Method for directly producing hydrogen peroxide by using high-energy electron beam to irradiate water

Abstract

The invention discloses a method for directly producing hydrogen peroxide by using high-energy electron beam irradiation water, which belongs to the technical field of inorganic compound preparation, and is characterized in that water is subjected to high-energy electron beam irradiation treatment in a closed container to obtain a hydrogen peroxide solution. The method provided by the invention can be realized in an air atmosphere at normal temperature and normal pressure, so that the method has higher safety and operability, and has the advantages of flexible process, safe operation, simple and controllable operation flow, no introduction of impurities, environmental friendliness and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of inorganic compound preparation, and particularly relates to a method for directly producing hydrogen peroxide by irradiating water with high-energy electron beams. Background Art

[0002] Hydrogen peroxide, also known as H2O2, is a very important inorganic chemical product. H2O2 not only has strong oxidation ability, but also only produces water (H2O) and oxygen (O2) after decomposition, without causing environmental pollution. Based on the above advantages, hydrogen peroxide has been widely used in many industrial fields such as the chemical industry, medicine and bioengineering, environmental remediation, and civil engineering. However, in the industrial production process of hydrogen peroxide, there are still some problems to be solved. The traditional anthraquinone method and electrolysis method have high energy consumption in the production process and may cause certain environmental pollution. In addition, these methods have high requirements for the purity and quality of raw materials, increasing the production cost. Therefore, it is of great significance to explore an efficient and environmentally friendly method for producing hydrogen peroxide.

[0003] The prior art CN 108500034 A discloses an antibiotic residue treatment process, which specifically discloses a method for irradiating antibiotic residues with electron beams. The electron beam can directly act on antibiotic molecules or antibiotic genes to destroy their internal structures, thereby achieving the purposes of sterilization, deodorization, and floc breakage. The above prior art proposes that during the process of irradiating with electron beams, hydrogen peroxide can be generated after the water in the reaction system is irradiated. However, in fact, a certain amount of hydrogen peroxide needs to be added before irradiation in the irradiation system to promote the decomposition of antibiotics. During the actual irradiation process, a part of the hydrogen peroxide added before the reaction is decomposed by the high-energy electron beam, and a part is used for the decomposition of antibiotics. Moreover, there is no control experiment to prove that the hydrogen peroxide in the reaction system at this time is generated by irradiation. And even if hydrogen peroxide can be generated under this condition, the generated dose is extremely small, and it cannot be well separated from the antibiotics, and thus cannot be applied to the production of hydrogen peroxide.

[0004] Therefore, how to provide a method for directly producing hydrogen peroxide by irradiating water with high-energy electron beams is a technical problem that needs to be urgently solved by those skilled in the art. Summary of the Invention

[0005] To solve the above technical problems, the present invention proposes a method for directly producing hydrogen peroxide by irradiating water with high-energy electron beams.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] A method for directly producing hydrogen peroxide by irradiating water with a high-energy electron beam. The water is irradiated with a high-energy electron beam in a closed container, and a hydrogen peroxide solution is obtained. The temperature of the closed container is lower than 40 °C during the high-energy electron beam irradiation process.

[0008] Beneficial effects: The high-energy electron beam irradiation of the present invention transfers the energy generated by the electron beam produced by the electron accelerator to water, thereby inducing the ionization and excitation of water molecules, releasing orbital electrons, forming hydroxyl radicals, and the hydroxyl radicals further react to produce hydrogen peroxide. At the same time, since hydrogen peroxide decomposes by 50% at 60 °C, about 10% at 40 °C, and 5% at room temperature, in order to ensure the best efficiency, the temperature should be controlled below 40 °C. Compared with the traditional production method, the method provided by the present invention has the advantages of low energy consumption and environmental protection. The advantage of irradiation is its high stability and strong penetration. Therefore, even for a relatively large volume, the high-energy electron beam can act on the irradiated object. And in industrial applications, special structures can be constructed to improve the effect of producing hydrogen peroxide, which is expected to provide a new way for the industrial production of hydrogen peroxide. At the same time, the application of this method will also further promote the wide application and development of hydrogen peroxide in various fields.

