A method for treating organic contaminants in chlorinated wastewater

Abstract

This application discloses a method for treating organic pollutants in chlorine-containing wastewater, belonging to the field of water treatment technology. The method includes the following steps: mixing organic pollutants, an oxidant, and chlorine-containing wastewater to obtain a reaction solution; adjusting the initial pH value of the reaction solution; and adding active aluminum-based oxide to the reaction solution. The advantage of this application is that it provides an improved method for treating organic pollutants in chlorine-containing wastewater.

Description

Technical Field

[0001] This application belongs to the field of water treatment technology, and more specifically, relates to a method for treating organic pollutants in chlorine-containing wastewater. Background Technology

[0002] Fenton technology is widely used for the oxidative degradation of new pollutants in wastewater because it can generate highly reactive hydroxyl radicals (·OH, E0 = 2.8V).

[0003] Much research and technology has focused on heterogeneous catalysts based on variable-valence metals such as iron, copper, and cobalt, utilizing the redox cycle of metal catalytic sites to activate oxidants. However, during the variable-valence process, metals are prone to precipitation, causing secondary pollution, and the induced free radical process is easily affected by coexisting ions and organic matter.

[0004] Wastewater often contains a large number of inorganic anions, among which chloride ions are the most common. The oxidative degradation of new pollutants in chlorine-containing industrial wastewater has always been an industry challenge in the water treatment field.

[0005] Aluminum metal oxides, especially activated alumina, have a large specific surface area and porosity. The Al sites, as strong Lewis acid sites, can coordinate and complex inorganic anions such as fluoride ions and arsenate ions.

[0006] In related technologies, such as Chinese patent document CN109718771B, a bimetallic doped alumina aerogel and its preparation and use method are provided. The method discloses that the alumina aerogel can obtain excellent catalytic activity by loading a small amount of transition metal.

[0007] In related technologies, alumina is used as a carrier, and Al2O3 plays a major role in the removal of organic matter. Al2O3 acts only as an inert carrier, and the active sites are generally controlled by other metal sites. Summary of the Invention

[0008] The summary section of this application is intended to provide a brief overview of the concepts, which will be described in detail in the detailed description section below. This summary section is not intended to identify key or essential features of the claimed technical solutions, nor is it intended to limit the scope of the claimed technical solutions.

[0009] Some embodiments of this application propose a method for treating organic pollutants in chlorine-containing wastewater to solve the technical problems mentioned in the background section above.

[0010] This invention addresses the technical problem that Al2O3 is only used as an inert carrier and the active sites are generally controlled by other metal sites. It provides a method for treating organic pollutants in chlorine-containing wastewater, comprising the following steps: mixing organic pollutants, an oxidant and chlorine-containing wastewater to obtain a reaction solution; adjusting the initial pH value of the reaction solution; and adding active aluminum-based oxides to the reaction solution.

[0011] Furthermore, active aluminum-based oxides include active alumina.

[0012] Furthermore, methods for preparing activated alumina include co-precipitation, sol-gel, and gas-phase methods.

[0013] Furthermore, the specific surface area of ​​activated alumina ranges from 100 m². 2 / g to 300m 2 / g; the oxygen content of surface hydroxyl groups accounts for 30% to 60% of the total oxygen content of activated alumina.

[0014] Furthermore, the dosage of activated alumina ranges from 0.50 g / L to 1.50 g / L, and is preferably 1.0 g / L based on the total volume of the reaction solution.

[0015] Furthermore, mixing the organic pollutants, oxidant, and chlorine-containing wastewater involves adjusting the pH of the reaction solution, with the pH ranging from 3.0 to 7.0. Preferably, the initial pH is 3.0.

[0016] Furthermore, the oxidizing agent is any one or a combination of persulfate, perdisulfate, peracetic acid, and hydrogen peroxide. Persulfate is preferred.

[0017] Furthermore, the molar ratio of organic pollutants to oxidant in the reactants is from 1:10 to 1:1. Preferably, it is 1:10.

[0018] Furthermore, the chloride ion concentration in the chlorine-containing wastewater is greater than or equal to 1.0 mM. Preferably, it is between 1.0 mM and 500.0 mM. More preferably, it is 250.0 mM.

[0019] Furthermore, organic pollutants include one or more of the following: phenols, amino acids, sulfonamides, or sulfoxides.

