Method for in-situ treatment of dibenzo-nitrogen hybrid organic pollutants in chlorine-containing water body

Abstract

The invention relates to the technical field of water treatment, and discloses a method for in-situ treatment of dibenzo-nitrogen hybrid organic pollutants in a chlorine-containing water body. The method comprises the following steps: adding pypocholoride and hydrosulfite into the chlorine-containing water body, and carrying out an oxidation-reduction reaction to degrade the dibenzo-nitrogen hybrid organic pollutants. According to the method provided by the invention, pypocholoride and hydrosulphite are added into the water body, inherent chloride ions in the water are used as an accelerant, free radicals are amplified through a chain reaction, generated. SO4 <->,. OH, Cl <-> and ClO <-> are high-activity free radicals, and dibenzazepine organic pollutants such as carbamazepine and the like can be efficiently degraded; the method can be used under the wide pH condition of pH 1-11, the reaction temperature is 10-50 DEG C, additional energy input is not needed, the reaction condition is mild, energy is saved, the method is environment-friendly, the operation is simple and convenient, and the cost is low; the method is suitable for seawater desalination wastewater, industrial high-salinity wastewater and other scenes.

Description

Technical Field

[0001] This invention relates to the field of water treatment technology, and particularly to an in-situ treatment method for dibenzo-p-ethylhexane in chlorinated water. Methods for dealing with organic pollutants. Background Technology

[0002] Persistent dibenzodiazepines Organic pollutants (OPCs) persist in the environment for a long time, pose significant hazards, are difficult to treat, and exhibit bioaccumulation. Research on technologies for treating these pollutants has been a hot topic in the environmental science and technology community, aiming to achieve efficient, low-cost, and environmentally friendly water purification and disinfection from source to point of use. Among these, advanced oxidation processes (AOPs) have attracted considerable attention due to their remarkable effectiveness in water disinfection and pollutant removal.

[0003] The core of AOPs lies in the in-situ generation of highly reactive substances, such as hydroxyl radicals (·OH) and superoxide radicals (·O2). - ) and sulfate radicals (·SO4) - These substances can effectively decompose organic pollutants and pathogens. Among them, ·OH has become a research hotspot due to its high oxidation potential. However, in complex aquatic environments, such as those containing hydroxyl radical scavengers (e.g., carbonate / bicarbonate anions and natural organic matter NOM), the treatment efficiency of ·OH-based AOPs may be affected. In contrast, ·SO4... - It has a relatively long half-life (4s), a standard redox potential of 2.5V, close to the strong oxidizing power of ·OH, and ·SO4 - It also has the advantages of high stability, long lifespan, and high reactivity, thus it is suitable for degrading dibenzo-p-azines. Regarding organic pollutants, based on SO4 - AOPs technology has gradually become a research hotspot both domestically and internationally.

[0004] SO4 - The formation of ·SO4 typically depends on the decomposition of persulfates and low-valent sulfates, a process that can be achieved under activated conditions such as heating, ultraviolet light irradiation, or metal catalysis. Low-valent sulfates include common sulfites and dithionites. In practice, ·SO4 - The generation mainly occurs through two pathways: one is through energy excitation, involving light energy, heat energy, and ultrasound; the other is through the utilization of transition metal ions such as cobalt ions (Co). 2+ ), iron ions (Fe) 2+ ) and nickel ions (Ni 2+Both methods, including energy-activated sulfite activation, are theoretically feasible but each has its limitations. Energy-activated sulfite activation is energy-intensive and requires strict technical conditions; while transition metal activation may introduce metal ions that cause metal toxicity, leading to secondary pollution. (SO4) - The aforementioned drawbacks of the generation technology severely limit the development of SO4-based technologies. - Advanced oxidation processes are widely used in the field of water treatment.