[0009] Preferably, the material of the closed container includes one or more of glass, quartz, and plastic. Since high temperature will cause the decomposition of the generated hydrogen peroxide, the material of the closed container is preferably a material that generates no or less Joule heat during irradiation.

[0010] Optionally, the plastic is selected from polyethylene (PE) or polypropylene (PP).

[0011] Preferably, the dose of the high-energy electron beam irradiation treatment is 15 - 90 KGy.

[0012] Preferably, when the material of the closed container is glass, the irradiation dose is 15 - 90 KGy.

[0013] Preferably, when the material of the closed container is quartz, the irradiation dose is 15 - 90 KGy.

[0014] Preferably, when the material of the closed container is plastic, the irradiation dose is 15 - 30 KGy.

[0015] Preferably, the temperature of the high-energy electron beam irradiation treatment is room temperature.

[0016] Preferably, the rate of the high-energy electron beam irradiation treatment is 18 KGy / s.

[0017] Preferably, the water is deionized water.

[0018] More preferably, the volume of the water is 1 - 100 mL.

[0019] Beneficial effects: In the present invention, only by placing a container filled with deionized water in an air atmosphere and directly irradiating the reaction container with a high-energy electron beam under normal temperature and pressure can hydrogen peroxide be produced to obtain a hydrogen peroxide solution. During the reaction process, no catalyst and sacrificial agent (such as ethanol, methanol, isopropanol, etc.) need to be added, and the production of hydrogen peroxide can be achieved only under pure water conditions.

[0020] Preferably, after obtaining the hydrogen peroxide solution, a color reagent is added thereto for a color reaction, and then the hydrogen peroxide content is measured and calculated using a UV-visible spectrophotometer.

[0021] More preferably, the color reagent is a 0.1 mol / L C8H5O4 solution and a 0.4 mol / L KI solution.

[0022] More preferably, the time for the color reaction is 30 min.

[0023] Compared with the prior art, the present invention has the following advantages and technical effects:

[0024] The method for directly producing hydrogen peroxide by irradiating water with a high-energy electron beam provided by the present invention does not require the addition of any catalyst, and at the same time, the production of hydrogen peroxide can be achieved without adding any organic solvent as a sacrificial agent, which not only effectively reduces the production cost but also does not introduce impurities. Moreover, the method for directly producing hydrogen peroxide by irradiating water with a high-energy electron beam in the present invention has a relatively high yield. The hydrogen peroxide content generated under the first irradiation condition (irradiation dose: 15 KGy) can reach 227.4 μmol / L, and with the increase of the irradiation dose, the yield of hydrogen peroxide continues to increase. The method provided by the present invention can be realized in an air atmosphere and under normal temperature and pressure, so it has higher safety and operability, and at the same time has the advantages of flexible process, safe operation, simple and controllable operation process, no introduction of impurities, and environmental friendliness. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] The drawings constituting a part of this application are used to provide a further understanding of this application. The schematic embodiments of this application and their descriptions are used to explain this application and do not constitute an improper limitation to this application. In the drawings:

[0026] Figure 1 It is a hydrogen peroxide yield diagram of the method for directly producing hydrogen peroxide by irradiating water with a high-energy electron beam in Example 1;

[0027] Figure 2 It is a hydrogen peroxide yield diagram of the method for directly producing hydrogen peroxide by irradiating water with a high-energy electron beam in Example 2;

[0028] Figure 3 It is the hydrogen peroxide yield graph of the method for directly producing hydrogen peroxide by irradiating water with a high-energy electron beam in Example 3;

[0029] Figure 4 It is the hydrogen peroxide yield graph of the method for directly producing hydrogen peroxide by irradiating water with a high-energy electron beam in Comparative Example 1;