[0020] Furthermore, the organic pollutants include one or more of o-methylphenol, carbamazepine, sulfamethoxazole, or methyl phenyl sulfoxide.

[0021] The beneficial effect of this application is that it provides a method for improving the treatment of organic pollutants in chlorine-containing wastewater.

[0022] More specifically, some embodiments of this application may produce the following specific beneficial effects:

[0023] Active aluminum-based oxides, especially active alumina as a heterogeneous Fenton-like catalyst, form surface complexes by coordinating oxidant anions within the inner spheres, which then react with coexisting chloride ions to generate active species such as free chlorine, singlet oxygen, hydroxyl radicals, and sulfate radicals.

[0024] The reaction process does not involve the redox cycle of metal catalytic sites, and the metal ions are stable and not easily precipitated; aluminum ions also have less biotoxicity compared to heavy metal ions such as cobalt and copper.

[0025] The main active species in this application are free chlorine, singlet oxygen, etc. These active species have strong selectivity for electron-rich pollutants, giving the invention a more controllable catalytic oxidation scenario and high oxidant utilization efficiency.

[0026] In addition to its ability to degrade organic pollutants, it also has a strong bactericidal activity against various pathogens in the effluent, preventing bacterial regeneration. Attached Figure Description

[0027] The accompanying drawings, which form part of this application, are used to provide a further understanding of the application and to make other features, objects, and advantages of the application more apparent. The illustrative embodiments and descriptions of this application are used to explain the application and do not constitute an undue limitation of the application.

[0028] Furthermore, throughout the accompanying drawings, the same or similar reference numerals denote the same or similar elements. It should be understood that the drawings are schematic, and the elements are not necessarily drawn to scale.

[0029] In the attached diagram:

[0030] Figure 1 The main steps of a method for treating organic pollutants in chlorine-containing wastewater according to an embodiment of this application are as follows:

[0031] Figure 2 This is a schematic diagram illustrating the oxidation effect of carbamazepine under different oxidant systems in Example 1;

[0032] Figure 3 This is a schematic diagram illustrating the oxidation effect of carbamazepine on different systems in Example 2;

[0033] Figure 4 This is a schematic diagram illustrating the oxidation effect of different alumina crystals on carbamazepine in Example 3.

[0034] Figure 5 This is a schematic diagram illustrating the oxidation effect of different heterogeneous catalysts on carbamazepine in chlorine-containing wastewater in Example 4.

[0035] Figure 6 This is a schematic diagram illustrating the oxidation effect of different chloride ion concentrations on carbamazepine in Example 5.

[0036] Figure 7 This is a schematic diagram illustrating the oxidation effect of carbamazepine in chlorine-containing wastewater under different pH conditions in Example 6;

[0037] Figure 8 This is a schematic diagram of the oxidation effect under different molar ratios of persulfate and carbamazepine in Example 7;

[0038] Figure 9 This is a schematic diagram illustrating the oxidation effect of activated alumina / persulfate / chloride ions on different organic pollutants in chlorine-containing wastewater in Example 8.

[0039] Figure 10 This is a schematic diagram illustrating the oxidation effect of different catalyst dosages on carbamazepine in chlorine-containing wastewater in Example 9.

[0040] Figure 11 This is a schematic diagram illustrating the destruction of two typical deoxynucleotides in Example 10;

[0041] Figure 12 The diagram shows the adsorption and pore size distribution of the activated alumina in this application in the examples;

[0042] Figure 13 In the examples, the oxygen content of the surface hydroxyl groups of the activated alumina in this application accounts for the proportion of the total oxygen content of the activated alumina. Detailed Implementation

[0043] Embodiments of this disclosure will now be described in more detail with reference to the accompanying drawings. While some embodiments of this disclosure are shown in the drawings, it should be understood that this disclosure can be implemented in various forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of this disclosure. It should be understood that the accompanying drawings and embodiments of this disclosure are for illustrative purposes only and are not intended to limit the scope of protection of this disclosure.

[0044] It should also be noted that, for ease of description, only the parts relevant to the invention are shown in the accompanying drawings. Unless otherwise specified, the embodiments and features described in this disclosure can be combined with each other.

[0045] It should be noted that the concepts of "first" and "second" mentioned in this disclosure are used only to distinguish different devices, modules or units, and are not used to limit the order of functions performed by these devices, modules or units or their interdependencies.

