Dual oxidant synergistic water purification technology

Abstract

The application relates to a dual-oxidant synergistic water purification technology and relates to the technical field of removal of organic pollutants in water bodies. By simultaneously adding high-periodate and perborate oxidants into organic acid wastewater containing phenolic pollutants to be treated and stirring, efficient removal of the organic pollutants is realized. The dual-oxidant synergistic efficient removal of phenolic pollutants in the advanced oxidation water treatment technology is excavated, the operation method is simple, the pollutants are efficiently removed, excessive instruments and equipment and energy are not needed, energy is saved, and the application range and application prospect are relatively wide.

Description

Technical Field

[0001] This invention relates to the field of water organic pollutant removal technology, and in particular to a dual-oxidant synergistic water purification technology based on the synergistic action of periodate and perborate dual oxidants for the purification of organic pollutants in water. Background Technology

[0002] Phenolic compounds are highly toxic organic pollutants, characterized by their high toxicity and difficulty in degradation. They are widely present in industries such as petrochemicals, dyeing and printing, and pesticides. The discharge of industrial wastewater easily pollutes surface water and groundwater, leading to the loss of human cell activity, crop death, and the death of aquatic organisms, causing serious harm to human health and the ecological environment. Therefore, the treatment of phenolic pollutants has become a key focus of ecological and environmental protection both domestically and internationally. Currently, advanced oxidation technologies have received widespread attention in the field of water purification. They can effectively solve the problem of existing biological treatment methods' difficulty in treating substances with poor biodegradability and high relative molecular mass. They can directly mineralize or decompose most organic matter, showing great application prospects.

[0003] Periodate and perborate exhibit good stability and are not easily decomposed or activated during transportation, making them commonly used as disinfectants and bactericides. However, like most oxidants, their ability to independently oxidize pollutants is poor, and their removal efficiency for most new pollutants is extremely low. Current activation methods, including ultrasound, ultraviolet light, and material activation, suffer from drawbacks such as easy decomposition of activators, high energy consumption, complex operation, and slow and incomplete pollutant degradation rates. Therefore, combining commercially available and widely used water oxidants with potent synergistic effects for the removal of phenolic pollutants warrants further research and application. Summary of the Invention

[0004] The purpose of this invention is to address the aforementioned problems in the prior art by providing a dual-oxidant synergistic water purification technology. This technology cleverly combines two commonly used oxidants, resulting in more efficient degradation and simpler operation in the removal of phenolic pollutants, while effectively saving energy and reducing the amount of equipment required.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] A dual-oxidant synergistic water purification technology involves adjusting the pH of the water containing organic pollutants to 3.0, while simultaneously adding periodate and perborate oxidants to form a mixed system. The mixture is then stirred and reacted to achieve efficient removal of organic pollutants.

[0007] The water body containing the organic pollutants to be treated is a water body containing phenolic substances.

[0008] In the mixed system, the concentration of periodate is not higher than 800.0 μM, preferably, the concentration of periodate is 50 to 800.0 μM.

[0009] In the mixed system, the concentration of perborate is not higher than 800.0 μM, preferably, the concentration of perborate is 50 to 800.0 μM.

[0010] In the mixed system, the molar ratio of perborate to periodate is not higher than 800:800. Preferably, the molar concentration ratio of perborate to periodate is 50:50 to 800:800 μM.

[0011] More preferably, in the mixed system, the concentrations of periodate and perborate are 500.0 μM, respectively.

[0012] Compared with the prior art, the outstanding technical effects and advantages of the present invention are:

[0013] This invention combines periodate and perborate as oxidants, primarily for the removal of phenolic pollutants from common industrial wastewater. This method can efficiently remove phenolic pollutants; the chemical reagents required are readily available; the operation is simple, has high application value, is easy to promote, requires minimal energy and equipment, and can effectively save energy. Attached Figure Description

[0014] Figure 1 The graph shows the effect of different ratios of periodate and perborate concentrations on the removal of bisphenol F from water. Figure 1 In this context, [BPF] / [BPF]0 represents the real-time concentration ratio of BPF to its original concentration, and [SPB]0 / [PI]0 represents the molar ratio of perborate to periodate.

[0015] Figure 2 The graph shows the removal of bisphenol F from water by different concentrations of perborate. Figure 2 In this context, [BPF] / [BPF]0 represents the real-time concentration ratio of BPF to its original concentration, and [SPB]0 represents the molar concentration of perborate.