[0030] Figure 5 It is the standard curve for calculating the hydrogen peroxide concentration required in the examples and comparative examples;

[0031] Figure 6 It is the hydrogen peroxide yield graph of the method for directly producing hydrogen peroxide by irradiating water with a high-energy electron beam in Comparative Example 2;

[0032] Figure 7 It is the hydrogen peroxide yield graph of the method for directly producing hydrogen peroxide by irradiating water with a high-energy electron beam in Comparative Example 3. Detailed implementation manners

[0033] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0034] To make the above objects, features, and advantages of the present invention more obvious and understandable, the present invention will be further described in detail below in conjunction with the drawings and specific implementation manners.

[0035] The embodiment of the present invention discloses a method for directly producing hydrogen peroxide by irradiating water with a high-energy electron beam. The water is irradiated with a high-energy electron beam in a closed container, and a hydrogen peroxide solution is obtained; the temperature of the closed container is lower than 40°C during the high-energy electron beam irradiation process.

[0036] The present invention directly produces hydrogen peroxide by irradiating water with a high-energy electron beam, induces water molecules to generate hydrogen peroxide by precisely controlling the irradiation dose and irradiation conditions. At the same time, the application of this method will further promote the wide application and development of hydrogen peroxide in various fields. The present invention not only has simple operation and mild reaction conditions, but also can achieve a high hydrogen peroxide production efficiency without adding any catalysts and sacrificial agents. This method not only improves the safety during the production process, reduces the production cost, but also avoids the pollution of hydrogen peroxide by organic solvents in the subsequent purification steps. Compared with the traditional production method, the method provided by the present invention has advantages such as low energy consumption and good environmental protection, and is expected to provide a new way for the industrial production of hydrogen peroxide.

[0037] In a preferred embodiment, the material of the closed container includes one or more of glass, quartz, and plastic.

[0038] In a preferred embodiment, the dose of the high-energy electron beam irradiation treatment is 15 - 90 KGy.

[0039] In a preferred embodiment, when the material of the closed container is glass, the irradiation dose is 15 - 30 KGy.

[0040] In a preferred embodiment, when the material of the closed container is glass, the irradiation dose is 15 - 30 KGy.

[0041] In a preferred embodiment, when the material of the closed container is plastic, the irradiation dose is 15 - KGy.

[0042] In a preferred embodiment, the temperature of the high-energy electron beam irradiation treatment is room temperature.

[0043] In a preferred embodiment, the rate of the temperature of the high-energy electron beam irradiation treatment is 18 KGy / s.

[0044] In a preferred embodiment, the water is deionized water.

[0045] In a more preferred embodiment, the volume of the water is 1 - 100 mL.

[0046] The present invention only needs to place a container filled with deionized water in an air atmosphere and directly irradiate the reaction container with a high-energy electron beam under normal temperature and pressure to produce hydrogen peroxide and obtain a hydrogen peroxide solution. During the reaction process, no catalysts and sacrificial agents (such as ethanol, methanol, isopropanol, etc.) need to be added, and the production of hydrogen peroxide can be achieved only under pure water conditions.

[0047] In a preferred embodiment, after obtaining the hydrogen peroxide solution, a color-developing agent is added thereto for a color-developing reaction, and then the hydrogen peroxide content is measured and calculated using an ultraviolet-visible spectrophotometer.

[0048] In a more preferred embodiment, the color-developing agent is a 0.1 mol / L C8H5O4 solution and a 0.4 mol / L KI solution.

[0049] In a more preferred embodiment, the time of the color-developing reaction is 30 min.

[0050] Unless otherwise specified, the raw materials in the embodiments of the present invention are all obtained through commercial channels;

[0051] Unless otherwise specified, the room temperature or normal temperature in the embodiments of the present invention both refer to 25 ± 3°C.

