Method for rapidly oxidizing and degrading antibiotics in water through high-frequency ultrasonic activation of permanganate / periodate

Abstract

A method for rapid oxidative degradation of antibiotics in water by high-frequency ultrasonic activation of permanganate / periodate comprises the following steps: injecting to-be-treated water containing trace organic pollutants into a high-frequency ultrasonic reactor, then adding potassium permanganate and periodate at the same time, and then starting ultrasonic treatment for 5-30 minutes, thereby completing the treatment of the trace organic pollutants in the water. The high-frequency ultrasonic synergistic activation permanganate / periodate provided by the invention is used for degrading trace organic pollutants in water, the permanganate and periodate serve as oxidants, and manganese oxide generated by rapid reaction of the permanganate and periodate serves as a high-frequency ultrasonic inner core, so that the ultrasonic cavitation effect is enhanced, and the removal of the pollutants is accelerated. Compared with the traditional advanced oxidation technology, the method provided by the invention has higher organic carbon removal efficiency, and the degraded product has no biotoxicity. The treatment efficiency of micropollutants in water is improved, and the method is safe and free of secondary pollution risk.

Description

Technical Field

[0001] The present invention relates to a method for rapidly oxidizing and degrading antibiotics in water by high-frequency ultrasound-activated permanganate / periodate, belonging to the technical field of water treatment. Background Art

[0002] At present, the rapid expansion of global manufacturing and the widespread application of chemical products have led to new pollutant challenges in the water environment. Such emerging pollutants mainly refer to trace and refractory organic compounds, which are characterized by low concentration, high toxicity and persistent residue, covering categories such as organochlorine pesticides, environmental hormones (EDCs), antibiotics and POPs. Research shows that although such substances exist in trace amounts in nature, they have significant bioaccumulation effects and potential ecological risks. Pollutants can produce amplification effects through the gradual transmission of the ecological chain, not only destroying the dynamic balance of biological populations, but also having a significant correlation with a variety of chronic diseases. Epidemiological investigations have confirmed that long-term exposure to such substances may induce health problems such as malignant tumors, metabolic syndrome and reproductive dysfunction. In the face of the technical bottleneck of the existing water treatment system in removing trace pollutants, the development of new treatment technologies based on the synergistic effects of advanced oxidation, biological enhancement and membrane separation has become an urgent issue in the field of environmental engineering.

[0003] Chemical oxidation is an effective method for removing organic matter in water. Oxidants such as permanganate and periodate, as a kind of green reagent, have been widely used in the field of water treatment. However, the slow oxidation rate restricts their wide application. When using chemical reagents alone, there are problems such as slow self-decomposition rate, low oxidation rate, and interference by various matrices in water. Therefore, it is urgent to develop a new type of percarbonate-enhanced oxidation water treatment technology that is efficient, economical, and environmentally friendly. Advanced oxidation processes (AOPs) can rapidly decompose trace organic pollutants (such as antibiotics, drug residues, endocrine disruptors, etc.) that are difficult to treat by traditional processes by generating strongly oxidizing free radicals and non-free radicals, and have advantages such as fast reaction rate and strong environmental compatibility. Invention patent CN118894588 A discloses a method for rapidly activating periodate oxidation degradation of antibiotic wastewater by visible light synergistic carbonate / bicarbonate ions. By mixing 0.5 mM sodium carbonate solution and 1 mM sodium periodate solution and adding them to tetracycline, a removal rate of 90.3% of tetracycline and a mineralization rate of 65% can be achieved in a reactor with a light intensity of 20 A for 5 minutes, and the reaction is a detoxification process; Invention patent CN 119430428 A uses boron nitride-modified copper ferrite (CFBN10) to catalyze sodium periodate, and nearly 90% of oxytetracycline can be removed within 60 minutes, and the catalyst still retains 80% of its catalytic activity after 5 cycles; Invention patent CN 118005129 A uses ultrathin carbon nitride photocatalysis to activate periodate to degrade pollutants in water. When the dosage of carbon nitride is 125 mg / L, periodate is 2 mM, and pH = 9, about 93% of ciprofloxacin can be removed in 16 minutes; Invention patent CN118616069 A proposes a method for activating periodate to degrade 2,4,6-trichlorophenol in water by using few-layer Mxene anchored nano-zero valent iron. The 2,4,6-trichlorophenol pollutant (10 mg / L) in actual water can be removed within 60 minutes. In summary, the catalytic activation of periodate advanced oxidation technology can effectively remove micro-pollutants in water, and strengthening the oxidation degradation of trace organic pollutants in water by periodate has important research significance and application prospects. Summary of the Invention

[0004] The purpose of the present invention is to solve the problems of slow self-decomposition rate, low oxidation rate, and interference by various matrices in water of existing oxidants, and to give full play to the role of the advanced oxidation system based on oxidants (such as permanganate and periodate), and to disclose a method for rapidly oxidizing and degrading antibiotics in water by high-frequency ultrasonic activation of permanganate / periodate.

