Preparation method and application of gel type sodium hydrogen sulfite activated potassium permanganate slow-release composite medicament taking silica sol as carrier

Abstract

The invention discloses a preparation method and application of a gel type sodium hydrogen sulfite activated potassium permanganate slow-release composite medicament taking silica sol as a carrier, and relates to the technical field of pollution treatment and environmental remediation. The invention aims to solve the problems of instantaneous release of an oxidizing agent, self-quenching of free radicals, difficulty in continuous reaction control and excessive oxidation reaction caused by over-high instantaneous concentration of the free radicals in a traditional active free radical oxidation treatment mode. According to the slow-release composite medicament, potassium permanganate and sodium hydrogen sulfite are dissolved into silica sol, a three-dimensional gel network structure is formed by utilizing an electrolyte-induced double-electrode-layer compression effect and particle aggregation caused by Van der Waals force, water molecules and the two medicaments are fixed in the gel network structure, and due to the action of osmotic pressure in water, the water molecules and the two medicaments are separated from each other. Medicament molecules can be gradually dissolved into water, so that the slow release control of the medicament is finally realized. The invention can obtain the preparation method and the application of the gel type sodium hydrogen sulfite activated potassium permanganate slow-release composite medicament taking the silica sol as the carrier.

Description

Technical Field

[0001] The present invention relates to the technical field of pollution control and environmental remediation, and particularly relates to a preparation method and application of a gel-type sodium bisulfite-activated potassium permanganate slow-release composite agent with silica sol as a carrier. Background Art

[0002] With the rapid development of modern industry and agriculture, the safety of surface water environment has been greatly challenged and threatened. Pollutants such as refractory organic matters, heavy metals, and microorganisms often exist in water sources, seriously threatening the safety of human drinking water. Therefore, water treatment agents that are safe, effective, and have continuous treatment effects have become the focus of research. In the process of water treatment, potassium permanganate is a commonly used pretreatment oxidant, which can remove organic pollutants in water through strong oxidizing properties and reduce the difficulty of subsequent process treatment.

[0003] In recent years, with in-depth research, it has been found that activating potassium permanganate with sodium bisulfite can significantly improve the oxidation ability and reaction rate of potassium permanganate. At the same time, sodium bisulfite can hydrolyze to generate sulfite ions, which participate in the reaction as a reducing agent to produce more strongly oxidizing active free radicals, proving that the above activation method can not only improve the pollutant removal efficiency, but also achieve more complete degradation and effectively deal with complex pollutants.

[0004] However, traditional active free radical oxidation treatment methods usually have the disadvantages of instantaneous release of oxidants, self-quenching of free radicals, and difficulty in continuously controlling the reaction. At the same time, too high an instantaneous concentration of free radicals will lead to over-oxidation reactions, which not only increase costs, but may also produce by-products and cause secondary pollution to water bodies. Summary of the Invention

[0005] The purpose of the present invention is to solve the above technical problems, and provide a preparation method and application of a gel-type sodium bisulfite-activated potassium permanganate slow-release composite agent with silica sol as a carrier.

[0006] A preparation method of a gel-type sodium bisulfite-activated potassium permanganate slow-release composite agent with silica sol as a carrier is carried out according to the following steps:

[0007] Step S1, preparing potassium permanganate slow-release gel:

[0008] Add potassium permanganate to the silica sol solution, stir evenly to obtain a mixed solution a; use a syringe to suck the mixed solution a and inject it into a hemispherical silica gel mold, demold after solidification to obtain potassium permanganate slow-release gel;

[0009] Step S2, preparing sodium bisulfite slow-release gel:

[0010] Sodium bisulfite was added to the silica sol solution, and after stirring evenly, a mixed solution b was obtained; the mixed solution b was sucked with a syringe and injected into a hemispherical silica gel mold, and after solidification, demolding was carried out to obtain a sodium bisulfite slow-release gel.

[0011] Step S3: Prepare a slow-release composite medicament sphere:

[0012] The potassium permanganate slow-release gel obtained in step S1 and the sodium bisulfite slow-release gel obtained in step S2 were adhered together with an organic silicone to obtain a gel-type sodium bisulfite-activated potassium permanganate slow-release composite medicament sphere using silica sol as a carrier; the molar ratio of potassium permanganate in the potassium permanganate slow-release gel to sodium bisulfite in the sodium bisulfite slow-release gel was (1:2.5), (1:5), or (1:10).