[0052] Example 1

[0053] A method for directly producing hydrogen peroxide by irradiating water with a high-energy electron beam comprises the following steps:

[0054] 1) Six portions of 50 mL of deionized water were placed in the same glass container, the caps were tightened, the containers were placed in air atmosphere, and irradiated at room temperature and pressure at an irradiation rate of 18 KGy / s to a dose of 15, 30, 45, 60, 75, and 90 KGy, respectively;

[0055] 2) diluting the solution obtained after high-energy electron beam irradiation in step 1), taking 3 mL of the diluted reaction solution, adding 1 mL of 0.1 mol / L C8H5O4 solution and 1 mL of 0.4 mol / L KI solution as a color developer, and mixing them thoroughly for reaction. After reacting for 30 min, using a UV-vis spectrometer at λ max =350nm wavelength, and the H2O2 concentration of the sample is calculated using the standard curve. The corresponding hydrogen peroxide yield is as follows: Figure 1 shown.

[0056] Figure 1 This is a graph showing the hydrogen peroxide yield at different doses of the aqueous solution in the glass container directly irradiated under air atmosphere in the present invention. It can be seen that the hydrogen peroxide concentration can reach 227.4 μmol / L at 15 KGy, and then the concentration of hydrogen peroxide gradually increases with the increase of irradiation dose, and reaches 293.1 μmol / L at 90 KGy. In the process of directly producing hydrogen peroxide by irradiating water in this embodiment, the content of hydrogen peroxide gradually increases with the increase of irradiation dose, indicating that radiation treatment technology can directly induce water to produce hydrogen peroxide.

[0057] Example 2

[0058] A method for directly producing hydrogen peroxide by irradiating water with a high-energy electron beam comprises the following steps:

[0059] 1) Six portions of 50 mL of deionized water were placed in the same quartz container, the caps were tightened, the containers were placed in air atmosphere, and irradiated at room temperature and pressure at an irradiation rate of 18 KGy / s to a dose of 15, 30, 45, 60, 75, and 90 KGy, respectively;

[0060] 2) diluting the solution obtained after high-energy electron beam irradiation in step 1), taking 3 mL of the diluted reaction solution, adding 1 mL of 0.1 mol / L C8H5O4 solution and 1 mL of 0.4 mol / L KI solution as a color developer, and mixing them thoroughly for reaction. After reacting for 30 min, using a UV-vis spectrometer at λ maxThe sample was measured at a wavelength of 350 nm, and the H2O2 concentration of the sample was calculated using the standard curve. The corresponding hydrogen peroxide yield is as Figure 2 shown.

[0061] Figure 2 This is a graph showing the hydrogen peroxide yield at different irradiation doses for the direct irradiation of an aqueous solution in a quartz container under an air atmosphere in the present invention. As can be seen from the graph, the hydrogen peroxide concentration can reach 274.2 μmol / L at 15 kGy. After that, as the irradiation dose increases, the concentration of hydrogen peroxide also gradually increases and reaches 343.7 μmol / L at 90 kGy. In the process of directly producing hydrogen peroxide by irradiating water in this example, as the irradiation dose increases, the content of hydrogen peroxide gradually increases, indicating that the radiation treatment technology can directly induce water to produce hydrogen peroxide. However, since the price of quartz material is much higher than that of a glass container, based on economic considerations, a glass container is selected as the optimal hydrogen peroxide production condition for this technology.

[0062] Example 3

[0063] A method for directly producing hydrogen peroxide by irradiating water with high-energy electron beams, comprising the following steps:

[0064] 1) Six portions of 50 mL of deionized water were respectively placed in the same plastic container, the bottle caps were tightened, placed under an air atmosphere, and irradiated at an irradiation rate of 18 kGy / s at normal temperature and pressure to doses of 15, 30, 45, 60, 75, and 90 kGy respectively;

[0065] 2) The solution obtained after irradiating with high-energy electron beams in step 1) was diluted. 3 mL of the diluted reaction solution was taken, 1 mL of 0.1 mol / L C8H5O4 solution and 1 mL of 0.4 mol / L KI solution were added thereto as color-developing agents, and they were fully mixed and reacted. After reacting for 30 min, a UV-vis spectrometer was used to measure the sample at a wavelength of λ max = 350 nm, and the H2O2 concentration of the sample was calculated using the standard curve. The corresponding hydrogen peroxide yield is as Figure 3 shown.