[0005] The technical solution achieved by the present invention is as follows. A method for rapidly oxidizing and degrading antibiotics in water by high-frequency ultrasonic activation of permanganate / periodate. In this method, water containing trace organic pollutants to be treated is injected into a high-frequency ultrasonic reactor, and then potassium permanganate and periodate are added simultaneously. After the dosages of potassium permanganate and periodate are 10-100 μM and 20-200 μM respectively, the ultrasonic treatment is then carried out for 5 min - 30 min, and the treatment of trace organic pollutants in water is completed.

[0006] The permanganate is one or both of sodium permanganate and potassium permanganate.

[0007] The periodate is one or both of sodium periodate and potassium periodate.

[0008] The permanganate and periodate are both added in the form of a solution.

[0009] The ultrasonic wave is a high-frequency ultrasonic wave, and the acoustic frequency is one or more of 200 kHz, 400 kHz, 600 kHz, 800 kHz, 1000 kHz, and the ultrasonic generators are all arranged at the lower end of the liquid surface.

[0010] The working principle of the present invention is as follows: Permanganate and periodate first undergo an oxidation-reduction reaction to generate manganese oxide nanoparticles and iodate. Subsequently, the in-situ generated manganese oxide nanoparticles catalyze iodate to generate a series of free radical and non-free radical active species (i.e., IO3 • 、HO • 、 1 O2), which oxidize pollutants. In addition, under the action of high-frequency ultrasonic waves, the nano manganese oxide nanoparticles can act as ultrasonic cavitation nuclei, causing cavitation effects and instantly generating temperatures of thousands of degrees, rapidly pyrolyzing organic pollutants.

[0011] The reaction process is as follows: ; The beneficial effect of the present invention is that the method for rapidly oxidizing and degrading antibiotics in water by high-frequency ultrasonic activation of permanganate / periodate proposed by the present invention uses permanganate as an oxidant and an activator. Without the need for additional catalysts, the in-situ generated manganese oxide, on the one hand, pyrolyzes pollutants under the ultrasonic cavitation effect; on the other hand, it acts as a catalyst to catalyze the decomposition of periodate to generate various types of free radicals, oxidizing pollutants. The three complement each other rather than being simply superimposed.

[0012] The present invention abandons the high-cost and complex-to-prepare heterogeneous catalytic system and innovatively uses environmentally friendly reagents that are easy to store and transport as reaction media. While significantly reducing the treatment cost, due to the thorough mineralization effect, it can suppress the generation of disinfection by-products at the source. Compared with the traditional transition metal catalytic system, the technical solution of the present invention enables the directional conversion of aqueous manganese elements into manganese dioxide form precipitation through the regulation of the reaction path, not only realizing the simple treatment of solid-liquid separation, but also fundamentally eliminating the risk of secondary pollution caused by the dissolution of transition metals.

[0013] Compared with the prior art disclosed in Publication Nos. CN 119430428A, CN 118616069A, and CN 118005129A which require the use of heterogeneous catalysts, the present invention omits the cumbersome catalyst preparation process and directly uses green and transportable permanganate and periodate reagents, saving the operating cost; under the same conditions, compared with the removal of organic pollutants (ciprofloxacin) in water by ultrasonic activation of periodate, the removal rate of ciprofloxacin is increased by 42%; compared with the removal of organic pollutants (ciprofloxacin) in water by potassium permanganate / periodate, the removal rate of ciprofloxacin is increased by 65%; compared with the removal of organic pollutants (ciprofloxacin) in water by ultrasonic activation of potassium manganate, the removal rate of ciprofloxacin is increased by 20%. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 It is a schematic diagram of the method for rapid oxidation and degradation of antibiotics in water by high-frequency ultrasonic activation of permanganate / periodate of the present invention; Figure 2 It is a removal effect diagram of the method for rapid oxidation and degradation of antibiotics in water by high-frequency ultrasonic activation of permanganate / periodate provided by the embodiment of the present invention, simple potassium permanganate oxidation, periodate oxidation, and their combined systems for typical organic substances (ciprofloxacin); Figure 3 It is an application effect diagram of the high-frequency ultrasonic activation of permanganate / periodate system in the actual water body for rapid oxidation and degradation of ciprofloxacin in water; Figure 4 It is a removal effect diagram of the organic carbon in antibiotics by the high-frequency ultrasonic activation of permanganate / periodate system in the method for rapid oxidation and degradation of antibiotics in water. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0015] As Figure 1 shown, a method for rapid oxidation and degradation of antibiotics in water by high-frequency ultrasonic activation of permanganate / periodate in this embodiment is as follows: (1) Inject the water containing organic pollutants to be treated into the reaction chamber where the ultrasonic generating device is placed, and turn on the ultrasonic generating device; (2) Adjust the frequency to 0.2 - 1.0 mHz and the power to 180 W / L, and simultaneously add aqueous solutions of permanganate and periodate. (3) After the dosages of permanganate and periodate are 10 - 100 μM and 20 - 200 μΜ respectively, treat for 5 min - 30 min to complete the treatment of organic pollutants in water.