[0046] It should be noted that the terms "a" and "a plurality of" used in this disclosure are illustrative rather than restrictive, and those skilled in the art should understand that, unless otherwise expressly indicated in the context, they should be understood as "one or more".

[0047] The names of messages or information exchanged between multiple devices in the embodiments of this disclosure are for illustrative purposes only and are not intended to limit the scope of such messages or information.

[0048] This disclosure will now be described in detail with reference to the accompanying drawings and embodiments.

[0049] Homogeneous Fenton reactions have several drawbacks in application, such as high susceptibility to environmental substrates, narrow pH range, and the tendency to generate large amounts of iron sludge. To overcome these drawbacks, much research and technology has focused on heterogeneous catalysts based on variable-valence metals such as iron, copper, and cobalt. These catalysts utilize the redox cycle of metal catalytic sites to activate the oxidant. However, the metal valence cycle inevitably leads to the precipitation of metal ions, causing secondary pollution of water bodies. Moreover, the induced free radical process is greatly affected by the coexisting substrate, resulting in low oxidant utilization efficiency (Environ. Sci. Technol. 2023, 57, 4266-4275; Environ. Sci. Technol. 2022, 56, 15, 10710-10720).

[0050] Fenton-like catalysts, such as iron oxide, copper oxide, and cobalt oxide, release heavy metal ions during use, causing secondary pollution to water bodies. Additionally, in general induced free radical processes, free radicals react with chloride ions to generate less reactive chlorine free radicals and chlorohydroxyl free radicals, thus affecting the reaction rate.

[0051] like Figure 1 As shown, one embodiment of this application describes a method for treating organic pollutants in chlorine-containing wastewater. The method includes the following steps:

[0052] S100: Organic pollutants, oxidants and chlorine-containing wastewater are mixed to obtain a reaction solution.

[0053] S200: Adjusts the initial pH value of the reaction solution;

[0054] S300: Add active aluminum-based oxides to the reaction solution;

[0055] Among them, active aluminum-based oxides include active alumina.

[0056] In this application, aluminum metal oxides, particularly activated alumina, possess a large specific surface area and porosity (Environ. Sci. Technol. 2018, 52, 2, 581-588). The Al sites, as strong Lewis acid sites, can coordinate and complex inorganic anions such as fluoride and arsenate. However, in advanced oxidation fields, existing technologies generally use them as stable supports, with active sites typically controlled by other metal sites. For example, Ahn et al. used Al₂O₃ as a support to load precious metals such as Pd and Pt to activate persulfate, thereby degrading organic matter. In this study, Al₂O₃ was only used as an inert support (Environ. Sci. Technol. 2016, 50, 10187-10197). The application of aluminum-based metal oxides directly as Fenton-like catalysts, utilizing their coordination and complexation with oxidants to enhance pollutant degradation, has not yet been reported.

[0057] Methods for preparing active aluminum-based oxides include co-precipitation, sol-gel, and gas-phase methods. Co-precipitation is preferred, and its general steps are as follows:

[0058] ① Solution preparation: Dissolve an appropriate amount of aluminum salt (such as aluminum nitrate, aluminum sulfate, etc.) and alkaline precipitant (such as ammonia, ammonium bicarbonate, etc.) in a suitable solvent according to a certain molar ratio to form two reactant solutions.

[0059] ② Mixing reactant solutions: Slowly add the aluminum salt solution dropwise to the alkaline precipitant solution while stirring the solution to ensure that the two solutions are fully mixed.

[0060] ③Precipitation formation: As the reaction between aluminum salt and alkaline precipitant proceeds, a precipitate is formed, ensuring that the pH value of the reaction solution is within the appropriate range (8-10).

[0061] ④ Calcination treatment: The obtained precipitate is calcined and heated to 600-900℃ for 3 hours, washed repeatedly with water 6 times and vacuum dried to obtain the desired active aluminum-based oxide.

[0062] The specific surface area of ​​activated alumina ranges from 100 m². 2 / g to 300m 2 / g; the oxygen content of surface hydroxyl groups accounts for 30% to 60% of the total oxygen content of activated alumina;

[0063] The dosage of activated alumina ranges from 0.50 g / L to 1.50 g / L.

