to reactor 3 and mix thoroughly. Then, introduce compressed air into the reactor at a flow rate of 10 mL / min to form a reaction system. Use a 300W xenon lamp with a light power density of 560 mW / cm². 2 Under the irradiation and stirring of the xenon lamp, the reaction was carried out at 20°C for 4 hours. During the entire reaction process, compressed air was kept in the air and the air outlet 5 set on the side wall of the reactor 3 was kept open. After the reaction time was reached, a liquid system containing peroxynitric acid was obtained.

[0071] The concentration of peroxynitric acid in the liquid system containing peroxynitric acid obtained after 4 hours of reaction was determined by nitrite titration. Phenolphthalein was used as an indicator, and titration was performed with standard sodium nitrite solution. The titration endpoint was reached when the solution color changed from red to colorless. The concentration of peroxynitric acid in the liquid system was found to be 91.33 mM, with a yield of approximately 30.28%. The principle of nitrite titration is that peroxynitric acid can oxidize nitrite (NO2). - ) generates nitrous acid (HNO2);

[0072] (2) Cool the liquid system containing peroxynitric acid obtained in step (1) to 0°C to crystallize it, then filter it and centrifuge the obtained solid phase to remove water, and then dry it at 50°C for 300 min to obtain solid peroxynitric acid, which is 0.381 g.

[0073] The obtained solid peroxynitric acid was analyzed using the method described in Example 3. The mass fraction of active O was 15.5%, and the mass fraction of water was 2.3%.

[0074] Example 9

[0075] In this embodiment, phenylacetaldehyde and solid potassium bicarbonate at 40°C are used as raw materials, compressed air is used as the oxygen source, and a xenon lamp is used as the light source containing ultraviolet light. Figure 1 The reaction apparatus shown follows the steps below:

[0076] (1) 5 mL of phenylacetaldehyde and 2.5 g of potassium bicarbonate were added to reactor 3 and mixed thoroughly. Then, compressed air was introduced into the reactor at a flow rate of 15 mL / min to form a reaction system. The xenon lamp was 300 W with a light power density of 560 mW / cm². 2 Under the irradiation and stirring of the xenon lamp, the reaction was carried out at 30°C for 4 hours. During the entire reaction process, compressed air was kept in the air supply and the air outlet 5 set on the side wall of the reactor 3 was kept open. After the reaction time was reached, a liquid system containing potassium percarbonate was obtained.

[0077] The concentration of potassium percarbonate in the liquid system containing potassium percarbonate obtained after 4 hours of reaction was tested using the method described in industry standard HG / T 2764-2008. The concentration of potassium percarbonate in the liquid system was 7.37 mM, and the yield was approximately 2.27%.

[0078] (2) The liquid system containing potassium percarbonate obtained in step (1) was allowed to stand and evaporate and crystallize naturally at room temperature. Then it was filtered and the solid phase obtained by filtration was centrifuged and dehydrated. Then it was dried at 90°C for 300 min to obtain solid potassium percarbonate with a mass of 0.023 g.

[0079] The obtained solid potassium percarbonate was analyzed using the method described in industry standard HG / T 2764-2008. The mass fraction of active oxygen was greater than 13.5%, and the mass fraction of moisture was less than 2.0%, classifying it as a type I product, which meets industry standards.

[0080] Example 10

[0081] In this embodiment, benzoic acid and a saturated aqueous solution of sodium bicarbonate at 60°C are used as raw materials, compressed air is used as the oxygen source, and a xenon lamp is used as the light source containing ultraviolet light. Figure 1 The reaction apparatus shown follows the steps below:

[0082] (1) 5 mL of benzoic acid and 2.5 mL of saturated sodium bicarbonate aqueous solution were added to reactor 3 and mixed thoroughly. Then, compressed air was introduced into the reactor at a flow rate of 10 mL / min to form a reaction system. The xenon lamp was 300 W with a light power density of 560 mW / cm². 2 Under the irradiation and stirring of the xenon lamp, the reaction was carried out at 60°C for 4 hours. During the entire reaction process, compressed air was kept in the air and the air outlet 5 set on the side wall of the reactor 3 was kept open. After the reaction time was reached, a liquid system containing sodium percarbonate was obtained.

