Preparation method and application of carbon-based adsorption material for water treatment
By using a heterogeneous catalytic system of carbon-based adsorbent materials, perborate, and persulfate, the problems of secondary pollution and low efficiency of traditional catalytic systems are solved, achieving high-efficiency water treatment and reducing equipment maintenance costs.
Patent Information
- Application Number
- CN202511130762.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-13
- Publication Date
- 2025-11-07
AI Technical Summary
Traditional homogeneous catalytic systems in water treatment suffer from secondary pollution from metal sludge and waste of resources. Furthermore, the binding efficiency of persulfate to the catalyst is low, and the electron transfer efficiency is slow, which affects the improvement of catalytic efficiency.
A heterogeneous catalytic system using carbon-based adsorbents and perborate and hydrogen persulfate was developed. The carbon-based adsorbents were prepared by electrospinning and calcination, and then mixed with water-soluble perborate and hydrogen persulfate at room temperature and pressure to promote the heterogeneous catalytic reaction.
It improves the activation efficiency of persulfate, enhances electron transfer and non-radical oxidation degradation efficiency, and makes the water neutral or weakly alkaline after the reaction, reducing equipment maintenance costs and producing hydrogen peroxide to enhance oxidation degradation efficiency.
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Figure CN120900583A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the field of water treatment, and particularly relates to a preparation method and application of a carbon-based adsorption material for water treatment. BACKGROUND
[0002] A large number of emerging organic pollutants are frequently detected in water environment. These organic pollutants have stable chemical properties, most of which can be enriched in organisms along the food chain, have potential ecological toxicity, and seriously endanger water safety and human health. The advanced oxidation technology based on sulfate radicals (SR-AOPs) is considered as a promising water treatment strategy due to its fast reaction speed, wide application range, mild reaction conditions, and good treatment effect. However, the traditional homogeneous reaction system is prone to produce metal sludge, causing secondary pollution, and the metal ions cannot be recycled, resulting in waste of resources. In order to effectively avoid the above disadvantages, the heterogeneous catalytic system has attracted widespread attention from researchers.
[0003] At present, in the heterogeneous catalytic system based on sulfate radicals, the combination efficiency of persulfate hydrogen salt and active sites on the catalyst is low, and the persulfate hydrogen salt is difficult to be effectively activated. In addition, the electron transfer efficiency on the surface of the catalyst in the catalytic process is slow, which seriously restricts the further improvement of the catalytic efficiency. In addition, with the continuous deepening of research, the advanced oxidation technology no longer simply relies on the generation of free radicals to oxidize and degrade pollutants in water, and the non-homogeneous catalytic system relying on the generation of singlet oxygen, high-valent metal ions and pollutant electron transfer and other non-radical oxidation pathways has attracted attention, which can further improve the efficiency of oxidative degradation. SUMMARY
[0004] The present application aims to provide a preparation method and application of a carbon-based adsorption material for water treatment to solve the above technical problems.
[0005] To solve the above technical problems, the present application adopts the following technical solutions: A preparation method of a carbon-based adsorption material for water treatment, comprising the following steps: S1, 2.7g of PAN is dissolved in 25g of DMF, and mechanical stirring is performed until complete dissolution to obtain 10% PAN spinning solution; S2, the 10% PAN spinning solution obtained in S1 is electrospun under the conditions that the spinning voltage is 15-18kV, the distance between the electrostatic spinning head and the collecting drum is 5-9cm, the rotating speed of the collecting drum is 380rpm, and the advancing speed of the spinning head is 0.8-1.0mL / h, the spinning time is 4 hours, and a spinning sheet is obtained; S3, the spinning sheet obtained in S2 is compressed with a high-temperature-resistant glass plate in a muffle furnace, the temperature is raised to 280℃ at a temperature raising rate of 1℃ / min, and the temperature is kept for 2h; S4, the material obtained in S3 is uniformly mixed with sublimed sulfur at a mass ratio of 1:10, and then placed in a tube furnace under nitrogen protection, heated to 800℃ at a heating rate of 5℃ / min, and calcined for 2 hours.