[0064] The oxidizing agent is any one or a combination of persulfate, perdisulfate, peracetic acid, and hydrogen peroxide. The persulfate can be a commercially available compound salt, such as sodium persulfate compound salt or potassium persulfate compound salt.

[0065] The molar ratio of organic pollutants to oxidant in the reactants is 1:10 to 1:1.

[0066] The chloride ion concentration in the chlorine-containing wastewater is greater than or equal to 1.0 mM.

[0067] Wastewater often contains a large number of inorganic anions, among which chloride ions are the most common. The oxidative degradation of new pollutants in chlorinated industrial wastewater has always been an industry challenge in water treatment. This is because the free radicals generated during the Fenton / Fenton-like reaction can react with chloride ions to form chloride free radicals (·Cl, E0 = 2.5V), which have weaker redox capabilities. This not only leads to the ineffective loss of active free radicals but also produces chlorination disinfection byproducts, seriously endangering the ecological safety of water bodies.

[0068] like Figure 2 As shown, another embodiment of the method for treating organic pollutants in chlorine-containing wastewater according to this application specifically includes the following steps:

[0069] S210: Organic pollutants, oxidants and chlorine-containing wastewater are mixed to obtain a reaction solution.

[0070] S220: Adjusts the initial pH of the reaction solution to between 3.0 and 7.0.

[0071] S230: Add active aluminum-based oxides to the reaction solution.

[0072] The pH value of the reaction solution can be adjusted either before or after the addition of the aluminum-based oxide.

[0073] Organic pollutants include phenols, amino acids, sulfonamides, and sulfoxides.

[0074] Furthermore, the pollutants include o-methylphenol, carbamazepine, sulfamethoxazole, and methyl phenyl sulfoxide.

[0075] The present application will be further described below with reference to specific embodiments.

[0076] Example 1

[0077] Four reaction systems were designed: activated alumina / hydrogen peroxide / chloride ions, activated alumina / persulfate / chloride ions, activated alumina / peracetic acid / chloride ions, and activated alumina / permonosulfate / chloride ions. The mixed solutions contained carbamazepine at a concentration of 10 μM, activated alumina at a dosage of 1.0 g / L, hydrogen peroxide at a concentration of 10 mM, permonosulfate / persulfate / peracetic acid at a concentration of 40 μM, chloride ions at a concentration of 1.0 mM, and an initial pH of 3.0. The mixed solutions of the four reaction systems were placed in a constant temperature water bath at 25°C and magnetically stirred for 20 min.

[0078] The concentration of carbamazepine was determined using ultra-high performance liquid chromatography at a wavelength of 210 nm. The results are as follows: Figure 2 As shown, the removal rates of carbamazepine in the four reaction systems were 22.9%, 18.1%, 71.2%, and 86.0%, respectively.

[0079] The above experimental results show that the method for treating organic pollutants in chlorine-containing wastewater of this application can efficiently activate oxidants to treat organic pollutants in chlorine-containing wastewater. Persulfate has the highest catalytic efficiency, and subsequent embodiments will focus on persulfate as the target for further research.

[0080] Example 2

[0081] Four reaction systems were designed: activated alumina / permonosulfate, permonosulfate / chloride, activated alumina / chloride, and activated alumina / permonosulfate / chloride. The mixed solutions contained carbamazepine at a concentration of 10 μM, activated alumina at a dosage of 1.0 g / L, permonosulfate at a concentration of 40 μM, and chloride at a concentration of 1.0 mM, with an initial pH of 3.0. The mixed solutions of the four reaction systems were placed in a constant temperature water bath at 25℃ and magnetically stirred for 20 min. The concentration of carbamazepine was determined using ultra-high performance liquid chromatography (UHPLC) at a wavelength of 210 nm. The results are as follows: Figure 3 As shown, the removal rates of carbamazepine in the four reaction systems were 1.5%, 6.4%, 12.6%, and 86.0%, respectively, with apparent reaction rates of 0.0002 min. -1 0.0039min -1 0.0078min -1 0.10212min -1 .

[0082] Activated alumina alone has poor adsorption capacity for carbamazepine; persulfate alone has limited oxidation capacity; activated alumina / persulfate has poor catalytic ability and cannot catalyze the decomposition of PMS into free radicals; persulfate / chloride ions can react to generate HClO, etc., but its reaction rate is slow, its energy barrier is high, and its ability to catalyze the degradation of pollutants is poor.

