Potassium permanganate compound medicament for improving utilization efficiency of active intermediate state manganese and application thereof
By combining potassium permanganate with nitrogen-containing ligands to form complexes and surface interactions, the aggregation of tetravalent manganese particles is inhibited, and the active intermediate manganese is stabilized. This solves the problem of low oxidation potential of potassium permanganate under alkaline conditions and achieves the effect of highly efficient oxidation and degradation of organic pollutants.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- HARBIN INST OF TECH
- Filing Date
- 2026-06-05
- Publication Date
- 2026-07-03
AI Technical Summary
Existing potassium permanganate reagents have low oxidation potential under alkaline conditions, resulting in insufficient reactivity for some organic pollutants. Furthermore, the active intermediate manganese is prone to disproportionation or hydrolysis, making it difficult to effectively participate in the oxidation reaction of pollutants.
Introducing nitrogen-containing ligands in combination with potassium permanganate forms complexes or surface interactions, which inhibits the aggregation of tetravalent manganese particles, increases the oxidation potential, and stabilizes the active intermediate manganese through the five-membered ring structure, thus promoting the recycling of manganese.
It significantly enhances the oxidative degradation capacity of organic matter, improves the stability and utilization efficiency of active intermediate manganese, is suitable for wastewater treatment with pH 5-9, and has good anti-interference ability and economy.
Smart Images
Figure CN122324973A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to a potassium permanganate compound agent for improving the utilization efficiency of active intermediate manganese and its application, belonging to the field of wastewater treatment. Background Technology
[0002] Potassium permanganate (Mn(VII)) is widely used in water and wastewater treatment due to its advantages such as good stability, wide applicable pH range, low cost, and ease of operation. However, potassium permanganate has a low oxidation potential under alkaline conditions, resulting in insufficient reactivity for some organic pollutants. Furthermore, while the active intermediate manganese forms such as Mn(III), Mn(V), and Mn(VI) generated during the reaction have strong oxidizing capabilities, they are prone to disproportionation or hydrolysis. The resulting Mn(IV) (usually existing as MnO2) has catalytic, adsorption, and oxidizing capabilities, but Mn(IV) easily aggregates into large precipitates, making it difficult to effectively participate in pollutant oxidation reactions.
[0003] Existing technologies primarily promote the decomposition of potassium permanganate by introducing reducing agents or applying external energy to increase the generation rate of active intermediate manganese. However, these methods generally neglect the utilization efficiency of active intermediate manganese. Furthermore, some studies have attempted to stabilize Mn(III) by introducing ligands to inhibit its disproportionation reaction, thereby extending the existence time of active intermediate manganese to some extent. However, these ligands typically only act on manganese in a single valence state, mainly focusing on the stabilization of Mn(III), and lack effective regulation of Mn(IV) particle aggregation, particle size variation, and electron transport behavior. Summary of the Invention
[0004] In order to solve the problem of low utilization efficiency of active intermediate manganese in existing potassium permanganate agents, this invention proposes a potassium permanganate compound agent and its application to improve the utilization efficiency of active intermediate manganese.
[0005] The present invention provides a potassium permanganate compound reagent for improving the utilization efficiency of active intermediate manganese, comprising potassium permanganate and a nitrogen-containing ligand; the molar ratio of the nitrogen-containing ligand to potassium permanganate is 1~5:1~10; the nitrogen-containing ligand is an organic ligand with a nitrogen-donating electron site.
[0006] This invention relates to a potassium permanganate compound reagent that improves the utilization efficiency of active intermediate manganese and is applied to the oxidative degradation of organic pollutants in wastewater.