[0006] Application of carbon-based adsorbent material in oxidation treatment of organic pollutants in water plants, comprising the following steps: S1, providing a water source to be treated containing organic pollutants; S2, mixing and stirring water-soluble perborate, water-soluble persulfate, carbon-based adsorbent material with the above-mentioned water source to be treated containing organic pollutants.
[0007] Further, the organic pollutants are one or more of geosmin, 2-methylisoborneol, microcystin-LR, sulfadiazine, carbamazepine, bisphenol A.
[0008] Further, the concentration of organic pollutants in the water to be treated is less than 40 μM (i.e. μmol / L), preferably 20-30 μM.
[0009] Further, the pH value of the water source to be treated is ≤7, preferably 3-7.
[0010] Further, the water-soluble perborate includes one or more of sodium perborate (NaBO3), potassium perborate.
[0011] Further, the water-soluble persulfate includes one or more of sodium hydrogen persulfate, potassium hydrogen persulfate (PMS).
[0012] Further, the molar ratio of water-soluble perborate to water-soluble persulfate is 1-3: 1-3.
[0013] Further, the initial molar ratio of organic pollutants to water-soluble persulfate is 1:10-100, further 1:20-50.
[0014] Further, after mixing the water-soluble perborate, water-soluble persulfate, carbon-based adsorbent material and water, the initial concentration of water-soluble persulfate is 1-3 mM, the initial concentration of water-soluble perborate is 1-3 mM, further 1-2 mM, and the initial concentration of carbon-based adsorbent material is 0.05-0.30 g / L.
[0015] Further, the reaction is carried out under normal temperature and pressure conditions.
[0016] The beneficial effects of the present application are: 1. The perborate and persulfate heterogeneous catalytic system can increase the adsorption energy between persulfate and catalyst, effectively improving the activation efficiency of persulfate in heterogeneous reaction.
[0017] 2. The perborate effectively enhances the loss of electrons of the pollutant molecules on the surface of the catalyst, thereby enhancing the non-radical oxidative degradation pathway of the electron transfer of the pollutants.
[0018] 3. The perborate has alkalinity, which can effectively neutralize the acidity generated in the peroxymonosulfate dissolution process. The water body after the reaction is neutral or weakly alkaline, eliminating the subsequent step of adjusting the pH value, which is conducive to reducing the equipment maintenance cost.
[0019] 4. A large amount of hydrogen peroxide is generated during the reaction process, and this part of the oxidant can be further activated by the catalyst to generate hydroxyl radicals, thereby enhancing the oxidative degradation efficiency of the pollutants. BRIEF DESCRIPTION OF DRAWINGS
[0020] Figure 1 Transmission electron micrograph of carbon nanofiber loaded nickel elemental adsorbent material; Figure 2 Energy spectrum scanning graph of carbon nanofiber loaded nickel elemental adsorbent material; Figure 3 X-ray diffraction graph of carbon nanofiber loaded nickel elemental adsorbent material; Figure 4 Comparison chart of sulfonamide pyrimidine removal effect of carbon nanofiber loaded nickel elemental adsorbent material in different systems; Figure 5 Comparison chart of sulfonamide pyrimidine removal effect of carbon nanofiber loaded nickel elemental adsorbent material at different pH values; Figure 6 Comparison of sulfonamide pyrimidine degradation effects of different catalytic systems; Figure 7 Effect of perborate concentration on the degradation of sulfonamide pyrimidine by the catalytic system; Figure 8 Effect of peroxymonosulfate concentration on the degradation of sulfonamide pyrimidine by the catalytic system; Figure 9 Change of pH in the catalytic system under different initial pH conditions of the sulfonamide pyrimidine solution; Figure 10 Degradation effect of the catalytic system on various PPCPs; Figure 11 Comparison of adsorption energy of PMS on Cu-CNF and BO3- / Cu-CNF. DETAILED DESCRIPTION
[0021] In order to make the technical means, creative features, purposes and effects of the present application easy to understand, the present application is further described below in conjunction with specific embodiments and drawings. However, the following embodiments are only preferred embodiments of the present application, not all. Based on the embodiments in the embodiments, other embodiments obtained by those skilled in the art without creative labor are within the protection scope of the present application.
[0022] The specific embodiments of the present application are described below in conjunction with the drawings.