[0016] Figure 2 Shown is the removal effect of a method for rapidly oxidizing and degrading antibiotics in water by high - frequency ultrasonic activation of permanganate / periodate provided by an embodiment of the present invention, pure potassium permanganate oxidation, periodate oxidation, and their combined systems on a typical organic substance (ciprofloxacin).

[0017] A total of seven experimental comparisons were set in this example: (1) Add permanganate / periodate and ultrasonic intensification; (2) Add permanganate and ultrasonic intensification; (3) Add periodate and ultrasonic intensification; (4) Only add permanganate / periodate; (5) Only add permanganate; (6) Only add periodate; (7) Do not add any substance. The first six settings are completed by the following examples.

[0018] Figure 3 Shown is the application effect of the high - frequency ultrasonic activation of permanganate / periodate system in the actual water body in a method for rapidly oxidizing and degrading the antibiotic ciprofloxacin in water by high - frequency ultrasonic activation of permanganate / periodate provided by an embodiment of the present invention; the water bodies are: pure water, tap water, and lake water.

[0019] Figure 4 Shown is the removal effect of organic carbon in antibiotics by the high - frequency ultrasonic activation of permanganate / periodate system in a method for rapidly oxidizing and degrading antibiotics in water by high - frequency ultrasonic activation of permanganate / periodate provided by an embodiment of the present invention. The TOC treatment times are: 10 min, 20 min, and 30 min.

[0020] Example 1 A method for rapidly oxidizing and degrading antibiotics in water by high - frequency ultrasonic activation of permanganate / periodate in this example is specifically carried out according to the following steps: First, inject the water containing organic pollutants to be treated into the reaction chamber; simultaneously turn on the ultrasonic generating device, adjust the frequency to 1 mHz, and the power to 180 W / L; simultaneously add permanganate and periodate. After the dosages of permanganate and periodate are 100 μM and 50 μΜ respectively, treat for 30 min to complete the treatment of organic pollutants in water. The organic wastewater to be treated contains 20 μM of ciprofloxacin.

[0021] In this example, the permanganate and periodate are added in the form of a solution, and the permanganate and periodate are potassium permanganate and sodium periodate, respectively. Record the change in the ciprofloxacin concentration in the wastewater to be treated in this verification example, and draw a time-concentration curve. The time-concentration curve of this example is shown in Figure 2 the ultrasonic / potassium permanganate / periodate curve in

[0022] Example 2 This example is a control experimental group of a method for rapidly oxidizing and degrading antibiotics in water by high-frequency ultrasonic activation of permanganate / periodate, that is, ultrasonic / potassium permanganate; specifically, it is carried out according to the following steps: First, inject the water containing organic pollutants to be treated into the reaction chamber; at the same time, turn on the ultrasonic generating device, adjust the frequency to 1 mHz, and the power to 180 W / L; at the same time, add permanganate. After the dosage of permanganate reaches 100 μΜ, treat for 30 min, and the treatment of organic pollutants in water is completed. The organic wastewater to be treated contains 20 μM of ciprofloxacin.

[0023] In this example, the permanganate is added in the form of a solution, and the permanganate is potassium permanganate. Record the change in the ciprofloxacin concentration in the wastewater to be treated in this verification example, and draw a time-concentration curve. The time-concentration curve of this example is shown in Figure 2 the ultrasonic / permnaganate curve in

[0024] Example 3 This example is a control experimental group of a method for rapidly oxidizing and degrading antibiotics in water by high-frequency ultrasonic activation of permanganate / periodate, that is, ultrasonic / sodium periodate; specifically, it is carried out according to the following steps: First, inject the water containing organic pollutants to be treated into the reaction chamber; at the same time, turn on the ultrasonic generating device, adjust the frequency to 1 mHz, and the power to 180 W / L; at the same time, add periodate. After the dosage of periodate reaches 50 μΜ, treat for 30 min, and the treatment of organic pollutants in water is completed. The organic wastewater to be treated contains 20 μM of ciprofloxacin.