[0013] Application of a gel-type sodium bisulfite-activated potassium permanganate slow-release composite medicament using silica sol as a carrier, and application of the gel-type sodium bisulfite-activated potassium permanganate slow-release composite medicament using silica sol as a carrier in removing algae or refractory organic pollutants in drinking water.

[0014] Principle of the present invention:

[0015] The present invention develops a slow-release composite water treatment medicament that is safe, effective and has a continuous treatment effect for the front end of drinking water treatment. Silica sol is a colloidal solution in which nanoscale silica particles are uniformly dispersed and suspended in water. The sizes of these silica particles are usually between 1 and 100 nm. Therefore, silica sol has certain colloidal properties. The silica particles in silica sol are usually amorphous (non-crystalline) and carry negative charges. After adding a certain amount of concentration of Na + , K + salt ions, due to the action of electrostatic force, positive ions are attracted by the silica particles. These metal ions neutralize or reduce the negative charges on the surface of the silica particles through electrostatic adsorption, the repulsion between the silica particles decreases, and at the same time the distance becomes smaller, and the van der Waals force begins to play a dominant role, ultimately causing the silica particles to gradually aggregate with each other to form a gel-like three-dimensional network structure. The two medicament molecules and water molecules are trapped inside the gel by the network structure to form a slow-release composite medicament. When the slow-release composite medicament is put into water, the surface layer medicament is dissolved first and carried away by the water flow, and the inner layer medicament gradually dissolves and oozes out under the action of osmotic pressure, ultimately achieving the purpose of slow and controllable release and improving the sustainability of water body purification.

[0016] Beneficial effects of the present invention:

[0017] (1) The present invention utilizes the intermediate-valence manganese and highly reactive free radicals generated by the activation of potassium permanganate with sodium bisulfite to oxidize and degrade organic pollutants in water. Among them, a slow-release gel is used to slow down the release rate of the oxidant, and by controlling the instantaneous concentration of active species, the phenomenon of over-oxidation is reduced. This not only improves the utilization efficiency of the reagent and reduces the raw material cost, but also avoids the problem of exacerbating pollution caused by the release of the contents of broken algal cells in natural water bodies due to over-oxidation.

[0018] (2) The raw materials of the present invention are inexpensive and the preparation process is simple. Silica sol is a green and safe reagent in the environmental field that is harmless to soil and water environment. Its main component is silicon dioxide, and after forming a gel and releasing the internal reagent, it can be recovered and reused. Sodium bisulfite and potassium permanganate are both common chemical reagents in water treatment. The newly formed manganese dioxide is in floc form and can be removed in the subsequent coagulation and precipitation process, having no negative impact on the safety of drinking water.

[0019] (3) The slow-release composite reagent of the present invention uses silica sol as a carrier. Potassium permanganate and sodium bisulfite are dissolved into the silica sol, and the double-layer compression effect induced by the electrolyte and the particle aggregation caused by van der Waals force are utilized to finally form a three-dimensional gel network structure, fixing water molecules and the two reagents in the gel network structure. Due to the osmotic pressure in water, the reagent molecules will gradually dissolve into the water, ultimately realizing the slow-release control of the reagent.

[0020] (4) The present invention can prepare a slow-release composite reagent with reliable performance, safety and high efficiency. It not only has a low cost but also has a high pollutant removal efficiency, and is a new type of drinking water pretreatment reagent.