[0023] Embodiment 1 As shown in the figure, a preparation method of a carbon-based adsorption material for water treatment comprises the following steps: Figures 1-5 S1, 2.7 g of PAN is dissolved in 25 g of DMF, and mechanical stirring is performed until complete dissolution to obtain 10% PAN spinning solution; S2, the 10% PAN spinning solution obtained in S1 is electrospun under the conditions of a spinning voltage of 15-18 kV, a distance between the electrostatic spinning head and the collection drum of 5-9 cm, a rotation speed of the collection drum of 380 rpm, and a push speed of the spinning head of 0.8-1.0 mL / h, and the spinning time is 4 hours to obtain a spinning sheet; S3, the spinning sheet obtained in S2 is compressed with a high-temperature-resistant glass plate in a muffle furnace, and the temperature is raised to 280℃ at a heating rate of 1℃ / min, and the temperature is maintained for 2 h; S4, the material obtained in S3 is uniformly mixed with sublimed sulfur at a mass ratio of 1:10, and then placed in a tube furnace under nitrogen protection, and the temperature is raised to 800℃ at a heating rate of 5℃ / min, and the calcination time is 2 hours Embodiment 2 As shown in the figure, in the case that other parts are the same as embodiment 1, the difference between this embodiment and embodiment 1 is that the carbon-based adsorption material is applied to the oxidation treatment of organic pollutants in a water plant, comprising the following steps: S1, providing a water source to be treated, which contains organic pollutants; Figure 6 S2, mixing and stirring water-soluble perborate, water-soluble persulfate hydrogen salt, and carbon-based adsorption material with the above-mentioned water source to be treated containing organic pollutants; The organic pollutants are one or several of geosmin, 2-methylisoborneol, microcystin-LR, sulfadiazine, carbamazepine, and bisphenol A. The concentration of organic pollutants in the water to be treated is less than 40 μM (i.e. μmol / L), and is preferably 20-30 μM.
[0024] The pH value of the water source to be treated is ≤7, and is preferably 3-7.
[0025] The pH value of the water source to be treated is ≤7, and is preferably 3-7.
[0026] The water-soluble perborate salt includes one or more of sodium perborate (NaBO3) and potassium perborate.
[0027] The water-soluble persulfate hydrogen salt includes one or more of sodium hydrogen persulfate and potassium hydrogen persulfate (PMS).
[0028] The molar ratio of the water-soluble perborate salt and the water-soluble persulfate hydrogen salt is 1-3: 1-3.
[0029] The initial molar ratio of the organic pollutants and the water-soluble persulfate hydrogen salt is 1: 10-100, and further 1: 20-50.
[0030] After mixing the water-soluble perborate salt, the water-soluble persulfate hydrogen salt, the carbon-based adsorption material and water, the initial concentration of the water-soluble persulfate hydrogen salt is 1-3 mM, the initial concentration of the water-soluble perborate salt is 1-3 mM, and further 1-2 mM, and the initial concentration of the carbon-based adsorption material is 0.05-0.30 g / L.
[0031] The reaction is carried out under normal temperature and pressure conditions. The method for promoting the removal of organic pollutants in water by a heterogeneous catalytic system by using a perborate salt includes the following steps: 50 mL of a sulfadiazine (SDZ) solution with a concentration of 40 μM (initial pH = 6.32) is taken into a 100 mL reaction container, and one or more combinations of a perborate salt (BO3 - ), a persulfate hydrogen salt (PMS) and a copper-loaded carbon nanofiber catalyst (Cu-CNF) are added to form a catalytic system (PMS system, BO3 - system, PMS / BO3 - system, PMS / Cu-CNF system, BO3 - / Cu-CNF system, PMS / BO3 - / Cu-CNF system), which is stirred uniformly, and then the reaction is carried out under normal temperature and pressure conditions for 30 min, and the degradation effect is compared; the initial concentrations of PMS and BO3 - are 1 mM, and the concentration of Cu-CNF is 0.1 g / L.
[0032] The systems of adding PMS, NaBO3 and Cu-CNF alone and the BO3 - / Cu-CNF system cannot effectively remove SDZ, the PMS / NaBO3 system and the PMS / Cu-CNF system can remove 50% and 57% of SDZ respectively within 30 min, and the PMS / BO3 - / Cu-CNF system can quickly remove SDZ within 5 min. This shows that the perborate salt can effectively promote the removal of organic pollutants in water by a heterogeneous catalytic system.
