Ozone long-term storage process with fertilizer efficiency and low cost
By preparing ozone through electrolysis and combining it with potassium nitrate to form stable ozone compounds, the problem of easy decomposition of ozone has been solved, enabling low-cost long-term storage and controlled release, thus expanding its application in the agricultural field.
Patent Information
- Application Number
- CN202511690036.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-18
- Publication Date
- 2026-01-23
AI Technical Summary
Ozone is unstable and difficult to store and transport for long periods. Existing low-temperature storage equipment is expensive, which limits its widespread application in agriculture and other fields.
Ozone is prepared by electrolysis and then passed into a potassium nitrate solution to form stable ozone compounds. The π-π interaction is used to achieve effective ozone storage. Combined with water bath and stirring processes, the equipment requirements are simplified.
It enables long-term preservation of ozone at room temperature, reduces storage costs, has sterilization and insect-repellent functions, is suitable for industrial production, and allows for the controlled release of ozone compounds.
Smart Images
Figure CN121377894A_ABST
Abstract
Description
TECHNICAL FIELD
[0002] The application belongs to the technical field of ozone storage, and particularly relates to an ozone long-term storage process with fertilizer effect and low cost. BACKGROUND
[0003] Ozone, as a strong oxidizing green bactericide, can play a role in both gas and liquid environments, and its bactericidal efficiency is much higher than that of traditional disinfection methods such as chlorine and ultraviolet light. Ozone has a rapid and broad-spectrum inactivation effect on bacteria, fungi and other microorganisms. At the same time, ozone mainly generates oxygen and water after reaction in water, and does not produce drug resistance or harmful residues, so it has broad application prospects in many fields such as agriculture, medical treatment and food preservation.
[0004] However, the practical popularization and application of ozone is limited by its poor stability and strict storage conditions. Although the solubility of ozone in water reaches 230 mL / kg (significantly higher than that of oxygen and air), its chemical stability is extremely poor at normal temperature and pressure, and it is easily affected by environmental impurities and temperature to accelerate decomposition. For example, the half-life of 1% ozone aqueous solution is only about 16 min at 25℃, and if there are environmental impurities, the decomposition rate will be further accelerated; the increase of temperature will also significantly accelerate the decomposition of ozone, making it difficult to be stored for a long time.
[0005] In the prior art, although the low-temperature environment (such as ice water mixture) can improve the stability of ozone to a certain extent, it needs to be matched with complex low-temperature storage equipment, which has high energy consumption and cost, and cannot meet the application requirements of large scale and low cost, so that ozone can only be prepared and used at present, which seriously limits its wide application in various fields.
[0006] In agricultural production, the control of diseases usually relies on pesticide spraying, but long-term and excessive use of pesticides may lead to the decline of crop quality, the development of pest resistance, and the harm of pesticide residues to the environment and ecological system. Therefore, it is a key requirement to develop a technology that can not only maintain the strong oxidizing property and antibacterial performance of ozone, but also significantly improve its stability, facilitate storage and transportation, and expand its application range in the field of agriculture and other fields, which has important practical application value. SUMMARY
[0007] The purpose of the present application is to overcome the defects of the prior art and provide an ozone long-term storage process with fertilizer effect and low cost.
[0008] The purpose of the present application can be achieved by the following technical solutions: An ozone long-term storage process with fertilizer effect and low cost comprises the following steps: A1, using electrolysis method, ozone is prepared by using electrolytic ozone generator; A2, under the conditions of water bath and stirring, ozone is introduced into potassium nitrate solution to form ozone compound for storage.
[0009] Further, the current of the electrolysis method is 2-12 A.
[0010] Further, the ozone gas flow generated by the electrolysis is 5-50 mL / min.
[0011] Further, the temperature of the water bath is 5-65℃, preferably 25℃.
[0012] Further, the stirring rate is 0-2500 r / min.
[0013] Further, the ozone is introduced for 0-12 h, preferably 10 h.
[0014] Further, the concentration of the potassium nitrate solution is 10-50 mM.