[0005] In water treatment, the effectiveness of chlorine disinfection primarily stems from the generation of ·OH and chlorine free radicals (Cl·), which are key reactive species driving water purification. ·OH, as a non-selective reactive free radical, exhibits excellent oxidizing power in advanced oxidation processes. In contrast, Cl· shows similar or even higher reactivity to ·OH in reactions with various aromatic compounds. Therefore, chlorine disinfection performs exceptionally well in water pollution treatment. However, in seawater desalination, industrial wastewater treatment, and some groundwater treatment processes, the increased salt concentration in high-salinity environments negatively impacts the effectiveness of traditional chlorine disinfection. Summary of the Invention

[0006] The present invention aims to at least solve one of the aforementioned technical problems existing in the prior art. Therefore, the object of the present invention is to provide an in-situ treatment method for dibenzo-p-ethylhexane (DBX) in chlorinated water. Methods for dealing with organic pollutants.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0008] This invention provides an in-situ treatment method for dibenzo-p-ethylhexane in chlorinated water. A method for treating dibenzo-p-ethylhexane pollutants includes the following steps: adding hypochlorite and bisulfite to chlorinated water to carry out an oxidation-reduction reaction and degrade the dibenzo-p-ethylhexane. Organic pollutants.

[0009] In some embodiments of the present invention, in the chlorinated water, Cl - The concentration is greater than or equal to 1 mmol / L.

[0010] In some preferred embodiments of the present invention, the concentration of Cl- in the chlorinated water is 3-550 mmol / L.

[0011] In some embodiments of the present invention, the pH of the chlorinated water is 1-11.

[0012] In some preferred embodiments of the present invention, the pH of the chlorinated water is 3-8.

[0013] In some embodiments of the present invention, the chlorinated water contains dibenzo-p-ethylhexane. The concentration of organic pollutants is 1-20 μmol / L.

[0014] In some preferred embodiments of the present invention, the chlorinated water contains dibenzo-p-ethylhexane. The concentration of organic pollutants is 1-15 μmol / L.

[0015] In some embodiments of the present invention, the dibenzo-azobis(II) Organic pollutants include at least one of carbamazepine, imipramine, and oxcarbazepine.

[0016] In some embodiments of the present invention, the dosage of hypochlorite is 10-400 μmol / L.

[0017] In some preferred embodiments of the present invention, the dosage of hypochlorite is 50-200 μmol / L.

[0018] In some embodiments of the present invention, the amount of bisulfite added is 100-400 μmol / L.

[0019] In some preferred embodiments of the present invention, the amount of bisulfite added is 110-250 μmol / L.

[0020] In some embodiments of the present invention, the hypochlorite is selected from at least one of calcium hypochlorite and sodium hypochlorite.

[0021] In some preferred embodiments of the present invention, the hypochlorite is calcium hypochlorite.

[0022] In some embodiments of the present invention, the bisulfite is selected from at least one of sodium bisulfite, potassium bisulfite, and sodium sulfite.

[0023] In some preferred embodiments of the present invention, the bisulfite is selected from sodium bisulfite or potassium bisulfite.

[0024] In some embodiments of the present invention, the temperature of the redox reaction is 10-50°C and the time is greater than or equal to 60 min.

[0025] In some preferred embodiments of the present invention, the temperature of the redox reaction is 25-40°C and the time is 60-120 min.

[0026] In some embodiments of the present invention, the redox reaction process is aided by stirring, and the stirring speed is 200-1200 r / min.

[0027] In some preferred embodiments of the present invention, the stirring speed is 500-1200 r / min.

[0028] The basic principles of this invention are explained as follows:

[0029] An increase in salt concentration in water can decrease the content of hypochlorous acid, thus affecting the effectiveness of traditional chlorine disinfection. This invention utilizes the inherent Cl- in chlorinated water... - As a promoter, hypochlorite (ClO) is produced by the slow release of hypochlorite, which has oxidizing properties and is slightly soluble in water. - ), and with bisulfite (HSO3) - A redox reaction occurs, activating bisulfite and generating various highly reactive free radicals (·SO4) in situ during the reaction. - Free radicals (·OH, Cl·, ClO·) exhibit excellent oxidizing power due to their high redox potentials, capable of breaking unsaturated chemical bonds in recalcitrant organic matter and thus playing a degrading role; ·SO4 - It has similar oxidizing power to ·OH and a longer half-life. It can synergistically attack the unsaturated bonds of organic matter with Cl· (highly reactive), and efficiently degrade stubborn pollutants. The reaction formulas involved are shown in Equations 1-7:

[0030] ClO - +2H + +Cl - →Cl2(aq)+H2O Equation 1;

[0031]

[0032]

[0033]

[0034]

[0035]

[0036] ·OH+Cl - →ClO·+H + Formula 7.