[0033] Example 3: As Figure 7 shown, in the case of other parts are the same as example 1, the difference between this embodiment and example 1 is that: the effect of BO3 - / Cu-CNF system on the degradation of organic pollutants in the catalytic system is investigated. -
[0034] The operation steps are basically the same as example 2: 50 mL of sulfadiazine (SDZ) solution with a concentration of 40 μM (initial pH = 6.32) is placed in a 100 mL reaction container, and perborate (BO3 - ), persulfate (PMS) and copper-loaded carbon nanofiber catalyst (Cu-CNF) are added, stirred uniformly, and after 30 min of reaction under normal temperature and pressure, the degradation effect is compared. The initial concentration of PMS is 1 mM, the initial concentration of BO3 - is 0.25-2 mM, and the concentration of Cu-CNF is 0.1 g / L. With the increase of the amount of BO3 - , the removal effect of SDZ first increases and then decreases, so the amount of BO3 - added is best when it is consistent with the concentration of PMS.
[0035] Example 4: As Figure 8 shown, in the case of other parts are the same as example 1, the difference between this embodiment and example 1 is that: the effect of BO3 - / Cu-CNF system on the degradation of organic pollutants in the catalytic system is investigated.
[0036] The operation steps are basically the same as example 2: 50 mL of sulfadiazine (SDZ) solution with a concentration of 40 μM (initial pH = 6.32) is placed in a 100 mL reaction container, and perborate (BO3 - ), persulfate (PMS) and copper-loaded carbon nanofiber catalyst (Cu-CNF) are added, stirred uniformly, and after 30 min of reaction under normal temperature and pressure, the degradation effect is compared. The initial concentration of PMS is 0.25-2 mM, the initial concentration of BO3 - is 1 mM, and the concentration of Cu-CNF is 0.1 g / L. With the increase of the amount of PMS from 0.25 mM to 1 mM, the removal effect of SDZ increases rapidly, and when the concentration of PMS continues to increase to 2 mM, the removal effect of SDZ is basically unchanged, so the concentration of PMS is best when it is 1 mM.
[0037] Example 5: As Figure 9 As shown, while all other parts are the same as in Example 1, the difference between this example and Example 1 lies in the examination of PMS / BO3. - pH changes during the reaction process under different initial pH conditions in the Cu-CNF system.
[0038] The procedure is essentially the same as in Example 2, but the steps are as follows: 50 mL of a 40 μM sulfadiazine (SDZ) solution (initial pH adjusted to 3, 5, 7, 9, 10) is placed in a 100 mL reaction vessel, and perborate (BO3) is added. - The degradation effects of PMS (polysulfate persulfate) and copper-supported carbon nanofiber catalyst (Cu-CNF) were compared after stirring and reacting at room temperature and pressure for 30 min. The initial concentration of PMS was 1 mM, and the BO3 content was 1 mM. - The initial concentration was 1 mM Cu-CNF and the concentration was 0.1 g / L.
[0039] With an initial pH range of 5-9, the pH of the solution stabilizes at around 7-8 after the reaction, indicating that within the normal pH range of water bodies, the heterogeneous catalytic system promoted by perborate can effectively alleviate water acidification without the need for subsequent pH adjustment.
[0040] Example 6: like Figure 10 As shown, while all other parts are the same as in Example 1, the difference between this example and Example 1 lies in the examination of PMS / BO3. - The effect of the Cu-CNF system on the degradation of different organic pollutants.
[0041] The procedure is essentially the same as in Example 2, except that: 50 mL of a 40 μM organic pollutant solution is placed in a 100 mL reaction vessel, and perborate (BO3) is added. - The degradation effects of PMS (polysulfate persulfate) and copper-supported carbon nanofiber catalyst (Cu-CNF) were compared after stirring and reacting at room temperature and pressure for 30 min. The initial concentration of PMS was 1 mM, and the BO3 content was 1 mM. - The initial concentration was 1 mM Cu-CNF and the concentration was 0.1 g / L. The organic pollutants included multiple PPCPs such as sulfamethoxazole (SMX), naproxen (NPX), carbamazepine (CBZ), and coumarin (CM).