[0025] In this example, the periodate is added in the form of a solution, and the periodate is sodium periodate. Record the change in the ciprofloxacin concentration in the wastewater to be treated in this verification example, and draw a time-concentration curve. The time-concentration curve of this example is shown in Figure 2 the ultrasonic / sodium periodate curve in

[0026] Example 4 This example is a control experimental group of a method for rapidly oxidizing and degrading antibiotics in water by high-frequency ultrasonic activation of permanganate / periodate, that is, permanganate / periodate; specifically, it is carried out according to the following steps: First, the water containing organic pollutants to be treated is injected into the reaction chamber, and at the same time, permanganate and periodate are added. After the addition amounts of permanganate and periodate are 100 μΜ and 50 μΜ respectively, the treatment is carried out for 30 min, and thus the treatment of organic pollutants in the water is completed. The organic wastewater to be treated contains 20 μM of ciprofloxacin.

[0027] In this example, the way of adding permanganate and periodate is solution addition, and the permanganate and periodate are potassium permanganate and sodium periodate. Record the change of ciprofloxacin concentration in the sewage to be treated in this verification example, and draw a time-concentration curve graph. The time-concentration curve of this example is shown in Figure 2 the potassium permanganate / periodate curve in

[0028] Example 5 This example is a control experimental group of a method for rapidly oxidizing and degrading antibiotics in water by high-frequency ultrasonic activation of permanganate / periodate, that is, only treated with potassium permanganate; specifically, it is carried out according to the following steps: First, the water containing organic pollutants to be treated is injected into the reaction chamber; only potassium permanganate is added, and after the addition amount of potassium permanganate is 100 μM, the treatment is carried out for 30 min, and thus the treatment of organic pollutants in the water is completed. The organic wastewater to be treated contains 20 μM of ciprofloxacin.

[0029] In this example, the way of adding permanganate is solution addition. Record the change of ciprofloxacin concentration in the sewage to be treated in this verification example, and draw a time-concentration curve graph. The time-concentration curve of this example is shown in Figure 2 the potassium permanganate curve in

[0030] Example 6 This example is a control experimental group of a method for rapidly oxidizing and degrading antibiotics in water by high-frequency ultrasonic activation of permanganate / periodate, that is, only treated with periodate; specifically, it is carried out according to the following steps: First, the water containing organic pollutants to be treated is injected into the reaction chamber; only periodate is added, and after the addition amount of periodate is 50 µΜ, the treatment is carried out for 30 min, and thus the treatment of organic pollutants in the water is completed. The organic wastewater to be treated contains 20 μM of ciprofloxacin.

[0031] In this example, the way of adding periodate is solution addition. Record the change of ciprofloxacin concentration in the sewage to be treated in this verification example, and draw a time-concentration curve graph. The time-concentration curve of this example is shown in Figure 2 the periodate curve in

Claims

1. A method for rapidly oxidizing and degrading antibiotics in water by high-frequency ultrasound-activated permanganate / periodate, characterized in that, In the method, water containing trace organic pollutants to be treated is injected into a high-frequency ultrasonic reactor, and then potassium permanganate and periodate are added simultaneously. After the dosages of potassium permanganate and periodate are 10 - 100 μM and 20 - 200 μM respectively, the ultrasonic treatment is then turned on and maintained for 5 min - 30 min, thus completing the treatment of trace organic pollutants in the water.

2. A method for rapidly oxidizing and degrading antibiotics in water by high-frequency ultrasound-activated permanganate / periodate, characterized in that, The permanganate is one or more of sodium permanganate and potassium permanganate; 3. A method for rapidly oxidizing and degrading antibiotics in water by high-frequency ultrasound-activated permanganate / periodate, characterized in that, The periodate is one or more of sodium periodate and potassium periodate; 4. The method for rapid oxidative degradation of antibiotics in water by high-frequency ultrasound-activated permanganate / periodate according to claim 1, characterized in that, The permanganate and periodate are both added in the form of a solution.

5. The method for rapid oxidative degradation of antibiotics in water by high-frequency ultrasound-activated permanganate / periodate according to claim 1, characterized in that, The ultrasonic wave is a high-frequency ultrasonic wave, and the sound wave frequency is one or more of 200 kHz, 400 kHz, 600 kHz, 800 kHz, and 1000 kHz, and the ultrasonic generators are all arranged at the lower end of the liquid surface.

Images