[0083] The sodium percarbonate concentration in the liquid system containing sodium percarbonate obtained after 4 hours of reaction was tested using the method described in industry standard HG / T 2764-2008. The concentration of sodium percarbonate in the liquid system was 59.37 mM, and the yield was approximately 18.83%.

[0084] (2) The liquid system containing sodium percarbonate obtained in step (1) was allowed to stand and evaporate and crystallize naturally at room temperature. Then it was filtered and the solid phase obtained by filtration was centrifuged and dehydrated. Then it was dried at 90°C for 300 min to obtain solid sodium percarbonate with a mass of 0.192 g.

[0085] The obtained solid sodium percarbonate was analyzed using the method described in industry standard HG / T 2764-2008. The mass fraction of active oxygen was greater than 13.5%, and the mass fraction of moisture was less than 2.0%, classifying it as a type I product, which meets industry standards.

[0086] Example 11

[0087] In this embodiment, 1,4-phenylenediacetic acid and a saturated aqueous solution of urea at 20°C are used as raw materials, natural air is used as the oxygen source, and a xenon lamp is used as the light source containing ultraviolet light. Figure 1 The reaction apparatus shown follows the steps below:

[0088] (1) Add 5 mL of 1,4-phenylenediacetic acid and 5 mL of urea saturated aqueous solution to reactor 3 and mix thoroughly. Use a 300W xenon lamp with a light power density of 560 mW / cm². 2 Under the irradiation and stirring of the xenon lamp, the reaction was carried out at 20°C for 4 hours. During the entire reaction process, the air inlet 4 and air outlet 5 set on the side wall of the reactor 3 were in an open state. After the reaction time was reached, a liquid system containing CO(NH2)2·H2O2 adduct was obtained.

[0089] The concentration of CO(NH2)2·H2O2 adduct in the liquid system obtained after 4 hours of reaction was tested using the method described in enterprise standard Q / SXSA034-2016. The concentration of CO(NH2)2·H2O2 adduct in the liquid system was 72.23 mM, and the yield was approximately 22.67%.

[0090] (2) Cool the liquid system containing CO(NH2)2·H2O2 adduct obtained in step (1) to 10°C to crystallize it, then filter it and centrifuge the obtained solid phase to remove water, and then dry it at 10°C for 300 min to obtain solid CO(NH2)2·H2O2 adduct with a mass of 0.275 g.

[0091] The obtained solid CO(NH2)2·H2O2 adduct was analyzed using the method described in enterprise standard Q / SXSA034-2016. The mass fraction of active O was greater than 16.0%, and the mass fraction of H2O2 was greater than 35.0%, which meets the industry standard.

[0092] Example 12

[0093] In this embodiment, benzyl methyl ether and a urea-saturated ethanol solution at 20°C are used as raw materials, compressed air is used as the oxygen source, and a high-pressure mercury lamp is used as the light source containing ultraviolet light. Figure 1 The reaction apparatus shown follows the steps below:

[0094] (1) 5 mL of benzyl methyl ether and 10 mL of urea saturated ethanol solution were loaded into reactor 3 and mixed thoroughly. Then, compressed air was introduced into the reactor at a flow rate of 10 mL / min to form a reaction system. A 300W high-pressure mercury lamp with a light power density of 400 mW / cm² was used. 2 Under the irradiation and stirring of the mercury lamp, the reaction was carried out at 20°C for 4 hours. During the entire reaction process, compressed air was kept in the air and the air outlet 5 set on the side wall of the reactor 3 was kept open. After the reaction time was reached, a liquid system containing CO(NH2)2·H2O2 adduct was obtained.

[0095] The concentration of CO(NH2)2·H2O2 adduct in the liquid system obtained after 4 hours of reaction was tested using the method described in enterprise standard Q / SXSA034-2016. The concentration of CO(NH2)2·H2O2 adduct in the liquid system was 181.16 mM, and the yield was approximately 43.72%.

[0096] (2) Cool the liquid system containing CO(NH2)2·H2O2 adduct obtained in step (1) to 10°C to crystallize it, then filter it and centrifuge the obtained solid phase to remove water, and then dry it at 10°C for 300 min to obtain solid CO(NH2)2·H2O2 adduct with a mass of 0.594 g.