[0007] Compared with the prior art, the present invention has the following beneficial effects:
[0008] 1. The nitrogen-containing ligands introduced into the potassium permanganate compound of this invention can form complexes with manganese of different valence states, or can interact with Mn(IV) on the surface. The carboxyl group H of the pyridine nitrogen in the nitrogen-containing ligand can act as a hydrogen bond donor, and pyridine nitrogen is a good hydrogen bond acceptor. Both can be connected to the manganese oxygen bond on the surface of tetravalent manganese through hydrogen bonds, thus increasing the steric hindrance of the aggregation between tetravalent manganese particles and inhibiting the growth of tetravalent manganese particles. At the same time, the formed Mn(IV)-ligand-potassium permanganate composite structure has a higher oxidation potential, which is more conducive to electron transfer and significantly improves the system's ability to oxidize and degrade organic matter. In addition, the pyridine nitrogen, carboxyl oxygen and trivalent manganese of the nitrogen-containing ligand form a five-membered ring structure, which inhibits the disproportionation of active intermediate manganese and improves the stability of intermediate manganese.
[0009] 2. The nitrogen-containing ligand introduced into the potassium permanganate compound of the present invention can reduce the reduction potential of divalent manganese and promote the disproportionation reaction between divalent manganese and hypervalent manganese to generate Mn(III) and Mn(IV), thereby helping to maintain the continuous recycling of manganese and further improving the utilization efficiency of active intermediate manganese.
[0010] 3. The potassium permanganate compound reagent of the present invention is applied to the oxidative degradation of organic pollutants in wastewater with pH of 5-9, and has good treatment effect. It is suitable for complex water environment. Common anions and metal ions do not react with the compound reagent and have little impact on the degradation efficiency of the compound reagent system. It has good anti-interference ability.
[0011] 4. In this invention, a carrier is introduced into the potassium permanganate compound reagent. Nitrogen-containing ligands are loaded onto the carrier and compounded with potassium permanganate. The nitrogen-containing ligands only act as coordination agents and do not react with intermediate manganese. They do not directly participate in the degradation of organic matter, and the coordination product Mn... 2+ -Pyridinecarboxylic acid can promote manganese cycling. Therefore, in actual water treatment, the carrier and nitrogen-containing ligand can be recycled multiple times, exhibiting good stability and economy. Attached Figure Description
[0012] Figure 1 The graph shows the removal efficiency of 2,6-dichlorophenol in different embodiments;
[0013] Figure 2 A graph showing the degradation rate of pollutants at different pH values;
[0014] Figure 3 The graph shows the effect of different 2-pyridinecarboxylic acid concentrations on the degradation rate of pollutants.
[0015] Figure 4 This is a graph showing the recycling performance of the nitrogen-containing ligand in Example 5;
[0016] Figure 5The graph shows the utilization efficiency of active intermediate manganese by different ligands or activation systems. Detailed Implementation
[0017] The technical solution of the present invention is not limited to the specific embodiments listed below, but also includes any reasonable combination of the specific embodiments.
[0018] Specific Implementation Method 1: The potassium permanganate compound agent used in this implementation method to improve the utilization efficiency of active intermediate manganese includes potassium permanganate and nitrogen-containing ligands;
[0019] The molar ratio of the nitrogen-containing ligand to potassium permanganate is 1~5:1~10;
[0020] The nitrogen-containing ligand is an organic ligand with a nitrogen-donating electron site.
[0021] This embodiment has the following beneficial effects:
[0022] 1. In this embodiment, the nitrogen-containing ligands introduced into the potassium permanganate compound can form complexes with manganese of different valence states, or can interact with Mn(IV) on the surface. The carboxyl group H of the pyridine nitrogen in the nitrogen-containing ligand can act as a hydrogen bond donor, and pyridine nitrogen is a good hydrogen bond acceptor. Both can be connected to the manganese oxygen bond on the surface of tetravalent manganese through hydrogen bonds, thus increasing the steric hindrance of the aggregation between tetravalent manganese particles and inhibiting the growth of tetravalent manganese particles. At the same time, the formed Mn(IV)-ligand-potassium permanganate composite structure has a higher oxidation potential, which is more conducive to electron transfer and significantly improves the system's ability to oxidize and degrade organic matter. In addition, the pyridine nitrogen, carboxyl oxygen, and trivalent manganese of the nitrogen-containing ligand form a five-membered ring structure, which inhibits the disproportionation of active intermediate manganese and improves the stability of intermediate manganese.