[0021] The present invention can obtain a preparation method and application of a gel-type slow-release composite reagent for activating potassium permanganate with sodium bisulfite using silica sol as a carrier. Description of the Drawings

[0022] Figure 1 It shows a schematic diagram of the preparation process of the gel-type slow-release composite reagent for activating potassium permanganate with sodium bisulfite using silica sol as a carrier in the present invention;

[0023] Figure 2 It shows a schematic diagram of simulating the treatment of polluted sewage under laboratory conditions in the present invention;

[0024] Figure 3 It shows the degradation effect diagrams of bisphenol A by the gel-type slow-release composite reagent for activating potassium permanganate with sodium bisulfite prepared in Examples 1 - 3 using silica sol as a carrier. Detailed Embodiments

[0025] Embodiment 1: A preparation method of a gel-type sodium bisulfite-activated potassium permanganate sustained-release composite agent with silica sol as the carrier is carried out according to the following steps:

[0026] Step S1: Prepare potassium permanganate sustained-release gel:

[0027] Add potassium permanganate to the silica sol solution, stir evenly to obtain a mixed solution a; use a syringe to suck the mixed solution a and inject it into a hemispherical silica gel mold, and demold after solidification to obtain potassium permanganate sustained-release gel;

[0028] Step S2: Prepare sodium bisulfite sustained-release gel:

[0029] Add sodium bisulfite to the silica sol solution, stir evenly to obtain a mixed solution b; use a syringe to suck the mixed solution b and inject it into a hemispherical silica gel mold, and demold after solidification to obtain sodium bisulfite sustained-release gel;

[0030] Step S3: Prepare a sustained-release composite agent sphere:

[0031] Adhere the potassium permanganate sustained-release gel obtained in step S1 and the sodium bisulfite sustained-release gel obtained in step S2 together with organosilicon glue to obtain a gel-type sodium bisulfite-activated potassium permanganate sustained-release composite agent sphere with silica sol as the carrier; the molar ratio of potassium permanganate in the potassium permanganate sustained-release gel to sodium bisulfite in the sodium bisulfite sustained-release gel is (1:2.5), (1:5) or (1:10).

[0032] Embodiment 2: The difference between this embodiment and Embodiment 1 is that the ratio of the mass of potassium permanganate to the volume of the silica sol solution in step S1 is (0.316 - 0.632) g: 20 mL.

[0033] Other steps are the same as those in Embodiment 1.

[0034] Embodiment 3: The difference between this embodiment and Embodiment 1 or 2 is that after the mixed solution a is injected into the hemispherical silica gel mold in step S1, it is solidified for 12 - 24 h at a temperature of 25 - 30 °C and then demolded. If it is not used immediately, it is sealed and stored in a 4 °C refrigerator.

[0035] Other steps are the same as those in Embodiment 1 or 2.

[0036] Embodiment 4: The difference between this embodiment and any one of Embodiments 1 to 3 is that the ratio of the mass of sodium bisulfite to the volume of the silica sol solution in step S2 is (1.04 - 4.16) g: 20 mL.

[0037] Other steps are the same as those in Embodiments 1 to 3.

[0038] Embodiment 5: The difference between this embodiment and any one of Embodiments 1 to 4 is that after the mixed solution b is injected into the hemispherical silica gel mold in Step S2, it is solidified for 12 to 24 hours at a temperature of 25 to 30 °C and then demolded. If it is not used immediately, it is sealed and stored in a refrigerator at 4 °C.

[0039] Other steps are the same as those in Embodiments 1 to 4.

[0040] Embodiment 6: The difference between this embodiment and any one of Embodiments 1 to 5 is that the mass fraction of silica sol in the silica sol solution described in Step S1 and Step S2 is 19 to 41%.

[0041] Other steps are the same as those in Embodiments 1 to 5.

[0042] Embodiment 7: The difference between this embodiment and any one of Embodiments 1 to 6 is that a magnetic stirrer is used for stirring in both Step S1 and Step S2.

[0043] Other steps are the same as those in Embodiments 1 to 6.

[0044] Embodiment 8: The difference between this embodiment and any one of Embodiments 1 to 7 is that the volumes of the mixed solution a and the mixed solution b aspirated in Step S1 and Step S2 are 1 mL, 2 mL, 3 mL, or 4 mL.

[0045] Other steps are the same as those in Embodiments 1 to 7.

[0046] Embodiment 9: The difference between this embodiment and any one of Embodiments 1 to 8 is that the diameter of the gel-type sodium bisulfite-activated potassium permanganate slow-release composite agent sphere described in Step S2 is 1.56 to 2.48 cm.

[0047] Other steps are the same as those in Embodiments 1 to 8.