[0083] The above experimental results show that the method for treating organic pollutants in chlorine-containing wastewater proposed in this application can efficiently activate persulfate to treat organic pollutants in chlorine-containing wastewater, providing a new method for the advanced treatment of chlorine-containing wastewater.

[0084] Example 3

[0085] Two reaction systems were designed: αAl₂O₃ / permonosulfate / chloride and γAl₂O₃ / permonosulfate / chloride. The mixed solutions contained 10 μM carbamazepine, 1.0 g / L activated alumina, 40 μM permonosulfate, and 1.0 mM chloride, with an initial pH of 3.0. The mixed solutions of both reaction systems were magnetically stirred in a 25°C water bath for 20 min.

[0086] The concentration of carbamazepine was determined using ultra-high performance liquid chromatography at a wavelength of 210 nm. The results are as follows: Figure 4 As shown, the removal rates of carbamazepine in the two reaction systems were 11.2% and 86.0%, respectively.

[0087] The above experimental results show that, compared with α-crystal alumina, γ-crystal activated alumina has higher catalytic efficiency.

[0088] In this embodiment, αAl2O3 was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., with an average particle size of 209.87 nm.

[0089] Example 4

[0090] Six reaction systems were prepared: manganese dioxide / persulfate / chloride, manganese tetroxide / persulfate / chloride, ferric oxide / persulfate / chloride, cobalt tetroxide / persulfate / chloride, copper oxide / persulfate / chloride, and activated alumina / persulfate / chloride. The mixed solutions contained carbamazepine at a concentration of 10 μM, activated alumina at a dosage of 1.0 g / L, persulfate at a concentration of 40 μM, chloride at a concentration of 1.0 mM, and an initial pH of 3.0. The mixed solutions of the six reaction systems were placed in a constant temperature water bath at 25°C and magnetically stirred for 20 min.

[0091] The concentration of carbamazepine was determined using ultra-high performance liquid chromatography at a wavelength of 210 nm. The results are as follows: Figure 5 As shown, the removal rates of carbamazepine in the six reaction systems were 2.7%, 4.4%, 17.7%, 8.8%, 46.1%, and 86.0%, respectively, with apparent reaction rates of 0.00194 min. -1 0.0036min -1 0.01042min -1 0.00567min -1 0.03718min -1 0.10212min -1 .

[0092] The above experimental results show that, compared with traditional Fenton-like catalysts, activated alumina, as a Fenton-like catalyst, can significantly enhance the removal of organic pollutants from chlorine-containing wastewater.

[0093] Example 5

[0094] Six mixed solutions of activated alumina, persulfate, and chloride were prepared. The carbamazepine concentration in each solution was 10 μM, the activated alumina dosage was 1.0 g / L, the persulfate concentration was 40 μM, and the chloride ion concentrations were 0.1 mM, 1.0 mM, 10.0 mM, 100.0 mM, 250.0 mM, and 500.0 mM, respectively. The initial pH was 3.0. All six mixed solutions were placed in a constant temperature water bath at 25°C and magnetically stirred for 20 min.

[0095] The concentration of carbamazepine was determined using ultra-high performance liquid chromatography at a wavelength of 210 nm, and the degradation rates of carbamazepine in six mixed solutions were fitted. The results are as follows: Figure 6 As shown. In the six mixed solutions, the surface rates were 0.01407 min. -1 0.11214min -1 0.13987min -1 0.25144min -1 0.52488min -1 0.50697min -1 .

[0096] The above experimental results show that the target pollutants can be efficiently degraded in chlorine-containing wastewater with a chloride ion concentration range of 1.0-500.0 mM.

[0097] Example 6

[0098] Three mixed solutions were prepared, consisting of activated alumina, persulfate, and chloride ions. The carbamazepine concentration in each solution was 10 μM, the activated alumina dosage was 1.0 g / L, the persulfate concentration was 40 μM, and the chloride ion concentration was 1.0 mM. The initial pH values ​​were 3.0, 5.0, and 7.0, respectively. All three solutions were placed in a constant-temperature water bath at 25°C and magnetically stirred for 20 min.

[0099] The concentration of carbamazepine was determined using ultra-high performance liquid chromatography at a wavelength of 210 nm. The results are as follows: Figure 7 As shown, the removal rates of carbamazepine in the three mixed solutions were 86.0%, 77.4%, and 57.8%, respectively.