[0016] Figure 3 This diagram shows the removal of bisphenol F from water bodies under different water quality parameters. Figure 3 In the figure, [BPF] / [BPF]0 represents the real-time concentration ratio of BPF to the original concentration of BPF, and [Cl] - ]0、[NO3 - ]0、[Fe 2+ ]0、[Cu 2+ ]0 is Cl - NO3 - Fe 2+ Cu2+ The initial molar concentration of the water quality factor.

[0017] Figure 4 This diagram shows the removal of different phenolic pollutants from water bodies. Figure 4 In the middle, k obs The pseudo-first-order degradation rate constant represents the rate of degradation of pollutants, which include acetaminophen (4-AP), p-chlorophenol (4-CP), bisphenol A (BPA), bisphenol AF (BPAF), bisphenol S (BPS), and phenol (Phenol). Detailed Implementation

[0018] To make the technical problems, technical solutions and beneficial effects of the present invention clearer and more understandable, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments.

[0019] This invention provides a dual-oxidant synergistic water purification technology. In a water body containing organic pollutants, the pH is adjusted to 3.0, and periodate and perborate, two oxidants, are added to form a mixed system. The system is then stirred and reacted to achieve efficient removal of the organic pollutants. The water body containing the organic pollutants is a water body containing phenolic substances (taking bisphenol F (BPF) as an example).

[0020] Periodate and perborate are two commonly used oxidants. Perborate is rarely used in water treatment, and the combined use of the two is unprecedented. This invention proposes a synergistic water purification technology using periodate and perborate as dual oxidants. The following is a preliminary discussion of the combined mechanism and application of periodate and perborate.

[0021] Both periodate (NaIO4) and perborate (NaBO3·4H2O) are strong oxidants and can work synergistically in water treatment to enhance oxidation capacity. Periodate has strong oxidizing power and can oxidize various organic and inorganic substances into harmless substances such as carbon dioxide, water, and nitrates. Perborate has high oxidizing power under acidic conditions and can oxidize and remove various heavy metal ions and organic pollutants.

[0022] In combined applications, periodate and perborate can complement each other, achieving simultaneous removal of multiple pollutants. Furthermore, perborate can generate hydroxyl radicals (·OH) with high oxidizing power under acidic conditions, further enhancing the oxidation effect. The synergistic effect of periodate and perborate can be expressed as:

[0023] IO 4- +8H + +5e - →IO 3- +4H2O

[0024] B(OH) 4- +4H + →B(OH) 3+ +H2O

[0025] B(OH) 3+ +H₂O→B(OH) 2+ +·OH

[0026] In practical applications, periodate and perborate can complement each other to achieve the simultaneous removal of multiple pollutants. Periodate has strong oxidizing power, capable of oxidizing various organic and inorganic substances into harmless substances such as carbon dioxide, water, and nitrates. Perborate exhibits high oxidizing power under acidic conditions, effectively removing various heavy metal ions and organic pollutants. During combined application, the hydroxyl radicals (·OH) generated by perborate can further enhance the oxidation effect.

[0027] Example 1

[0028] Effects of different ratios of periodate and perborate concentrations on the removal of bisphenol F from water.

[0029] Using 20.0 mL of a 10.0 mM phosphate buffer solution as a solvent, 1.0 μM bisphenol F was added. The pH was adjusted to 3.0 with sodium hydroxide and phosphoric acid solutions to obtain the water body containing the organic pollutants to be treated. Perborate (SPB) and periodate (PI) were added to the above water body at a molar ratio of 1:1, resulting in molar concentrations of 0, 50.0, 100.0, 200.0, 300.0, 500.0, and 800.0 μM, respectively, to optimize the molar concentration. The mixture was thoroughly stirred using a magnetic stirrer to obtain a mixed system. The reaction temperature was room temperature (20°C).

[0030] During the reaction, 1.0 mL samples were taken at fixed reaction time points of 0, 5, 10, 15, 20 and 30 min and added to 10 μL of 1.0 M sodium thiosulfate to stop the reaction and obtain the remaining bisphenol F solution.

[0031] The method for determining the concentration of organic pollutants in this invention is high-performance liquid chromatography (HPLC, Shimadzu LC-20AD), coupled with an Agilent XDB-C18 column (ZORBAX Eclipse, 4.6 × 150 mm, particle size 5.74 μm) and a diode array detector. The mobile phase is methanol and ultrapure water in a ratio of 60:40, the flow rate is 0.8 mL / min, the elution time is 4.92 min, and the detection wavelength is 228 nm.