[0023] 2. The nitrogen-containing ligands introduced into the potassium permanganate compound in this embodiment can reduce the reduction potential of divalent manganese and promote the disproportionation reaction between divalent manganese and hypervalent manganese to generate Mn(III) and Mn(IV), thereby helping to maintain the continuous recycling of manganese and further improving the utilization efficiency of active intermediate manganese.
[0024] 3. The potassium permanganate compound reagent in this embodiment is applied to the oxidative degradation of organic pollutants in wastewater with a pH of 5-9, and it has good treatment effect. It is suitable for complex water environments. Common anions and metal ions do not react with the compound reagent and have little impact on the degradation efficiency of the compound reagent system. It has good anti-interference ability.
[0025] 4. In this embodiment, a carrier is introduced into the potassium permanganate compound agent. Nitrogen-containing ligands are loaded onto the carrier and compounded with potassium permanganate. The nitrogen-containing ligands only act as coordination agents and do not react with intermediate manganese. They do not directly participate in the degradation of organic matter, and the coordination product Mn... 2+-Pyridinecarboxylic acid can promote manganese cycling. Therefore, in actual water treatment, the carrier and nitrogen-containing ligand can be recycled multiple times, exhibiting good stability and economy.
[0026] Specific Implementation Method Two: This implementation method differs from Specific Implementation Method One in that the organic ligand with the nitrogen-donating electron site is at least one selected from 2-pyridinecarboxylic acid, 2,2'-bipyridine, 1,10-phenanthroline, a 2-pyridinecarboxylic acid derivative, a 2,2'-bipyridine derivative, and a 1,10-phenanthroline derivative. Among the organic ligands, 2-pyridinecarboxylic acid exhibits good environmental compatibility and biodegradability, while also effectively regulating the behavior of manganese in the potassium permanganate system.
[0027] Specific Implementation Method 3: This implementation method differs from Specific Implementation Method 1 in that the potassium permanganate compound agent for improving the utilization efficiency of active intermediate manganese also includes a carrier, on which nitrogen-containing ligands are loaded and compounded with potassium permanganate.
[0028] Specific Implementation Method Four: This implementation method differs from Specific Implementation Method Three in that the nitrogen-containing ligand loading on the carrier is 50~150μmol / g.
[0029] Specific Implementation Method Five: This implementation method differs from Specific Implementation Method Three in that the carrier is montmorillonite.
[0030] Specific Implementation Method Six: This implementation method differs from Specific Implementation Method Three in that the loading method is as follows: the carrier is dispersed in an aqueous solution of 2-pyridinecarboxylic acid, stirred for 120 minutes, centrifuged to separate the solid, and finally washed and freeze-dried.
[0031] Specific Implementation Method Seven: This implementation method improves the utilization efficiency of active intermediate manganese by applying potassium permanganate compound reagents to the oxidative degradation of organic pollutants in wastewater.
[0032] Specific Implementation Method Eight: This implementation method differs from Specific Implementation Method Seven in that the organic pollutants in the wastewater are phenolic organic pollutants.
[0033] Specific Implementation Method Nine: This implementation method differs from Specific Implementation Method Seven in that the pH of the wastewater is 5-9.
[0034] Specific Implementation Method 10: This implementation method differs from Specific Implementation Method 7 in that the amount of potassium permanganate added to the wastewater is 10~500μmol / L.