[0048] Embodiment 10: The application of a gel-type sodium bisulfite-activated potassium permanganate slow-release composite agent using silica sol as a carrier, and the application of the gel-type sodium bisulfite-activated potassium permanganate slow-release composite agent using silica sol as a carrier in removing algae and refractory organic pollutants in surface water and removing pesticides and refractory organic pollutants in soil.

[0049] The effective oxidation components of the gel-type sodium bisulfite-activated potassium permanganate slow-release composite agent are reactive manganese (RMnS), hydroxyl radical (HO·), and sulfate radical (SO 4 · -), mainly generated by the activation of potassium permanganate with sodium bisulfite. The first step of the reaction between the two is to snatch electrons from sodium bisulfite to generate Mn(Ⅵ) and SO 3 · - . Subsequently, under the action of HSO 3 - , Mn(Ⅵ) is further reduced to Mn(Ⅴ), Mn(Ⅳ), Mn(Ⅲ) and Mn(Ⅱ), and a large amount of SO 3 · - is generated. Dissolved oxygen in water combines with SO 3 · - to form SO 5 · - , and SO 5 · - reacts with HSO 3 - to produce SO 4 · - . Once SO 4 · - is generated in the system, it will react with HO - / H 2 O to produce HO·. Therefore, reactive manganese (RMnS), HO· and SO 4 · - are the main active species for degrading pollutants in this slow-release composite agent. The specific reaction equations are as follows (Equations 1-1) to (1-8).

[0050] Mn (Ⅶ) + HSO 3 - → Mn (Ⅵ) + SO 3 · - + H + (1-1)

[0051] Mn (Ⅵ) + HSO 3 - → Mn (Ⅴ) + SO 3 · - + H + (1-2)

[0052] Mn (Ⅴ) + HSO 3 - → Mn (Ⅳ) + SO 3 · - + H+ (1-3)

[0053] Mn (Ⅳ) + HSO 3 - → Mn (Ⅲ) + SO 3 · -+ H + (1-4)

[0054] Mn (Ⅲ) + HSO 3 - → Mn(Ⅱ) + SO 3 · - + H + (1-5)

[0055] SO 3 · - + O 2 → SO 5 · - (1-6)

[0056] SO 5 · - + HSO 3 - → SO 4 · - + SO 4 2- + H + (1-7)

[0057] SO 4 · - +HO - →SO 4 2- +HO·(1-8).

[0058] The beneficial effects of the present invention are verified by the following examples:

[0059] Example 1: A preparation method of a gel-type sodium bisulfite-activated potassium permanganate sustained-release composite agent using silica sol as a carrier is carried out according to the following steps:

[0060] Step S1: Prepare potassium permanganate sustained-release gel:

[0061] Weigh 0.632 g of potassium permanganate, and add the potassium permanganate to a conical flask containing 20 mL of silica sol (29-31%). After using a magnetic stirrer to stir until the potassium permanganate and silica sol are fully mixed and uniform, a mixed solution a is obtained; use a syringe to suck 2 mL of the mixed solution a and inject it into a hemispherical silica gel mold, and store it at a temperature of 28 °C. After solidifying for 12 h, demold to obtain a hemispherical solid potassium permanganate sustained-release gel, and the sphere diameter is about 1.97 cm;

[0062] Step S2: Prepare sodium bisulfite sustained-release gel:

[0063] Weigh 2.08 g of sodium bisulfite and add the sodium bisulfite to a conical flask containing 20 mL of silica sol (29 - 31%). Use a magnetic stirrer to stir until the sodium bisulfite and silica sol are fully and evenly mixed to obtain mixture b. Use a syringe to draw 2 mL of mixture b and inject it into a hemispherical silica gel mold. Store it at a temperature of 28 °C, demold after solidifying for 12 h to obtain a hemispherical solid sodium bisulfite slow-release gel, and the sphere diameter is about 1.97 cm.