[0097] The obtained solid CO(NH2)2·H2O2 adduct was analyzed using the method described in enterprise standard Q / SXSA034-2016. The mass fraction of active O was greater than 16.0%, and the mass fraction of H2O2 was greater than 35.0%, which meets the industry standard.

[0098] Example 13

[0099] In this embodiment, 3-phenyl-1-propanol and solid urea are used as raw materials, compressed air is used as the oxygen source, and a high-pressure mercury lamp is used as the light source containing ultraviolet light. Figure 1 The reaction apparatus shown follows the steps below:

[0100] (1) 5 mL of 3-phenyl-1-propanol and 2.25 g of urea were loaded into reactor 3. Then, compressed air was introduced into the reactor at a flow rate of 10 mL / min to form a reaction system. A 300 W high-pressure mercury lamp with a light power density of 400 mW / cm² was used. 2 Under the irradiation and stirring of the mercury lamp, the reaction was carried out at 40°C for 4 hours. During the entire reaction process, compressed air was kept in the air and the air outlet 5 set on the side wall of the reactor 3 was kept open. After the reaction time was reached, a liquid system containing CO(NH2)2·H2O2 adduct was obtained.

[0101] The concentration of CO(NH2)2·H2O2 adduct in the liquid system obtained after 4 hours of reaction was tested using the method described in enterprise standard Q / SXSA034-2016. The concentration of CO(NH2)2·H2O2 adduct in the liquid system was 101.16 mM, and the yield was approximately 33.72%.

[0102] (2) Cool the liquid system containing CO(NH2)2·H2O2 adduct obtained in step (1) to 10°C to crystallize it, then filter it and centrifuge the obtained solid phase to remove water, and then dry it at 10°C for 300 min to obtain solid CO(NH2)2·H2O2 adduct with a mass of 0.396 g.

[0103] The obtained solid CO(NH2)2·H2O2 adduct was analyzed using the method described in enterprise standard Q / SXSA034-2016. The mass fraction of active O was greater than 16.0%, and the mass fraction of H2O2 was greater than 35.0%, which meets the industry standard.

[0104] Example 14

[0105] In this embodiment, dibenzyl ether and liquid anhydrous acetic acid are used as raw materials, compressed air is used as the oxygen source, and a xenon lamp is used as the light source containing ultraviolet light. Figure 1 The reaction apparatus shown follows the steps below:

[0106] (1) 5 mL of dibenzyl ether and 5 mL of anhydrous acetic acid were loaded into reactor 3 and mixed thoroughly. Then, compressed air was introduced into the reactor at a flow rate of 10 mL / min to form a reaction system. The xenon lamp was 300 W with a light power density of 560 mW / cm². 2Under the irradiation and stirring of the xenon lamp, the reaction was carried out at 20°C for 4 hours. During the entire reaction process, compressed air was kept in the air supply and the air outlet 5 set on the side wall of the reactor 3 was kept open. After the reaction time was reached, a liquid system containing peracetic acid was obtained.

[0107] The concentration of peracetic acid in the liquid system containing peracetic acid obtained after 4 hours of reaction was tested using the method described in GB / T 19104-2008. The concentration of peracetic acid in the liquid system was 57.74 mM, and the yield was approximately 15.32%.

[0108] (2) Cool the liquid system containing peracetic acid obtained in step (1) to 10°C to crystallize it, then filter it and centrifuge the obtained solid phase to remove water, and then dry it at 10°C for 300 min to obtain solid peracetic acid with a mass of 0.184 g.

[0109] The obtained solid peracetic acid was analyzed using the method described in the national standard GB / T 19104-2008. The mass fraction of C2H4O3 was greater than 15%, the mass fraction of sulfate was less than 3%, and the mass fraction of residue on ignition was less than 0.1%, which indicates it is a type I product and meets industry standards.