[0100] The above experimental results show that the method for treating organic pollutants in chlorine-containing wastewater proposed in this application can achieve efficient removal of target pollutants under acidic / neutral conditions.

[0101] Example 7

[0102] Three mixed solutions were prepared, consisting of activated alumina, persulfate, and chloride ions. The carbamazepine concentration in each solution was 10 μM, the activated alumina dosage was 1.0 g / L, the chloride ion concentration was 1.0 mM, the initial pH was 3.0, and the molar ratios of carbamazepine to persulfate were 1:1, 1:4, and 1:10, respectively. All three mixed solutions were placed in a constant-temperature water bath at 25°C and magnetically stirred for 20 min.

[0103] The concentration of carbamazepine was determined using ultra-high performance liquid chromatography at a wavelength of 210 nm. The results are as follows: Figure 8 As shown, the removal rates of carbamazepine in the three mixed solutions were 83.2%, 86.0%, and 90.0%, respectively.

[0104] The above experimental results show that when the molar ratio of carbamazepine to persulfate is 1:10 to 1:1, the target pollutant can be efficiently degraded.

[0105] Example 8

[0106] Four mixed solutions were prepared, consisting of activated alumina, persulfate, and chloride ions. The organic matter concentration in each solution was 10 μM, the activated alumina dosage was 1.0 g / L, the persulfate concentration was 40 μM, the chloride ion concentration was 1.0 mM, and the initial pH was 3.0. Representative pollutants were selected: o-methylphenol (a phenol), carbamazepine (an amino group), sulfamethoxazole (a sulfonamide), and methylphenyl sulfoxide (a sulfoxide group). All four mixed solutions were placed in a constant-temperature water bath at 25°C and magnetically stirred for 20 min.

[0107] The concentration of pollutants was determined using ultra-high performance liquid chromatography (UHPLC), and the results are as follows: Figure 9 As shown, the removal rates of organic matter in the four mixed solutions were 100%, 86.0%, 97.7%, and 100.0%, respectively.

[0108] The above results show that the method for treating organic pollutants in chlorine-containing wastewater of this application achieves efficient degradation of phenols, amino acids, sulfonamides and sulfoxides within 20 minutes, indicating that this application has universality and great application potential in the organic treatment of wastewater.

[0109] Example 9

[0110] Six mixed solutions of activated alumina, persulfate, and chloride were prepared. The carbamazepine concentration in each solution was 10 μM, the persulfate concentration was 40 μM, and the chloride ion concentration was 1.0 mM. The initial pH was 3.0, and the activated alumina dosages were 0.25 g / L, 0.50 g / L, 0.75 g / L, 1.0 g / L, 1.25 g / L, and 1.50 g / L, respectively. All six mixed solutions were placed in a constant temperature water bath at 25°C and magnetically stirred for 20 min.

[0111] The concentration of carbamazepine was determined using ultra-high performance liquid chromatography at a wavelength of 210 nm, and the degradation rates of carbamazepine in six mixed solutions were fitted. The results are as follows: Figure 10 As shown, the removal rates of carbamazepine in the six mixed solutions were 17.9%, 79.5%, 94.5%, 93.1%, 84.9%, and 60.4%, respectively.

[0112] The above experimental results show that the system of this application can achieve efficient removal of carbamazepine within 20 minutes in the range of activated alumina dosage from 0.5 g / L to 1.5 g / L.

[0113] Example 10

[0114] Two mixed solutions were prepared: one containing activated alumina, the other persulfate, and the third containing chloride ions. The concentrations of the persulfate and chloride ions in both solutions were 40 μM and 10.0 mM respectively, with an initial pH of 3.0. The activated alumina dosage was 1.0 g / L, and the representative deoxynucleotides were 2'-deoxyguanosine and 2',3'-dideoxythymidine, with an initial concentration of 2.0 μM. Both mixed solutions were placed in a constant temperature water bath at 25°C and magnetically stirred for 20 min.

[0115] The concentration of deoxynucleotides was determined using ultra-high performance liquid chromatography (UHPLC), and the degradation rates of carbamazepine in two mixed solutions were fitted. The results are as follows: Figure 11 As shown in the figure, the removal rates of 2'-deoxyguanosine and 2',3'-dideoxythymidine in the two mixed solutions were 85.5% and 64.5%, respectively.