[0064] Step S3: Prepare the slow-release composite agent sphere:

[0065] Adhere the potassium permanganate slow-release gel obtained in step S1 and the sodium bisulfite slow-release gel obtained in step S2 together using organic silicone to finally form a complete sphere. Half of the sphere is the potassium permanganate slow-release gel and the other half is the sodium bisulfite slow-release gel, and the sphere diameter is about 1.97 cm. The molar ratio of potassium permanganate in the potassium permanganate slow-release gel to sodium bisulfite in the sodium bisulfite slow-release gel is 1:5.

[0066] Step S4: Degradation experiment of model pollutant bisphenol A:

[0067] Place the slow-release composite agent obtained in step S3 in the column of a fluidized bed reactor (as Figure 2 shown). Configure a bisphenol A solution with a concentration of 0.5 μmmol / L as simulated sewage. Use a peristaltic pump to make the simulated sewage pass through the reaction column at a flow rate of 10 mL / min uniformly. Take the reacted solution from the storage bucket at different reaction times to measure the concentration of bisphenol A. The reaction temperature is room temperature (20.2 °C), and the pH of the simulated sewage is about 6.7.

[0068] Example 2: A preparation method of a gel-type sodium bisulfite-activated potassium permanganate slow-release composite agent using silica sol as a carrier is carried out according to the following steps:

[0069] Step S1: Prepare the potassium permanganate slow-release gel:

[0070] Weigh 0.632 g of potassium permanganate and add the potassium permanganate to a conical flask containing 20 mL of silica sol (29 - 31%). Use a magnetic stirrer to stir until the potassium permanganate and silica sol are fully and evenly mixed to obtain mixture a. Use a syringe to draw 2 mL of mixture a and inject it into a hemispherical silica gel mold. Store it at a temperature of 28 °C, demold after solidifying for 12 h to obtain a hemispherical solid potassium permanganate slow-release gel, and the sphere diameter is about 1.97 cm.

[0071] Step S2: Prepare the sodium bisulfite slow-release gel:

[0072] Weigh 4.16 g of sodium bisulfite, and add the sodium bisulfite to a conical flask containing 20 mL of silica sol (29 - 31%). Use a magnetic stirrer to stir until the sodium bisulfite and the silica sol are fully mixed and uniform, obtaining a mixed solution b. Use a syringe to suck 2 mL of the mixed solution b and inject it into a hemispherical silica gel mold, and store it under the temperature condition of 28 °C. After solidifying for 12 h, demold to obtain a hemispherical solid sodium bisulfite slow-release gel, with the sphere diameter being approximately 1.97 cm.

[0073] Step S3: Prepare the slow-release composite agent sphere:

[0074] Adhere the potassium permanganate slow-release gel obtained in Step S1 and the sodium bisulfite slow-release gel obtained in Step S2 together using organic silicone to finally form a complete sphere. Half of the sphere is the potassium permanganate slow-release gel, and the other half is the sodium bisulfite slow-release gel, with the sphere diameter being approximately 1.97 cm. The molar ratio of potassium permanganate in the potassium permanganate slow-release gel to sodium bisulfite in the sodium bisulfite slow-release gel is 1:10.

[0075] Step S4: Degradation experiment of the model pollutant bisphenol A:

[0076] Place the slow-release composite agent obtained in Step S3 in the column of a fluidized bed reactor (as shown in Figure 2 ) and configure a bisphenol A solution with a concentration of 0.5 μmmol / L as simulated sewage. Use a peristaltic pump to make the simulated sewage pass through the reaction column at a flow rate of 10 mL / min uniformly. Take the reacted solution from the storage tank at different reaction times to measure the concentration of bisphenol A. The reaction temperature is room temperature (20.2 °C), and the pH of the simulated sewage is approximately 6.7.

[0077] Example 3: A preparation method of a gel-type sodium bisulfite-activated potassium permanganate slow-release composite agent using silica sol as a carrier is carried out according to the following steps:

[0078] Step S1: Prepare the potassium permanganate slow-release gel:

[0079] Weigh 0.632 g of potassium permanganate, and add the potassium permanganate to a conical flask containing 20 mL of silica sol (29 - 31%). Use a magnetic stirrer to stir until the potassium permanganate and the silica sol are fully mixed and uniform, obtaining a mixed solution a. Use a syringe to suck 3 mL of the mixed solution a and inject it into a hemispherical silica gel mold, and store it under the temperature condition of 28 °C. After solidifying for 12 h, demold to obtain a hemispherical solid potassium permanganate slow-release gel, with the sphere diameter being approximately 2.25 cm.