[0015] Potassium nitrate (KNO3) is a colorless transparent rhombic crystal or white powder, easily soluble in water, with a solubility of 31.6 g / 100 g water in water at 20℃, and almost insoluble in alcohol. In the field of agriculture, potassium nitrate is used as a common nitrogen-potassium compound fertilizer, which can be rapidly absorbed by crops, and is widely used in the planting of tobacco, vegetables and fruits, etc. In the present application, ozone is introduced into an aqueous solution containing potassium nitrate, and the nitrate ion (NO3 - ) in the solution has a planar triangular structure, forming a delocalized resonance system between the nitrogen atom and the oxygen atom. The ozone molecule also has a delocalized electronic structure. When the two are in contact in an aqueous solution, a stable ozone compound can be formed through π-π interaction, thereby achieving effective storage of ozone. When the water content in the solution gradually decreases, the ozone compound can slowly release ozone to achieve a controllable release effect.
[0016] Advantages of the present application: 1. The present application combines ozone with potassium nitrate to form a stable ozone compound, effectively solving the problem of ozone decomposition at room temperature, and achieving long-term storage in a conventional environment. 2. The electrolysis method is used to prepare ozone, combined with a water bath stirring process, which is simple in process flow and does not require complex equipment, suitable for industrialization and large-scale production. 3. The selected potassium nitrate raw material is widely available and low in price, significantly reducing the overall cost of ozone storage. 4. The obtained potassium nitrate ozone compound has good stability at room temperature and can be stored for a long time without failure. 5. The ozone compound can play a role in sterilization and insect prevention while being rapidly absorbed by crops as a nitrogen-potassium compound fertilizer, realizing the combined function of fertilizer and fungicide.
[0017] In conclusion, the ozone storage method has the advantages of low cost, simple process and stable application effect, and can effectively overcome the problems of fast decomposition, difficult preservation and inconvenient transportation in the existing ozone storage technology, and has important application value in the fields of ozone storage and agricultural application. BRIEF DESCRIPTION OF DRAWINGS
[0018] The application will be further described below with reference to the drawings.
[0019] Figure 1 The broken line graph of the ozone content (peroxide value) of the ozone compound of the application from left to right (a-d) changes with the time of ozone passing in, the temperature of water bath, the stirring rate and the concentration of potassium nitrate.
[0020] Figure 2 The broken line graph of the ozone content (peroxide value) of the ozone compound of the application from left to right (a-c) changes with time after long-term stability, thermal stability and light stability experiments. DETAILED DESCRIPTION
[0021] The technical solutions in the embodiments of the application will be clearly and completely described below with reference to the embodiments of the application. Obviously, the described embodiments are only a part of the embodiments of the application, not all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the application.
[0022] In the following examples, the raw materials and reagents used are as follows: ozone is prepared by electrolysis of water using existing laboratory technology; chloroform, glacial acetic acid, potassium iodide, sodium thiosulfate and starch indicator are all analytical pure reagents provided by Sinopharm Chemical Reagent Co., Ltd. Instrument source: YM-K voltage and current stabilizing switching power supply is used to provide electric energy, and DF-101S heat collecting type heating magnetic stirrer is used to provide constant temperature and stirring environment.
[0023] The ozone content determination method of the ozone compound in the embodiments of the application refers to the requirements of GB5009.227-2016 determination of peroxide value, and the specific steps are as follows: (1) Take 1ml of ozone compound in a conical flask with a pipette, and add 30ml of chloroform glacial acetic acid (2:3) mixed solution.
[0024] (2) Then accurately add 1mL of saturated potassium iodide solution, tightly plug the bottle cap, and gently shake for 1min, and place in the dark for 3min.
[0025] (3) Add 100 mL of water into the conical flask, shake it well, then immediately titrate the precipitated iodine with sodium thiosulfate standard solution (0.01 mol / L) until it is light yellow, add 1 mL of starch indicator, continue to titrate and shake it vigorously until the solution is blue, and the end point is reached. Meanwhile, carry out a blank test, and the volume of 0.01 mol / L sodium thiosulfate solution consumed in the theoretical blank test should not exceed 0.1 mL.