[0037] Compared with the prior art, the beneficial effects of the present invention are:

[0038] The present invention provides an in-situ treatment method for dibenzo-p-ethylhexane in chlorinated water. The method for treating organic pollutants involves adding hypochlorite and bisulfite to water bodies and utilizing the inherent chloride ions in the water as a promoter to amplify free radicals through a chain reaction, producing SO42-. -·OH, Cl·, and ClO· are all highly reactive free radicals that can efficiently degrade carbamazepine and other dibenzo-azines. This method is suitable for the degradation of organic pollutants. It can be used under a wide pH range of 1-11, with a reaction temperature of 10-50℃. It requires no additional energy input, has mild reaction conditions, saves energy, and is environmentally friendly, easy to operate, and low in cost. It is applicable to scenarios such as seawater desalination wastewater and industrial high-salinity wastewater. Attached Figure Description

[0039] Figure 1 The degradation rates of carbamazepine in Example 1 and Comparative Examples 1-3 are shown in the graph.

[0040] Figure 2 This is a graph showing the degradation rate of carbamazepine under different reaction atmospheres in Example 2;

[0041] Figure 3 For different Cl in Example 3 - Degradation rate of carbamazepine at different concentrations;

[0042] Figure 4 The graph shows the degradation rate of carbamazepine under different amounts of bisulfite added in Example 4.

[0043] Figure 5 The graph shows the degradation rate of carbamazepine under different pH conditions in Example 5. Detailed Implementation

[0044] The present invention will be further described in detail below through specific embodiments. Unless otherwise specified, the raw materials, reagents, or apparatus used in the embodiments and comparative examples are all available from conventional commercial sources or can be obtained by existing technical methods. Unless otherwise specified, the test or experimental methods are conventional methods in the art.

[0045] Example 1

[0046] This embodiment provides an in-situ treatment method for dibenzo[a]azine in chlorinated water. The method for dealing with organic pollutants involves the following steps:

[0047] Organic simulated wastewater containing 2 μmol / L carbamazepine and pH=7.0 was prepared using pure water. Calcium hypochlorite, sodium bisulfite solution, and sodium chloride solution were added to the water to make the concentrations of calcium hypochlorite, sodium bisulfite, and sodium chloride in the water 100 μmol / L, 100 μmol / L, and 5.0 mmol / L, respectively. The wastewater was subjected to an oxidation-reduction reaction at 30℃ and shaking (800 r / min) for 60 min. After the reaction, the residual concentration of carbamazepine in the wastewater was measured.

[0048] Example 2

[0049] This embodiment investigates the reaction atmosphere for dibenzodiazepines. The impact of the degradation effect on organic pollutants is investigated through the following steps:

[0050] Take three identical opaque reaction vessels, number them reaction vessels 1-3, and prepare organic simulated wastewater containing 2 μmol / L carbamazepine and pH=7.0 with pure water respectively;

[0051] Calcium hypochlorite solution, sodium bisulfite solution and sodium chloride solution were added to reaction vessel 1 to make the concentrations of calcium hypochlorite, sodium bisulfite and sodium chloride in the water 100 μmol / L, 150 μmol / L and 5.0 mmol / L respectively. No aeration was performed and the dissolved oxygen concentration was about 7.6 mg / L.

[0052] Calcium hypochlorite solution, sodium bisulfite solution, and sodium chloride solution were added to reaction vessel 2 to make the concentrations of calcium hypochlorite, sodium bisulfite, and sodium chloride in the water 100 μmol / L, 150 μmol / L, and 5.0 mmol / L, respectively. Oxygen was aerated, and the dissolved oxygen concentration was approximately 12.4 mg / L.

[0053] Calcium hypochlorite solution, sodium bisulfite solution, and sodium chloride solution were added to reaction vessel 3 to make the concentrations of calcium hypochlorite, sodium bisulfite, and sodium chloride in the water 100 μmol / L, 150 μmol / L, and 5.0 mmol / L, respectively. Nitrogen gas was aerated, and the dissolved oxygen concentration was approximately 0.2 mg / L.