[0035] Example 1
[0036] The potassium permanganate compound preparation in this embodiment includes potassium permanganate and a nitrogen-containing ligand; the molar ratio of the nitrogen-containing ligand to potassium permanganate is 1:5, and the nitrogen-containing ligand is 2-pyridinecarboxylic acid;
[0037] This embodiment demonstrates the application of a potassium permanganate compound reagent to improve the utilization efficiency of active intermediate manganese in the oxidative degradation of organic pollutants in wastewater. The organic pollutant in the wastewater is 2,6-dichlorophenol with a concentration of 5 μmol / L. The pH of the wastewater is adjusted to 5.0 using 2 mmol / L acetate buffer. The amount of potassium permanganate added to the wastewater is 50 μmol / L.
[0038] After potassium permanganate compound reagent was added to the wastewater, the reaction was carried out at 25℃ for 7.5 min. After the reaction, the removal rate of 2,6-dichlorophenol exceeded 90%, and the reaction rate constant was 1.18 min. -1 , significantly higher than control 1.
[0039] Comparative Example 1
[0040] The difference between this embodiment and Embodiment 1 is that only potassium permanganate is used for the oxidative degradation of organic pollutants in wastewater, without the addition of nitrogen-containing ligands. Other processes and parameters are the same as in Embodiment 1.
[0041] After potassium permanganate was added to the wastewater, the reaction proceeded at 25°C for 7.5 min. After the reaction, the removal rate of 2,6-dichlorophenol was less than 30%, and the reaction rate constant was only 0.04 min. -1 .
[0042] Example 2
[0043] The difference between this embodiment and Embodiment 1 is that a buffer solution was used to adjust the pH of the wastewater to 5-9 for the experiment, while other processes and parameters were the same as in Embodiment 1.
[0044] Figure 2 A graph showing the degradation rate of pollutants at different pH values; Figure 2 This indicates that the pollutant degradation reaction is most effective in the pH range of 5 to 7, and the degradation effect is significantly enhanced in the pH range of 5 to 9.
[0045] Example 3
[0046] The difference between this embodiment and Example 1 is that the amount of 2-pyridinecarboxylic acid added is 0-45 μmol / L. Other processes and parameters are the same as in Example 1.
[0047] Figure 3 The graph shows the effect of different 2-pyridinecarboxylic acid concentrations on the degradation rate of pollutants. Figure 3 This indicates that the reaction rate increases significantly with increasing 2-pyridinecarboxylic acid concentration.
[0048] Example 4
[0049] The utilization efficiency of active intermediate manganese in the system of 2-pyridinecarboxylic acid (0–1000 μmol / L) and potassium permanganate (5.7 μmol / L) was tested using the ABTS probe method.
[0050] like Figure 5 As shown, with increasing ligand concentration, the utilization efficiency of active intermediate manganese species increases from about 50% to nearly 100%.
[0051] Example 5
[0052] The potassium permanganate compound preparation in this embodiment includes potassium permanganate, a nitrogen-containing ligand, and a carrier; the molar ratio of the nitrogen-containing ligand to potassium permanganate is 1:5, the nitrogen-containing ligand is 2-pyridinecarboxylic acid; the nitrogen-containing ligand loading on the carrier is 50 μmol / g; the carrier is montmorillonite.
[0053] This embodiment demonstrates the application of a potassium permanganate compound reagent to improve the utilization efficiency of active intermediate manganese in the oxidative degradation of organic pollutants in wastewater. The organic pollutant in the wastewater is 2,6-dichlorophenol at a concentration of 5 μmol / L, and the pH of the wastewater is 6.8. The amount of potassium permanganate added to the wastewater is 50 μmol / L, and 5 g / L of montmorillonite loaded with nitrogen-containing ligands is added. After the potassium permanganate compound reagent is added to the wastewater, it is reacted at 25°C for 20 min. After the reaction, the wastewater is centrifuged, the carrier is recovered, and the mixture is recombined with potassium permanganate for repeated pollutant treatment. Figure 4 This is a graph showing the recycling performance of the nitrogen-containing ligand in Example 5. Figure 4 This indicates that the nitrogen-containing ligand in this embodiment still maintains a high degradation efficiency after being recycled 5 times.