[0026] The calculation formula of peroxide value is wherein: X is the peroxide value (g / 100g); is the concentration (mol / L) of Na2S2O3 standard solution; is the volume (mL) of Na2S2O3 titration solution consumed; is the volume (mL) of Na2S2O3 titration solution consumed in the blank test; is the mass (g) of ozonized compound.
[0027] Example 1 A1, ozone is prepared by electrolysis, and an electrolytic ozone generator is used to operate under the condition of a current of 12 A, and the ozone gas flow is controlled to be 50 mL / min; A2, under the condition of a 25℃ water bath, the stirring speed is 500 r / min, ozone gas is introduced into a 50 mM potassium nitrate solution, and the introduction time is 10 h to obtain a stable ozonized compound; the obtained ozonized compound is collected and stored at room temperature.
[0028] Example 2 A1, ozone is prepared by electrolysis, and an electrolytic ozone generator is used to operate under the condition of a current of 12 A, and the ozone gas flow is controlled to be 50 mL / min; A2, under the condition of a 25℃ water bath, the stirring speed is 500 r / min, ozone gas is introduced into a 50 mM potassium nitrate solution, and the introduction time is 0-12 h to obtain a stable ozonized compound; the obtained ozonized compound is collected and stored at room temperature; in this embodiment, the temperature of the water bath, the stirring speed and the concentration of the potassium nitrate solution are fixed, only the ozone introduction time is controlled, and finally the peroxide value of the obtained ozonized compound is calculated, and the broken line graph of the peroxide value change with the ozone introduction time is measured, as shown in Figure 1 (a).
[0029] Example 3 A1, ozone is prepared by electrolysis, and an electrolytic ozone generator is used to operate under the condition of a current of 12 A, and the ozone gas flow is controlled to be 50 mL / min; A2, ozone gas was bubbled into 50 mM potassium nitrate solution under the condition of 15-65 °C water bath, the stirring speed was 500 r / min, the time of bubbling was 10 h, and stable ozone compound was obtained; the obtained ozone compound was collected and stored under normal temperature condition; in this example, the time of ozone bubbling, the stirring speed and the concentration of potassium nitrate solution were fixed, only the temperature of water bath was controlled, finally the peroxide value of the obtained ozone compound was calculated, and the broken line graph of the peroxide value changing with the time of ozone bubbling was measured, as shown in Figure 1 (b).
[0030] Example 4 A1, ozone was prepared by electrolysis method, electrolytic ozone generator was used, the ozone gas flow was controlled to be 50 mL / min under the condition of 12 A current; A2, ozone gas was bubbled into 50 mM potassium nitrate solution under the condition of 15-65 °C water bath, the stirring speed was 500 r / min, the time of bubbling was 10 h, and stable ozone compound was obtained; the obtained ozone compound was collected and stored under normal temperature condition; in this example, the time of ozone bubbling, the stirring speed and the concentration of potassium nitrate solution were fixed, only the temperature of water bath was controlled, finally the peroxide value of the obtained ozone compound was calculated, and the broken line graph of the peroxide value changing with the time of ozone bubbling was measured, as shown in Figure 1 (c).
[0031] Example 5 A1, ozone was prepared by electrolysis method, electrolytic ozone generator was used, the ozone gas flow was controlled to be 50 mL / min under the condition of 12 A current; A2, ozone gas was bubbled into 50 mM potassium nitrate solution under the condition of 15-65 °C water bath, the stirring speed was 500 r / min, the time of bubbling was 10 h, and stable ozone compound was obtained; the obtained ozone compound was collected and stored under normal temperature condition; in this example, the time of ozone bubbling, the stirring speed and the concentration of potassium nitrate solution were fixed, only the temperature of water bath was controlled, finally the peroxide value of the obtained ozone compound was calculated, and the broken line graph of the peroxide value changing with the time of ozone bubbling was measured, as shown in Figure 1 (d).
[0032] From Example 2 and Figure 1 (a), it can be known that with the prolongation of the time of ozone bubbling, the peroxide value of the obtained ozone compound gradually increased, but the growth rate gradually slowed down. This is because the reaction between ozone and potassium nitrate has reversibility, and with the increase of the concentration of the product, the consumption rate of the reactant gradually slows down. When the time of ozone bubbling reaches 10 h, the peroxide value tends to be stable, which indicates that the system basically reaches equilibrium at this time. Therefore, the optimal time of ozone bubbling is determined to be 10 h.