[0080] Step S2: Prepare the sodium bisulfite slow-release gel:

[0081] Weigh 2.08 g of sodium bisulfite and add it to a conical flask containing 20 mL of silica sol (29 - 31%). Use a magnetic stirrer to stir until the sodium bisulfite and silica sol are fully and evenly mixed to obtain mixture b. Use a syringe to draw 3 mL of mixture b and inject it into a hemispherical silica gel mold. Store it at a temperature of 28 °C, demold after solidifying for 12 h to obtain a hemispherical solid sodium bisulfite slow-release gel, with a sphere diameter of approximately 2.25 cm.

[0082] Step S3: Prepare the slow-release composite agent sphere:

[0083] Adhere the potassium permanganate slow-release gel obtained in step S1 and the sodium bisulfite slow-release gel obtained in step S2 together using silicone rubber to finally form a complete sphere. Half of the sphere is potassium permanganate slow-release gel and the other half is sodium bisulfite slow-release gel, with a sphere diameter of approximately 2.25 cm. The molar ratio of potassium permanganate in the potassium permanganate slow-release gel to sodium bisulfite in the sodium bisulfite slow-release gel is 1:5.

[0084] Step S4: Degradation experiment of the model pollutant bisphenol A:

[0085] Place the slow-release composite agent obtained in step S3 in the column of a fluidized bed reactor (as Figure 2 shown). Prepare a bisphenol A solution with a concentration of 0.5 μmmol / L as simulated sewage. Use a peristaltic pump to make the simulated sewage pass through the reaction column at a flow rate of 10 mL / min. Take the reacted solution from the storage tank at different reaction times to measure the concentration of bisphenol A. The reaction temperature is room temperature (20.2 °C), and the pH of the simulated sewage is approximately 6.7.

[0086] The degradation effect of bisphenol A in the above Examples 1 - 3 is as Figure 3 shown. It can be seen that both the size of the slow-release composite agent sphere and the addition amounts of potassium permanganate and sodium bisulfite have an impact on the degradation effect of bisphenol A. In Example 1, the molar ratio of potassium permanganate to sodium bisulfite is 1:5, and the diameter of the slow-release composite agent sphere is 1.97 cm. The degradation rate of bisphenol A reaches 58.8% at 5 min from the start of the reaction.

[0087] In Example 2 with the same sphere diameter, a higher proportion of sodium bisulfite (potassium permanganate:sodium bisulfite = 1:10) will dissolve in large amounts in the initial stage of the reaction. As a reducing agent itself, it will consume some of the generated oxidative active species, resulting in a bisphenol A degradation rate of only 29% in the first 5 min of the reaction. When the reaction proceeds to 60 min, due to the controlled release effect of the gel, the release of potassium permanganate and sodium bisulfite is stabilized within a reasonable concentration range, and the degradation rate of the composite agent for bisphenol A increases to 81.8%, and the oxidation efficiency of the active species is fully exerted.

[0088] In Example 3, the sphere diameter of the slow-release composite agent was enlarged to 2.25 cm, and the molar ratio of potassium permanganate to sodium bisulfite was 1:5. High-efficiency degradation of bisphenol A was observed. The degradation rate of bisphenol A was 100% from the 120th minute of the reaction to the 400th minute of the reaction end, which was higher than that in Example 1 (87.1% - 96.7%) and Example 2 (87.2% - 97.3%). The above Examples 1 - 3 show that the slow-release composite agent can quickly and effectively control the release of the internal agent in water, fully exert the degradation efficiency of oxidative active species on pollutants. The slow-release composite agent with a larger volume shows better removal effect on pollutants and longer pollution control time, and different specifications of slow-release composite agents can be carried according to the actual application scenarios.

[0089] The gel-type sodium bisulfite-activated potassium permanganate slow-release composite agent prepared with silica sol as the carrier in the above Examples 1 - 3 has excellent water treatment performance, greatly improves the degradation efficiency of pollutants, and reduces the dosage of the agent at the same time. It is an energy-saving, green and safe water treatment composite agent.