[0054] The wastewater in reaction vessels 1-3 was subjected to an oxidation-reduction reaction at 30°C and under shaking conditions (800 r / min) for 8 min. After the reaction, the residual concentration of carbamazepine in the wastewater was measured.

[0055] Example 3

[0056] This embodiment investigates Cl in water. - Concentration of p-dibenzo-p-ethyl The impact of the degradation effect on organic pollutants is investigated through the following steps:

[0057] Take seven identical opaque reaction vessels, number them 1-7, and prepare organic simulated wastewater containing 2 μmol / L carbamazepine and pH=7.0 with pure water.

[0058] Add calcium hypochlorite and sodium bisulfite solutions to reaction vessel 1 to make the concentrations of calcium hypochlorite and sodium bisulfite in the water 100 μmol / L and 150 μmol / L, respectively.

[0059] Add calcium hypochlorite solution, sodium bisulfite solution and sodium chloride solution to reaction vessel 2 to make the concentrations of calcium hypochlorite, sodium bisulfite and sodium chloride in the water 100 μmol / L, 150 μmol / L and 1 mmol / L, respectively;

[0060] Calcium hypochlorite solution, sodium bisulfite solution and sodium chloride solution were added to reaction vessel 3 to make the concentrations of calcium hypochlorite, sodium bisulfite and sodium chloride in the water 100 μmol / L, 150 μmol / L and 3 mmol / L, respectively;

[0061] Calcium hypochlorite solution, sodium bisulfite solution and sodium chloride solution were added to reaction vessel 4 to make the concentrations of calcium hypochlorite, sodium bisulfite and sodium chloride in the water 100 μmol / L, 150 μmol / L and 5 mmol / L, respectively.

[0062] Calcium hypochlorite solution, sodium bisulfite solution and sodium chloride solution were added to reaction vessel 5 to make the concentrations of calcium hypochlorite, sodium bisulfite and sodium chloride in the water 100 μmol / L, 150 μmol / L and 7 mmol / L, respectively.

[0063] Calcium hypochlorite solution, sodium bisulfite solution and sodium chloride solution were added to reaction vessel 6 to make the concentrations of calcium hypochlorite, sodium bisulfite and sodium chloride in the water 100 μmol / L, 150 μmol / L and 10 mmol / L, respectively.

[0064] Calcium hypochlorite solution, sodium bisulfite solution and sodium chloride solution were added to reaction vessel 7 to make the concentrations of calcium hypochlorite, sodium bisulfite and sodium chloride in the water 100 μmol / L, 150 μmol / L and 35 mmol / L, respectively.

[0065] The wastewater in reaction vessels 1-7 was subjected to an oxidation-reduction reaction at 30°C and under shaking conditions (800 r / min) for 60 min. After the reaction was completed, the residual concentration of carbamazepine in the wastewater was measured.

[0066] Example 4

[0067] This embodiment investigates the dosage of bisulfite for dibenzo-p-benzodiazepines. The impact of the degradation effect on organic pollutants is investigated through the following steps:

[0068] Take six identical opaque reaction vessels, number them 1-6, and prepare organic simulated wastewater containing 2 μmol / L carbamazepine and pH=7.0 with pure water.

[0069] Add calcium hypochlorite solution, sodium bisulfite solution and sodium chloride solution to reaction vessel 1 to make the concentrations of calcium hypochlorite, sodium bisulfite and sodium chloride in the water 100 μmol / L, 50 μmol / L and 5 mmol / L, respectively;

[0070] Add calcium hypochlorite solution, sodium bisulfite solution and sodium chloride solution to reaction vessel 2 to make the concentrations of calcium hypochlorite, sodium bisulfite and sodium chloride in the water 100 μmol / L, 75 μmol / L and 5 mmol / L, respectively;

[0071] Add calcium hypochlorite solution, sodium bisulfite solution and sodium chloride solution to reaction vessel 3 to make the concentrations of calcium hypochlorite, sodium bisulfite and sodium chloride in the water 100 μmol / L, 100 μmol / L and 5 mmol / L, respectively;

[0072] Calcium hypochlorite solution, sodium bisulfite solution and sodium chloride solution were added to reaction vessel 4 to make the concentrations of calcium hypochlorite, sodium bisulfite and sodium chloride in the water 100 μmol / L, 125 μmol / L and 5 mmol / L, respectively.