[0033] From Example 3 and Figure 1 (b) It can be seen that the peroxide value of the peroxide compound gradually decreases as the reaction temperature increases. Although the increase in temperature helps to accelerate the reaction rate of ozone with potassium nitrate, it also significantly accelerates the decomposition rate of ozone, and the effect of decomposition is greater than the effect of the increase in reaction rate, resulting in a overall decrease in peroxide value. When the temperature is 15℃, the peroxide value reaches a maximum. Therefore, the optimal reaction temperature is determined to be 15℃.
[0034] From Example 4 and Figure 1 (c) It can be seen that the stirring rate also has an effect on the production of ozonated compounds. When the stirring changes from a static state to a certain rate, the peroxide value increases significantly, but when the stirring rate continues to increase, the peroxide value tends to be stable, indicating that stirring only plays a role in promoting uniform mixing of substances, and is not a major factor after reaching a certain rate.
[0035] From Example 5 and Figure 1 (d) It can be seen that the increase in potassium nitrate concentration can significantly increase the peroxide value of the ozonated compound. The reason is that there are more NO3 in the solution at a higher concentration, which can form stable ozonated compounds with ozone through π-π interaction, thereby promoting the reaction. When the concentration of potassium nitrate reaches 50mM, the peroxide value is the highest. Therefore, the optimal concentration of potassium nitrate solution is determined to be 50mM.
[0036] Reproducibility test: To verify the reproducibility of the method of the present application, the experimental conditions of Example 1 were repeated 8 times, respectively numbered as samples 1-8, the peroxide value of each sample was determined, and the volume of the consumed Na2S2O3 standard solution was recorded, and then the peroxide value (ozone content) was calculated. The determination results are shown in Table 1.
[0037] Table 1
[0038] From the results in Table 1, the relative standard deviation (RSD) of the data obtained by the method is 2.10%, indicating that the method has good reproducibility and reliability.
[0039] In addition, the ozonated compound prepared in Example 1 was placed under different conditions for stability investigation, including long-term stability (25℃, light-avoiding, static), thermal stability (40℃, light-avoiding, static), and light stability (25℃, light, static). Then the peroxide value (ozone content) was determined at different time points, and a line graph of the change with time was drawn, and the results are shown in Figure 2 (a, b, c), respectively.
[0040] In conclusion, the method for storing ozone provided by the application solves the problems of easy decomposition and difficult storage in traditional ozone application, and has important application value in the field of ozone storage technology.
[0041] In the description of the specification, the description of the terms "one embodiment", "example", "specific example" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the application. In the specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. The above is only an example and illustration of the application, and those skilled in the art can make various modifications or supplements or use similar ways to replace the described specific embodiments, as long as they do not deviate from the invention or exceed the scope defined by the claims.
Claims
1. An ozone long-term storage process with both fertilizer effect and low cost, characterized in that, The method comprises the following steps: A1, using electrolysis method, using electrolytic ozone generator to prepare ozone; A2, under the condition of water bath and stirring, ozone is introduced into potassium nitrate solution to form ozone compound and store.
2. The process for long-term storage of ozone with fertilizer effect and low cost according to claim 1, characterized in that, The current of the electrolysis method is 2-12 A.
3. The process for long-term storage of ozone with fertilizer effect and low cost according to claim 1, characterized in that, The ozone gas flow generated by electrolysis is 5-50 mL / min.
4. The process for long-term storage of ozone with fertilizer effect and low cost according to claim 1, characterized in that, The temperature of the water bath is 5-65℃.
5. The process for long-term storage of ozone with fertilizer effect and low cost according to claim 1, characterized in that, The stirring rate is 0-2500 r / min.
6. The process for long-term storage of ozone with fertilizer effect and low cost according to claim 1, characterized in that, The ozone introduction time is 0-12 h.
7. The process for long-term storage of ozone with fertilizer effect and low cost according to claim 1, characterized in that, The concentration of the potassium nitrate solution is 10-50 mM.