[0116] The above experimental results show that the system proposed in this application has great disinfection potential against bacteria in chlorine-containing wastewater, and this application has potential application prospects in the purification of chlorine-containing water systems.

[0117] The activated alumina in Examples 1 to 10 refers to γ-alumina. The specific surface area of ​​activated alumina ranges from 100 m². 2 / g to 300m 2 / g; the oxygen content of surface hydroxyl groups accounts for 30% to 60% of the total oxygen content of activated alumina.

[0118] In Examples 1 to 10, the specific surface area of ​​the activated alumina was 187.81 m². 2 / g, pore volume is 0.91cm 3 / g, see details Figure 12 .like Figure 13 The oxygen content of surface hydroxyl groups accounts for 51.3% of the total oxygen content of activated alumina.

[0119] The persulfate used in the embodiments of this application is commercially available potassium persulfate complex salt (≥42% KHSO5basis); the persulfate is commercially available potassium persulfate (K2S2O8, 99.5%).

[0120] This application has been described in detail above with reference to specific exemplary embodiments. However, it should be understood that various modifications and variations can be made without departing from the scope of this application as defined by the appended claims. The detailed description and drawings should be considered illustrative only and not restrictive, and any such modifications and variations shall fall within the scope of this application described herein. Furthermore, the background art is intended to illustrate the current state of research and development and significance of the technology, and is not intended to limit this application or its application field.

[0121] More specifically, although exemplary embodiments of this application have been described herein, this application is not limited to these embodiments, but includes any and all embodiments modified, omitted, such as combinations between various embodiments, adaptive changes, and / or substitutions, as would be apparent to those skilled in the art from the foregoing detailed description. The limitations in the claims are to be interpreted broadly as used in the language of the claims and are not limited to the examples described in the foregoing detailed description or during the implementation of this application, which should be considered non-exclusive. Any step enumerated in any method or process claim may be performed in any order and is not limited to the order presented in the claims. Therefore, the scope of this application should be determined solely by the appended claims and their legal equivalents, and not by the description and examples given above.

[0122] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains. In case of conflict, the definitions in this specification shall prevail. When mass, concentration, temperature, time, or other values ​​or parameters are expressed as ranges, preferred ranges, or a series of upper and lower preferred values, this shall be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether such range is disclosed individually. For example, the range 1-50 should be understood to include any number, combination of numbers, or subrange selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50, as well as all decimal values ​​between the integers mentioned above, such as 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9. Regarding subranges, specifically consider "nested subranges" extending from any endpoint of the range. For example, nested sub-ranges of the exemplary range 1-50 may include 1-10, 1-20, 1-30 and 1-40 in one direction, or 50-40, 50-30, 50-20 and 50-10 in another direction.

[0123] The above description is merely a selection of preferred embodiments of this disclosure and an explanation of the technical principles employed. Those skilled in the art should understand that the scope of the invention involved in the embodiments of this disclosure is not limited to technical solutions formed by specific combinations of the above-described technical features, but should also cover other technical solutions formed by arbitrary combinations of the above-described technical features or their equivalents without departing from the above-described inventive concept. For example, technical solutions formed by substituting the above-described features with (but not limited to) technical features with similar functions disclosed in the embodiments of this disclosure.

Claims

1. A method for treating organic pollutants in chlorinated wastewater, characterized in that: the method comprises the following main steps: mixing the organic pollutants, the oxidizing agent and the chlorinated wastewater to obtain a reaction solution, wherein the organic pollutants comprise one or more of o-methylphenol, carbamazepine, sulfamethoxazole or methylphenylsulfoxide, the oxidizing agent is any one or a combination of peroxymonosulfate and peroxyacetic acid, the molar ratio of the organic pollutants to the oxidizing agent is 1:10 to 1:1, and the concentration of chloride ions in the chlorinated wastewater is greater than or equal to 1.0 mM; adjusting the initial pH value of the reaction solution, and the initial pH value is 3.0 to 7.0; The active aluminum-based oxide is added into the reaction solution, wherein the active aluminum-based oxide includes active alumina, the specific surface area of the active alumina ranges from 100 m 2 / g to 300 m 2 / g, the content of surface hydroxyl oxygen in the total oxygen content of the active alumina accounts for 30% to 60%, and the dosage of the active alumina ranges from 0.50 g / L to 1.50 g / L.

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