Claims

1. A method for preparing a gel-type sodium bisulfite activated potassium permanganate sustained-release composite medicament using silica sol as a carrier, characterized in that The preparation method is carried out according to the following steps: Step S1, preparing potassium permanganate sustained-release gel: Potassium permanganate is added to the silica sol solution and stirred evenly to obtain a mixed solution a; the mixed solution a is sucked by a syringe and injected into a hemispherical silica gel mold, and the mold is removed after solidification to obtain a potassium permanganate sustained-release gel; Step S2, preparing sodium bisulfite sustained-release gel: Adding sodium bisulfite to the silica sol solution and stirring evenly to obtain a mixed solution b; using a syringe to draw the mixed solution b and injecting it into a hemispherical silicone mold, and demolding after solidification to obtain a sodium bisulfite sustained-release gel; Step S3, preparing sustained-release composite pharmaceutical spheres: The potassium permanganate sustained-release gel obtained in step S1 and the sodium bisulfite sustained-release gel obtained in step S2 are adhered together using organic silica gel to obtain a gel-type sodium bisulfite-activated potassium permanganate sustained-release composite pharmaceutical sphere with silica sol as a carrier; the molar ratio of potassium permanganate in the potassium permanganate sustained-release gel to sodium bisulfite in the sodium bisulfite sustained-release gel is (1:2.5), (1:5) or (1:10).

2. The method for preparing a gel-type sodium bisulfite activated potassium permanganate sustained-release composite medicament with silica sol as a carrier according to claim 1, characterized in that The ratio of the mass of potassium permanganate to the volume of the silica sol solution in step S1 is (0.316-0.632) g:20 mL.

3. The method for preparing a gel-type sodium bisulfite activated potassium permanganate sustained-release composite medicament with silica sol as a carrier according to claim 1, characterized in that In step S1, the mixed solution a is injected into the hemispherical silicone mold, solidified at a temperature of 25 to 30° C. for 12 to 24 hours, and then demoulded.

4. The method for preparing a gel-type sodium bisulfite activated potassium permanganate sustained-release composite medicament with silica sol as a carrier according to claim 1, characterized in that The ratio of the mass of sodium bisulfite to the volume of the silica sol solution in step S2 is (1.04-4.16) g:20 mL.

5. The method for preparing a gel-type sodium bisulfite activated potassium permanganate sustained-release composite medicament with silica sol as a carrier according to claim 1, characterized in that In step S2, the mixed solution b is injected into the hemispherical silicone mold, solidified at a temperature of 25 to 30° C. for 12 to 24 hours, and then demoulded.

6. The method for preparing a gel-type sodium bisulfite activated potassium permanganate sustained-release composite medicament with silica sol as a carrier according to claim 1, characterized in that The mass fraction of silica sol in the silica sol solutions described in step S1 and step S2 is 19-41%.

7. The method for preparing a gel-type sodium bisulfite activated potassium permanganate sustained-release composite medicament with silica sol as a carrier according to claim 1, characterized in that A magnetic stirrer is used for stirring in both step S1 and step S2.

8. The method for preparing a gel-type sodium bisulfite activated potassium permanganate sustained-release composite medicament with silica sol as a carrier according to claim 1, characterized in that The volumes of the mixed solution a and the mixed solution b absorbed in step S1 and step S2 are both 1 mL, 2 mL, 3 mL or 4 mL.

9. The method for preparing a gel-type sodium bisulfite activated potassium permanganate sustained-release composite medicament with silica sol as a carrier according to claim 1, characterized in that The diameter of the gel-type sodium bisulfite activated potassium permanganate sustained-release composite pharmaceutical sphere described in step S2 is 1.56 to 2.48 cm.

10. Use of a gel-type sodium bisulfite activated potassium permanganate sustained-release composite pharmaceutical agent with silica sol as a carrier as claimed in any one of claims 1 to 9, characterized in that The gel-type sodium bisulfite activated potassium permanganate slow-release composite agent using silica sol as a carrier is used in removing algae and difficult-to-degrade organic pollutants in surface water and removing pesticides and difficult-to-degrade organic pollutants in soil.

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