[0054] Example 6
[0055] The difference between this embodiment and Example 1 is that the nitrogen-containing ligand is 1,10-phenanthroline. Other processes and parameters are the same as in Example 1.
[0056] When potassium permanganate compound reagent is added to wastewater, the reaction proceeds at 25°C for 7.5 min; 2,6-dichlorophenol is completely removed, with a reaction rate constant of 1.38 min. -1 .
[0057] Example 7
[0058] The difference between this embodiment and Example 1 is that the nitrogen-containing ligand is 2,2'-bipyridine. Other processes and parameters are the same as in Example 1.
[0059] When potassium permanganate compound reagent is added to wastewater, the reaction proceeds at 25°C for 7.5 min; 2,6-dichlorophenol is completely removed, with a reaction rate constant of 0.71 min. -1 .
[0060] Figure 1The graph shows the removal efficiency of 2,6-dichlorophenol in different examples; it can be seen that the removal efficiency of 2,6-dichlorophenol in Examples 1, 6 and 7 is much higher than that in Comparative Example 1.
[0061] Example 8
[0062] The utilization efficiency of active intermediate manganese in the system of 1,10-phenanthroline (0–1000 μmol / L) and potassium permanganate (5.7 μmol / L) was tested using the ABTS probe method.
[0063] like Figure 5 As shown, the utilization efficiency of active intermediate manganese species can be increased to up to 100%.
[0064] Example 9
[0065] The utilization efficiency of active intermediate manganese in the system of 2,2'-bipyridine (0–1000 μmol / L) and potassium permanganate (5.7 μmol / L) was tested using the ABTS probe method.
[0066] like Figure 5 As shown, the utilization efficiency of active intermediate manganese species can be increased to up to 100%.
[0067] Comparative Example 2
[0068] The difference between this embodiment and Example 2 is that only potassium permanganate was used for the oxidative degradation of organic pollutants in wastewater, without the addition of nitrogen-containing ligands. Other processes and parameters were the same as in Example 2. After 10 minutes of treatment, the removal rate of organic pollutants was only 3%–69%, indicating that potassium permanganate has a limited effect on the degradation of 2,6-dichlorophenol within the pH range of 5–9.
[0069] Comparative Example 3
[0070] The utilization efficiency of active intermediate manganese in the sodium pyrophosphate (0–1000 μmol / L) and potassium permanganate (5.7 μmol / L) system was tested using the ABTS probe method.
[0071] like Figure 5 As shown, the highest utilization efficiency of active intermediate manganese is only 64.26%.
[0072] Comparative Example 4
[0073] The utilization efficiency of active intermediate manganese in the sodium bisulfite (0–1000 μmol / L) and potassium permanganate (5.7 μmol / L) system was tested using the ABTS probe method.
[0074] like Figure 5 As shown, the utilization efficiency of active intermediate manganese decreased from 51.80% to 9.07%.
[0075] Figure 5 The graphs show the utilization efficiency of active intermediate manganese for different ligands (2-pyridinecarboxylic acid, 1,10-phenanthroline, 1,10-phenanthroline) or other activation systems (pyrophosphate, bisulfite); the results show that in Examples 4, 8 and 9, the utilization efficiency of active intermediate manganese increased from about 50% to nearly 100% as the ligand concentration increased.
[0076] The utilization efficiency of active intermediate manganese was tested using the ABTS probe method. The utilization efficiency of the active intermediate manganese was calculated based on the reaction formula: Mn(VII) + 5ABTS → Mn(II) + 5ABTS· + Theoretically, the reaction ratio of potassium permanganate and ABTS is 5:1. However, under neutral conditions, due to the instability of intermediate manganese, the actual reaction ratio is 3:1. If 2-pyridinecarboxylic acid can improve the utilization efficiency of intermediate manganese, then the reaction ratio of potassium permanganate and ABTS should be between 3:1 and 5:1. The ABTS is 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid). 9 mL of the reaction solution was used as the test system. The reaction solution consisted of a 10 mM borate buffer solution at pH 7.0, 95.88 μmol ABTS, and different concentrations of 2-pyridinecarboxylic acid (0–1000 μmol / L). Subsequently, 1 mL of freshly prepared 57 μmol Mn(VII) solution was added to the above solution, and the reaction mixture was analyzed using a UV-Vis spectrophotometer.