[0073] Add calcium hypochlorite solution, sodium bisulfite solution and sodium chloride solution to reaction vessel 5 to make the concentrations of calcium hypochlorite, sodium bisulfite and sodium chloride in the water 100 μmol / L, 150 μmol / L and 5 mmol / L, respectively;

[0074] Calcium hypochlorite solution, sodium bisulfite solution and sodium chloride solution were added to reaction vessel 6 to make the concentrations of calcium hypochlorite, sodium bisulfite and sodium chloride in the water 100 μmol / L, 250 μmol / L and 5 mmol / L, respectively.

[0075] The wastewater in reaction vessels 1-6 was subjected to an oxidation-reduction reaction at 30°C and under shaking conditions (800 r / min) for 10 min. After the reaction was completed, the residual concentration of carbamazepine in the wastewater was measured.

[0076] Example 5

[0077] This embodiment investigates the effect of water pH on dibenzo[a]azine. The impact of the degradation effect on organic pollutants is investigated through the following steps:

[0078] Take six identical opaque reaction vessels, number them 1-6, and prepare organic simulated wastewater containing 2 μmol / L carbamazepine in pure water for each vessel.

[0079] Calcium hypochlorite, sodium bisulfite, and sodium chloride solutions were added to six reaction vessels to make the concentrations of calcium hypochlorite, sodium bisulfite, and sodium chloride in the water 100 μmol / L, 150 μmol / L, and 5 mmol / L, respectively. Then, the pH values ​​of the simulated organic wastewater in the six reaction vessels were adjusted to 1.0, 3.0, 5.0, 7.0, 9.0, and 11.0, respectively, using 0.1 mol / L NaOH solution and 0.1 mol / L dilute H2SO4.

[0080] The wastewater in reaction vessels 1-6 was subjected to an oxidation-reduction reaction at 30°C and under shaking conditions (800 r / min) for 12 min. After the reaction, the residual concentration of carbamazepine in the wastewater was measured.

[0081] Example 6

[0082] This embodiment investigates the effect of redox reaction temperature on dibenzoxazine. The impact of the degradation effect on organic pollutants is investigated through the following steps:

[0083] Take five identical opaque reaction vessels, number them 1-5, and prepare organic simulated wastewater containing 2 μmol / L carbamazepine and pH=7.0 with pure water.

[0084] Calcium hypochlorite solution, sodium bisulfite solution, and sodium chloride solution were added to five reaction vessels respectively, so that the concentrations of calcium hypochlorite, sodium bisulfite, and sodium chloride in the water were 100 μmol / L, 150 μmol / L, and 5 mmol / L, respectively.

[0085] The temperatures of the five reaction vessels were adjusted to 10℃, 20℃, 30℃, 40℃ and 50℃ respectively using a constant temperature water bath, and the redox reaction was carried out under shaking (800r / min) for 60min. After the reaction, the residual concentration of carbamazepine in the wastewater was measured.

[0086] Example 7

[0087] This embodiment investigates dibenzo[a]azine in water. The effect of the initial concentration of organic pollutants on their degradation efficiency is investigated through the following steps:

[0088] Take five identical opaque reaction vessels, numbered reaction vessels 1-5, and prepare organic simulated wastewater with pH=7.0 and carbamazepine concentrations of 2μmol / L, 4μmol / L, 6μmol / L, 8μmol / L and 10μmol / L respectively using pure water;

[0089] Calcium hypochlorite solution, sodium bisulfite solution, and sodium chloride solution were added to five reaction vessels respectively, so that the concentrations of calcium hypochlorite, sodium bisulfite, and sodium chloride in the water were 100 μmol / L, 150 μmol / L, and 5 mmol / L, respectively.

[0090] The wastewater in reaction vessels 1-5 was subjected to an oxidation-reduction reaction at 30°C and under shaking conditions (800 r / min) for 8 min. After the reaction, the residual concentration of carbamazepine in the wastewater was measured.