[0110] Example 15

[0111] In this embodiment, benzyl alcohol and a saturated aqueous solution of acetic acid are used as raw materials, compressed air is used as the oxygen source, and a xenon lamp is used as the light source containing ultraviolet light. Figure 1 The reaction apparatus shown follows the steps below:

[0112] (1) 5 mL of benzyl alcohol and 5 mL of saturated aqueous acetic acid solution were added to reactor 3 and mixed thoroughly. Then, compressed air was introduced into the reactor at a flow rate of 10 mL / min to form a reaction system. The xenon lamp was 300 W with a light power density of 560 mW / cm². 2 Under the irradiation and stirring of the xenon lamp, the reaction was carried out at 30°C for 4 hours. During the entire reaction process, compressed air was kept in the air and the air outlet 5 set on the side wall of the reactor 3 was kept open. After the reaction time was reached, a liquid system containing peracetic acid was obtained.

[0113] The concentration of peracetic acid in the liquid system containing peracetic acid obtained after 4 hours of reaction was tested using the method described in GB / T 19104-2008. The concentration of peracetic acid in the liquid system was 77.74 mM, and the yield was approximately 25.48%.

[0114] (2) Cool the liquid system containing peracetic acid obtained in step (1) to 10°C to crystallize it, then filter it and centrifuge the obtained solid phase to remove water, and then dry it at 10°C for 300 min to obtain solid peracetic acid with a mass of 0.273 g.

[0115] The obtained solid peracetic acid was analyzed using the method described in the national standard GB / T 19104-2008. The mass fraction of C2H4O3 was greater than 15%, the mass fraction of sulfate was less than 3%, and the mass fraction of residue on ignition was less than 0.1%, which indicates it is a type I product and meets industry standards.

[0116] Example 16

[0117] In this embodiment, 2-indanone and a saturated aqueous solution of sodium acetate at 20°C were used as raw materials, compressed air was used as the oxygen source, and a high-pressure mercury lamp was used as the light source containing ultraviolet light. Figure 1 The reaction apparatus shown follows the steps below:

[0118] (1) 5 mL of 2-indanone and 5 mL of saturated sodium acetate aqueous solution were added to reactor 3 and mixed thoroughly. Then, compressed air was introduced into the reactor at a flow rate of 10 mL / min to form a reaction system. The mercury lamp was 300 W with a light power density of 300 mW / cm². 2 Under the irradiation and stirring of the mercury lamp, the reaction was carried out at 20°C for 4 hours. During the entire reaction process, compressed air was kept in the air and the air outlet 5 set on the side wall of the reactor 3 was kept open. After the reaction time was reached, a liquid system containing sodium peracetate was obtained.

[0119] The concentration of sodium peracetate in the liquid system containing sodium peracetate obtained after 4 hours of reaction was determined by iodine titration. The concentration of sodium peracetate in the liquid system was 87.74 mM, and the yield was approximately 29.58%. The iodine titration method was performed in accordance with the national standard GB / T23940-2021. The basic principle is that sodium peracetate can oxidize iodide ions (I₂O₃). - Iodine (I2) is generated and then titrated with a standard iodine solution. The titration endpoint is when the mixed solution turns pale yellow.

[0120] (2) The liquid system containing sodium peracetate obtained in step (1) is evaporated, concentrated and crystallized at 70°C, then filtered and the solid phase obtained by filtration is centrifuged and dehydrated, and then dried at 60°C for 300 min to obtain solid sodium peracetate with a mass of 0.305 g.

[0121] The obtained solid sodium peracetate was analyzed using the method described in Example 3. The mass fraction of active O was 14.2%, and the mass fraction of water was 2.8%.

[0122] Example 17

[0123] In this embodiment, methoxyphenyl acetone and a saturated ethanol solution of calcium phosphate at 20°C are used as raw materials, oxygen is used as the oxygen source, and a xenon lamp is used as the light source containing ultraviolet light. Figure 1 The reaction apparatus shown follows the steps below:

[0124] (1) 5 mL of methoxyphenyl acetone and 5 mL of calcium phosphate saturated ethanol solution were added to reactor 3 and mixed thoroughly. Then, oxygen was introduced into the reactor at a flow rate of 10 mL / min to form a reaction system. The xenon lamp was 300 W with a light power density of 560 mW / cm². 2 Under the irradiation and stirring of the xenon lamp, the reaction was carried out at 20°C for 4 hours. During the entire reaction process, oxygen was kept in the air and the gas outlet 5 set on the side wall of the reactor 3 was kept open. After the reaction time was reached, a liquid system containing superphosphate was obtained.