[0077] ABTS· + The amount of ABTS generated is calculated according to Equation 1 (Lambert-Beer Law). The amount of ABTS consumed is calculated according to Equation 2, and the utilization efficiency η of manganese intermediates (Mn(VI), Mn(V), Mn(IV), Mn(III)) is calculated according to Equation 3.
[0078] (1)
[0079] In formula 1: =3.4×10 4 cm -1 M -1 , for ABTS· + Molar absorptivity at 415 nm; The difference in absorbance at 340 nm between the test system after adding 1 ml of potassium permanganate and 1 ml of water (control group);
[0080] (2)
[0081] In formula 2: =3.66×10 4 cm -1 M -1, where is the molar absorptivity of ABTS at 340 nm; =5.4×10 3 cm -1 M -1 , for ABTS· + The molar absorptivity at 340 nm; L is the thickness of the absorption layer, which is 1 cm;
[0082] (3)
[0083] In formula 3, This indicates the stoichiometric relationship of the reaction between intermediate manganese and ABTS under experimental conditions; The concentration of potassium permanganate is expressed in μmol / L; "5-1" indicates the stoichiometric relationship between the manganese intermediate and ABTS under ideal conditions with 100% utilization efficiency.
Claims
1. A potassium permanganate compound reagent for improving the utilization efficiency of active intermediate manganese, characterized in that: It includes potassium permanganate and a nitrogen-containing ligand; the molar ratio of the nitrogen-containing ligand to potassium permanganate is 1~5:1~10; the nitrogen-containing ligand is an organic ligand with a nitrogen-donating electron site.
2. The potassium permanganate compound reagent for improving the utilization efficiency of active intermediate manganese according to claim 1, characterized in that: The organic ligand having a nitrogen-donating electron site is at least one of 2-pyridinecarboxylic acid, 2,2'-bipyridine, 1,10-phenanthroline, a 2-pyridinecarboxylic acid derivative, a 2,2'-bipyridine derivative, and a 1,10-phenanthroline derivative.
3. The potassium permanganate compound reagent for improving the utilization efficiency of active intermediate manganese according to claim 1, characterized in that: The potassium permanganate compound agent for improving the utilization efficiency of active intermediate manganese also includes a carrier, on which nitrogen-containing ligands are loaded and compounded with potassium permanganate.
4. The potassium permanganate compound agent for improving the utilization efficiency of active intermediate manganese according to claim 3, characterized in that: The nitrogen-containing ligand loading on the support is 50~150 μmol / g.
5. The potassium permanganate compound agent for improving the utilization efficiency of active intermediate manganese according to claim 3, characterized in that: The carrier is montmorillonite.
6. The potassium permanganate compound agent for improving the utilization efficiency of active intermediate manganese according to claim 3, characterized in that: The loading method is as follows: the carrier is dispersed in an aqueous solution of 2-pyridinecarboxylic acid, stirred, centrifuged to separate the solid, and finally washed and freeze-dried.
7. The application of the potassium permanganate compound reagent for improving the utilization efficiency of active intermediate manganese as described in any one of claims 1 to 6, characterized in that: Potassium permanganate compound reagents that improve the utilization efficiency of active intermediate manganese are applied to the oxidative degradation of organic pollutants in wastewater.
8. The application according to claim 7, characterized in that: The organic pollutants in the wastewater are phenolic organic pollutants.
9. The application according to claim 7, characterized in that: The pH of the wastewater is 5-9.
10. The application according to claim 7, characterized in that: The amount of potassium permanganate added to the wastewater is 10~500 μmol / L.