[0042] PMS / BO3 - The / Cu-CNF system can effectively degrade various PPCPs, including sulfamethoxazole (SMX), naproxen (NPX), carbamazepine (CBZ), and coumarin (CM).
[0043] Example 7: As Figures 6-11 shown, in the case of other parts being the same as example 1, the difference between this embodiment and example 1 is that DFT is used to comparatively study the adsorption energy of PMS / BO3 - / Cu-CNF, PMS / Cu-CNF two systems.
[0044] It is calculated that the adsorption energy of PMS on Cu-CNF is 0.43 eV, and when BO3 - is introduced, the adsorption energy of Cu-CNF on PMS is greatly increased to 4.75 eV. The increase of adsorption energy can improve the utilization efficiency of PMS / Cu-CNF heterogeneous catalytic system on PMS, thereby improving the removal effect of the system on organic pollutants.
[0045] The above shows and describes the basic principles, main features and advantages of the present application. It should be understood by those skilled in the art that the present application is not limited by the above examples, and the above examples and descriptions in the specification are only preferred examples of the present application and are not intended to limit the present application. Without departing from the spirit and scope of the present application, various changes and improvements can be made to the present application, and these changes and improvements all fall within the scope of the present application. The scope of protection of the present application is defined by the appended claims and their equivalents.
Claims
1. A method for the preparation of carbon-based adsorbent material for water treatment, characterized by , comprising the following steps: S1, 2.7 g of PAN is dissolved in 25 g of DMF, and mechanical stirring is performed until complete dissolution to obtain a 10% PAN spinning solution; S2, the 10% PAN spinning solution obtained in S1 is electrospun under the conditions of a spinning voltage of 15-18 kV, a distance between the electrospinning head and the collection drum of 5-9 cm, a rotation speed of the collection drum of 380 rpm, and a push speed of the spinning head of 0.8-1.0 mL / h, and the spinning time is 4 hours to obtain a spinning sheet; S3, the spinning sheet obtained in S2 is compressed with a high-temperature-resistant glass plate in a muffle furnace, and the temperature is raised to 280°C at a rate of 1°C / min, and the temperature is maintained for 2 h; S4, the material obtained in S3 is uniformly mixed with sublimed sulfur at a mass ratio of 1:10, and then placed in a tube furnace under nitrogen protection, and the temperature is raised to 800°C at a rate of 5°C / min, and the calcination time is 2 hours.
2. Use of the carbon-based adsorbent material according to claim 1 for the oxidative treatment of organic pollutants in water plants, characterized in that, Comprising the following steps: S1, providing a water source to be treated containing organic pollutants; S2, mixing and stirring the water-soluble perborate, the water-soluble persulfate hydrogen salt, and the carbon-based adsorption material with the water source to be treated containing organic pollutants.
3. Use of the carbon-based adsorbent material according to claim 2 for the oxidative treatment of organic pollutants in water plants, characterized in that: The organic pollutants include one of PPCPs, endocrine disruptors, and pesticides.
4. Use of the carbon-based adsorbent material according to claim 2 for the oxidative treatment of organic pollutants in water plants, characterized by the fact that: The water-soluble perborate includes one of sodium perborate (NaBO3) and potassium perborate.
5. Use of the carbon-based adsorbent material according to claim 2 for the oxidative treatment of organic pollutants in water plants, characterized by the fact that: The water-soluble perborate, the water-soluble persulfate hydrogen salt, and the carbon-based adsorption material react with the water source to be treated containing organic pollutants under normal temperature and pressure.
6. Use of the carbon-based adsorbent material according to claim 2 for the oxidative treatment of organic pollutants in water plants, characterized by the fact that: The concentration of the organic pollutants is less than 50 μM.
7. Use of the carbon-based adsorbent material according to claim 2 for the oxidative treatment of organic pollutants in water plants, characterized by the fact that: The water-soluble persulfate hydrogen salt includes one of sodium hydrogen persulfate (PMS) and potassium hydrogen persulfate.
8. Use of the carbon-based adsorbent material according to claim 2 for the oxidative treatment of organic pollutants in water plants, characterized by the fact that: The molar ratio of the water-soluble perborate and the water-soluble persulfate hydrogen salt is 1-3: 1-3.