[0125] The concentration of superphosphate in the liquid system containing superphosphate obtained after 4 hours of reaction was tested using the method described in GB / T 20413-2017. The concentration of superphosphate in the liquid system was 66.65 mM, and the yield was approximately 17.81%.

[0126] (2) The liquid system containing superphosphate obtained in step (1) is evaporated, concentrated and crystallized at 70°C, then filtered and the filtered solid phase is centrifuged and dehydrated, and then dried at 50°C for 300 min to obtain solid superphosphate with a mass of 0.218 g.

[0127] The obtained solid superphosphate was analyzed using the method described in the national standard GB / T 20413-2017. The mass fraction of available phosphorus (calculated as P2O5) was greater than 18%; the mass fraction of water-soluble phosphorus (calculated as P2O5) was greater than 13%; and the mass fraction of free water was less than 12%. It is a superior product and meets the industry standard.

[0128] Example 18

[0129] In this embodiment, methoxyphenyl acetone and a saturated acidic aqueous solution of sodium sulfate at 20°C are used as raw materials, oxygen is used as the oxygen source, and a xenon lamp is used as the light source containing ultraviolet light. Figure 1 The reaction apparatus shown follows the steps below:

[0130] (1) 5 mL of methoxyphenyl acetone and 5 mL of saturated acidic sodium sulfate solution were added to reactor 3 and mixed thoroughly. Then, oxygen was introduced into the reactor at a flow rate of 10 mL / min to form a reaction system. The xenon lamp was 300 W with a light power density of 560 mW / cm². 2 Under the irradiation and stirring of the xenon lamp, the reaction was carried out at 20°C for 4 hours. During the entire reaction process, oxygen was kept in the air and the gas outlet 5 set on the side wall of the reactor 3 was kept open. After the reaction time was reached, a liquid system containing Na2S2O8 was obtained.

[0131] The concentration of Na2S2O8 in the liquid system containing Na2S2O8 obtained after 4 hours of reaction was tested using the method described in national standard GB / T23940-2021. The concentration of Na2S2O8 was 70.27 mM, and the yield was approximately 22.49%.

[0132] (2) The liquid system containing Na2S2O8 obtained by reacting in step (1) for 4 hours was allowed to stand and spontaneously crystallize at room temperature. Then, it was filtered and the solid phase obtained by filtration was centrifuged to remove water. Then, it was dried at 80℃ for 300 min to obtain solid Na2S2O8 with a mass of 0.262 g.

[0133] The obtained solid Na2S2O8 was analyzed using the method described in the national standard GB / T26519.1-2021. The mass fraction of Na2S2O8 was greater than 99%, the mass fraction of active O was greater than 6.65%, and the mass fraction of moisture was less than 0.1%, which is a superior product and meets the industry standard.

[0134] This example demonstrates that waste sodium sulfate can be used to prepare Na2S2O8, since the main component of sodium sulfate is sodium sulfate.

[0135] Example 19

[0136] In this embodiment, a saturated ethanol solution of heterochromatic phosphoric anhydride is used as the raw material, compressed air is used as the oxygen source, and a xenon lamp is used as the light source containing ultraviolet light. Figure 1 The reaction apparatus shown follows the steps below:

[0137] (1) 5 mL of a different colored saturated xenon lamp and 5 mL of phosphoric anhydride saturated ethanol solution were loaded into reactor 3. Then, compressed air was introduced into the reactor at a flow rate of 10 mL / min to form a reaction system. The xenon lamp was 300 W with a light power density of 560 mW / cm². 2 Under the irradiation and stirring of the xenon lamp, the reaction was carried out at 30°C for 4 hours. During the entire reaction process, compressed air was kept in the air supply and the air outlet 5 set on the side wall of the reactor 3 was kept open. After the reaction time was reached, a liquid system containing peroxyphosphoric acid was obtained.

[0138] The concentration of peroxyphosphoric acid in the liquid system containing peroxyphosphoric acid obtained after 4 hours of reaction was tested using the method described in the literature "Greenspan, FP and Mackellar, DG, Analytical Chemistry 20(11):106(1948). (Analytical Chemistry)". The concentration of peroxyphosphoric acid in the liquid system was 291.36 mM, and the yield was approximately 58.87%.