[0032] This embodiment uses the high-performance liquid chromatography method described above to determine the residual concentration of bisphenol F. The results are shown in [Figure number missing]. Figure 1 . Figure 1This indicates that periodate and perborate are not effective when used alone, but the synergistic effect of the two can produce better technical results. When the molar concentration ratio of periodate and perborate is 500:500 or higher, the pollutants can be removed within 30 minutes, and 800.0 μM can achieve rapid removal of pollutants within 5 minutes, proving that increasing the concentration of oxidant can greatly improve the oxidant removal rate.

[0033] Example 2

[0034] Removal of bisphenol F from water by different concentrations of perborate.

[0035] Example 1 was repeated with the following differences: the periodate concentration was maintained at 500.0 μM, the perborate concentration was adjusted to 100.0, 200.0, 300.0, 400.0, and 500.0 μM, the pH was adjusted to 3.0, and the sampling time points were 0, 5, 10, 15, 20, and 30 min. The results are shown in [Figure Number]. Figure 2 .

[0036] Figure 2 The results showed that the removal effect was optimal when the concentrations of periodate and perborate were 500.0 μM, achieving the removal of pollutants within 30 minutes.

[0037] Example 3

[0038] Removal of bisphenol F from water bodies under different water quality parameters.

[0039] Example 1 was repeated, with the following differences: the concentrations of periodate and perborate were maintained at 500.0 μM, the pH was adjusted to 3.0, and 0–50.0 mM Cl were added to each. - ( Figure 3 Figure (a) shows the concentrations of NO3 from 0 to 20.0 mM. - ( Figure 3 Figure (b) shows the Fe content from 0 to 1.0 mM. 2+ ( Figure 3 Figure (c) shows the Cu content from 0 to 1.0 mM. 2+ ( Figure 3 Figure (d) shows the sampling time points at 0, 5, 10, 15, 20, and 30 minutes. The results are shown in Figure (d). Figure 3 Figures (a) to (d) in the text.

[0040] Figure 3 The results show that different concentrations of water quality parameters have virtually no inhibitory effect on pollutant removal and mostly accelerate pollutant degradation, indicating that the system is highly selective, less affected by external conditions, and suitable for real wastewater treatment.

[0041] Example 4

[0042] Removal of different phenolic pollutants from water bodies.

[0043] Example 1 was repeated with the following differences: the water containing 1.0 μM bisphenol F was replaced with water containing 1.0 μM acetaminophen (4-AP), p-chlorophenol (4-CP), bisphenol A (BPA), bisphenol AF (BPAF), bisphenol S (BPS), and phenol (Phenol). The pH was adjusted to 3.0, and 500.0 μM periodate and perborate were added respectively. The sampling time points remained at 0, 5, 10, 15, 20, and 30 min. The results are shown in [Figure number missing]. Figure 4 .

[0044] Figure 4 This indicates that the technology has a certain removal effect on different phenols within 30 minutes, demonstrating that the system has a certain degree of universality and is applicable to water bodies polluted by various phenols.

[0045] This invention proposes a novel combined approach that primarily enhances the oxidizing power of the oxidant itself, a method not previously used, while also incorporating oxidizing properties. This invention purifies water by simultaneously adding periodate and perborate oxidants to water containing phenolic pollutants, thereby efficiently removing organic pollutants from the water. This invention explores the potential of advanced oxidation water treatment technology for the synergistic and efficient removal of phenolic pollutants using periodate and perborate oxidants. This technology is simple to operate, highly efficient in pollutant removal, requires minimal equipment and energy, saves energy, and has a wide range of applicability and application prospects.

[0046] The above embodiments are merely preferred embodiments of the present invention and should not be considered as limiting the scope of the present invention. All equivalent variations and improvements made within the scope of the present invention should still fall within the patent coverage of the present invention.

Claims

1. A dual-oxidant synergistic water purification technology, characterized in that: In the water body containing organic pollutants to be treated, the pH is adjusted and two oxidants, periodate and perborate, are added simultaneously to form a mixed system. The system is stirred and reacted to achieve the removal of phenolic organic pollutants. The water body containing organic pollutants to be treated is a water body containing phenolic substances; In the mixed system, the concentrations of periodate and perborate are 500.0 μM, and the pH is 3.0.

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