[0066] Figure 3This is a graph showing the hydrogen peroxide production yields at different irradiation doses for the direct irradiation of an aqueous solution in a plastic container under an air atmosphere in the present invention. As can be seen from the graph, the hydrogen peroxide concentration can reach 313.3 μmol / L at 15 kGy. However, as the irradiation dose increases, the hydrogen peroxide concentration gradually decreases and reaches 15.1 μmol / L at 90 kGy. In this example of directly producing hydrogen peroxide by irradiating water, as the irradiation dose increases, the content of hydrogen peroxide gradually decreases. This may be because during the irradiation process, as the irradiation dose increases, the heat generated by the plastic material is relatively high, and since hydrogen peroxide is easily decomposed by heat. Therefore, as the irradiation dose increases, the heat of the plastic tube promotes the decomposition of hydrogen peroxide, resulting in a decrease in the hydrogen peroxide concentration.

[0067] Comparative Example 1

[0068] A method for directly producing hydrogen peroxide by irradiating water with high-energy electron beams, comprising the following steps:

[0069] 1) Six portions of ethanol solution (prepared by mixing 4 mL of ethanol and 45 mL of deionized water) were respectively placed in the same glass container, the bottle caps were tightened, placed under an air atmosphere, and irradiated at an irradiation rate of 18 kGy / s at normal temperature and pressure to doses of 15, 30, 45, 60, 75, and 90 kGy respectively;

[0070] 2) Dilute the solution obtained after the high-energy electron beam irradiation in step 1). Take 3 mL of the diluted reaction solution, add 1 mL of 0.1 mol / L C8H5O4 solution and 1 mL of 0.4 mol / L KI solution as color-developing agents thereto, and mix well for reaction. After reacting for 30 min, measure the sample using a UV-vis spectrometer at a wavelength of λ max = 350 nm, and calculate the H2O2 concentration of the sample using a standard curve. The corresponding hydrogen peroxide production yields are as Figure 4 shown.

[0071] Figure 4In the present invention, when a certain amount of ethanol is added as a sacrificial agent to water in a glass container under an air atmosphere, it is a comparison chart of the hydrogen peroxide yield obtained by directly irradiating at different high-energy electron beam doses and the yield without adding a sacrificial agent. As can be seen from the figure, in the process of directly producing hydrogen peroxide by irradiating water in this example, as the irradiation dose increases, the hydrogen peroxide yield without adding a sacrificial agent is always greater than the hydrogen peroxide yield under the condition of adding a sacrificial agent. This may be because in the absence of ethanol as a sacrificial agent, when high-energy electron beams irradiate an aqueous solution, hydroxyl radicals (·OH) mainly participate in the reaction to produce hydrogen peroxide, and the yield is relatively high. After adding ethanol, ethanol undergoes a competitive reaction with ·OH, consuming a large amount of ·OH and triggering a series of side reactions, resulting in a significant decrease in the hydrogen peroxide yield. Therefore, the optimal hydrogen peroxide production efficiency can be achieved in a pure water state.

[0072] Comparative Example 2

[0073] A method for directly producing hydrogen peroxide by irradiating water with high-energy electron beams, which is different from Example 1 only in that: hydrogen peroxide (with a volume concentration of 3%) is mixed with water at an addition amount of 6% by volume to obtain a hydrogen peroxide solution, and the deionized water in step (1) is replaced with an equal volume of this hydrogen peroxide solution and placed in a glass container at an irradiation rate of 18 KGy / s, and irradiated to doses of 15, 30, 45, 60, 75, and 90 KGy respectively.