[0139] (2) Cool the liquid system containing peroxyphosphoric acid obtained in step (1) to 0°C to crystallize it, then filter it and centrifuge the obtained solid phase to remove water, and then dry it at 50°C for 300 min to obtain solid peroxyphosphoric acid with a mass of 0.637 g.

[0140] The phosphorus pentoxide content of the obtained solid perphosphoric acid was determined as follows: the solid perphosphoric acid sample was first boiled for 10 minutes to decompose most of the perphosphoric acid, then diluted with distilled water by about 5 times and boiled for another 5 minutes. The mass fraction of phosphorus pentoxide was determined by the quinomolybdate-limonene volumetric method (industry standard HJ 545-2017), and the result was 56.37%.

[0141] The calculation of reactive oxygen species was performed according to Example 3, and the mass fraction of reactive oxygen species in solid peroxyphosphoric acid was 14.46%.

Claims

1. A photochemical synthesis method for preparing solid hydrogen peroxide compounds, characterized in that... The process steps are as follows: (1) Benzyl compounds and salts, acids or urea are loaded into a reactor and oxygen or air is introduced to form a reaction system. The reaction system is irradiated with a light source containing ultraviolet light. The reaction temperature is controlled at room temperature to 60°C and the reaction time is at least 10 min. After the reaction time is reached, a liquid system containing hydrogen peroxide is obtained. The benzyl compounds are benzyl alcohols, benzyl ethers, benzyl acids, benzyl amines, benzyl aldehydes, benzyl alkanes, or benzyl ketones. The salt is a sulfate, carbonate, phosphate, borate, or acetate, which are either solid or saturated solutions at the reaction temperature; the acid is liquid anhydrous acetic acid, a saturated aqueous solution of acetic acid at the reaction temperature, a saturated ethanol solution of phosphoric anhydride at the reaction temperature, a saturated acidic aqueous solution of nitrite at the reaction temperature, or a saturated acidic aqueous solution of sulfate at the reaction temperature; the urea is solid urea or a saturated urea solution at the reaction temperature. (2) Crystallize, separate and dry the liquid system containing hydrogen peroxide to obtain solid hydrogen peroxide.

2. The photochemical synthesis method for preparing solid hydrogen peroxide according to claim 1, characterized in that: When sulfate, carbonate, phosphate, borate or acetate are in solid form and urea is in solid form, the mass-to-volume ratio of urea to benzyl compounds is 0.3 ~ 0.5:1, with mass units in g and volume units in mL, or mass units in kg and volume units in L. When the sulfate, carbonate, phosphate, borate, or acetate is a saturated solution at the reaction temperature, the acid is liquid anhydrous acetic acid, a saturated aqueous solution of acetic acid at the reaction temperature, a saturated ethanol solution of phosphoric anhydride at the reaction temperature, a saturated acidic aqueous solution of nitrite at the reaction temperature, or a saturated acidic aqueous solution of sulfate at the reaction temperature, and the urea is a saturated urea solution at the reaction temperature, the volume ratio of the sulfate to the benzyl compound is 0.5 to 2:

1.

3. The photochemical synthesis method for preparing solid hydrogen peroxide according to claim 1, characterized in that... The benzyl alcohol compound is dimethylbenzylmethanol, 2-phenylethanol, 3-phenyl-1-propanol, or benzyl alcohol; the benzyl ether compound is benzyl methyl ether, dibenzyl ether, or isochorium; the benzyl acid compound is benzoic acid or 1,4-phenylenediacetic acid; the benzyl amine compound is N,N-dimethylbenzylamine or 1,2,3,4-tetrahydroisoquinoline; the benzyl aldehyde compound is benzaldehyde or phenylacetaldehyde; the benzyl alkane compound is diphenylmethane or p-xylene; and the benzyl ketone compound is 2-indanone or methoxyphenylacetone.

4. The photochemical synthesis method for preparing solid hydrogen peroxide according to any one of claims 1 to 3, characterized in that... The light source containing ultraviolet light is either artificial or natural light.

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