[0074] Detect the hydrogen peroxide content in the obtained solution, and the corresponding hydrogen peroxide yield is as Figure 6 shown. As can be seen from the figure, the hydrogen peroxide content under the initial conditions of the comparative example is 152.3 mmol / L, but as the irradiation dose increases, the hydrogen peroxide content gradually decreases. The results show that adding a certain concentration of hydrogen peroxide to the reaction system before irradiation cannot promote the production of hydrogen peroxide. Therefore, the prior art cannot be used for the actual production of hydrogen peroxide.

[0075] Comparative Example 3

[0076] A method for directly producing hydrogen peroxide by irradiating water with high-energy electron beams, which is different from Example 1 only in that: hydrogen peroxide (with a volume concentration of 3%) is mixed with water at an addition amount of 6% by volume to obtain a hydrogen peroxide solution, and this hydrogen peroxide solution is mixed with an antibiotic to make the antibiotic concentration 200 mg / L to obtain an antibiotic-hydrogen peroxide solution, and then the deionized water in step (1) is replaced with an equal volume of this antibiotic-hydrogen peroxide solution and placed in a glass container at an irradiation rate of 18 KGy / s, and irradiated to doses of 15, 30, 45, 60, 75, and 90 KGy respectively.

[0077] Detect the hydrogen peroxide content in the finally obtained solution, and the corresponding hydrogen peroxide yield is asFigure 7 As shown. It can be seen from the figure that the hydrogen peroxide content under the initial conditions of the comparative example is 89.1 mmol / L, but as the irradiation dose increases, the hydrogen peroxide content gradually decreases. The results show that adding a certain concentration of hydrogen peroxide to the reaction system before irradiation cannot promote the production of hydrogen peroxide. Therefore, Comparative Example 3 cannot be used for the actual production of hydrogen peroxide.

[0078] The above is only a preferred specific embodiment of the present application, but the protection scope of the present application is not limited thereto. Any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed in the present application should be covered by the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A method for directly producing hydrogen peroxide by irradiating water with high-energy electron beams, characterized in that: Water is irradiated with high-energy electron beams in a sealed container to obtain a hydrogen peroxide solution; the temperature of the sealed container is lower than 40° C. during the high-energy electron beam irradiation process.

2. The method of directly producing hydrogen peroxide by irradiating water with high-energy electron beams according to claim 1, characterized in that: The dosage of the high energy electron beam irradiation treatment is 15-90 KGy.

3. The method of directly producing hydrogen peroxide by irradiating water with high-energy electron beams according to claim 1, characterized in that: The material of the sealed container includes one or more of glass, quartz and plastic.

4. The method of directly producing hydrogen peroxide by irradiating water with high-energy electron beams according to claim 3, characterized in that: When the sealed container is made of glass, the irradiation dose is 15-90 KGy.

5. The method of directly producing hydrogen peroxide by irradiating water with high-energy electron beams according to claim 3, characterized in that: When the sealed container is made of quartz, the irradiation dose is 15-90 KGy.

6. The method of directly producing hydrogen peroxide by irradiating water with high-energy electron beams according to claim 3, characterized in that: When the sealed container is made of plastic, the irradiation dose is 15-30 KGy.

7. The method of directly producing hydrogen peroxide by irradiating water with high-energy electron beams according to claim 1, characterized in that: The temperature of the high energy electron beam irradiation treatment is room temperature.

8. The method of directly producing hydrogen peroxide by irradiating water with high-energy electron beams according to claim 1, characterized in that: The high energy electron beam irradiation treatment rate is 18 KGy / s.

9. The method of directly producing hydrogen peroxide by irradiating water with high-energy electron beams according to claim 1, characterized in that: The water is deionized water.

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