[0091] Comparative Example 1

[0092] This comparative example provides an in-situ treatment method for dibenzo[a]azine in chlorinated water. The method for dealing with organic pollutants involves the following steps:

[0093] Organic simulated wastewater containing 2 μmol / L carbamazepine and pH=7.0 was prepared using pure water. Calcium hypochlorite was added to the water to make its concentration 100 μmol / L. The wastewater was subjected to an oxidation-reduction reaction at 30℃ and shaking (800 r / min) for 60 min. After the reaction was completed, the remaining concentration of carbamazepine in the wastewater was measured.

[0094] Comparative Example 2

[0095] This comparative example provides an in-situ treatment method for dibenzo[a]azine in chlorinated water. The method for dealing with organic pollutants involves the following steps:

[0096] Organic simulated wastewater containing 2 μmol / L carbamazepine and pH=7.0 was prepared using pure water. Sodium bisulfite solution was added to the water to make the concentration of sodium bisulfite in the water 100 μmol / L. The wastewater was subjected to an oxidation-reduction reaction at 30℃ and shaking (800 r / min) for 60 min. After the reaction was completed, the residual concentration of carbamazepine in the wastewater was measured.

[0097] Comparative Example 3

[0098] This comparative example provides an in-situ treatment method for dibenzo[a]azine in chlorinated water. The method for dealing with organic pollutants involves the following steps:

[0099] Organic simulated wastewater containing 2 μmol / L carbamazepine and pH=7.0 was prepared using pure water. Calcium hypochlorite and sodium bisulfite solutions were added to the water to make the concentrations of calcium hypochlorite and sodium bisulfite in the water both 100 μmol / L. The wastewater was subjected to an oxidation-reduction reaction at 30℃ and shaking (800 r / min) for 60 min. After the reaction was completed, the residual concentration of carbamazepine in the wastewater was measured.

[0100] Application Example 1

[0101] This application example provides an in-situ treatment method for dibenzo-p-ethylhexane (DABA) in chlorinated water. The application of methods for treating organic pollutants in actual water bodies involves the following steps:

[0102] Take three opaque reaction vessels, numbered 1-3, and add 100 mL of deionized water (Cl) to each vessel. - Concentration of 0), lake water (Cl) - Concentration 1.09 mmol / L) and near-seawater (Cl - (Concentration of 493 mmol / L), then carbamazepine solution and imipramine solution were added to all three reaction vessels to make the concentration of carbamazepine and imipramine in the three water bodies 2 μmol / L;

[0103] Calcium hypochlorite and sodium bisulfite solutions were added to three reaction vessels respectively, so that the concentrations of calcium hypochlorite and sodium bisulfite in the water were 100 μmol / L and 150 μmol / L respectively.

[0104] The wastewater in reaction vessels 1-3 was subjected to an oxidation-reduction reaction at 30°C and with shaking (800 r / min) for 1 min. After the reaction, the residual concentration of carbamazepine in the wastewater was measured.

[0105] Figure 1 The graph shows the degradation rate of carbamazepine in Example 1 and Comparative Examples 1-3. Figure 1 It can be seen that in Comparative Examples 1 and 2, the degradation rates of carbamazepine within 60 min were 3.9% and 0.7%, respectively, when only calcium hypochlorite or sodium bisulfite solution was added, indicating that the HClO / ClO ratio was relatively stable. - It has low degradation efficiency for carbamazepine, a recalcitrant organic compound, and HSO - Example 3 is a reducing agent with no oxidizing ability, resulting in extremely poor degradation. In Comparative Example 3, the combined use of calcium hypochlorite and sodium bisulfite solution resulted in a 77.1% degradation rate of carbamazepine within 60 minutes, indicating that calcium hypochlorite can slowly release ClO. - oxidize HSO - 3 generation With ClO - Reaction generation Hydrolysis produces ·OH, which continuously generates active species such as Cl· through free radical chain reactions, enhancing the degradation effect of carbamazepine. In Example 1, the degradation rate of carbamazepine reached 96.5% within 60 minutes, indicating that Cl· can be utilized in chloride-containing wastewater. - As a promoter, it amplifies free radicals through a chain reaction, further enhancing the degradation effect of carbamazepine.

[0106] Figure 2This is a graph showing the degradation rate of carbamazepine under different reaction atmospheres in Example 2. Figure 2 It can be seen that, compared with natural conditions, oxygen (high dissolved oxygen concentration) and nitrogen atmosphere have a slight inhibitory effect on the degradation of carbamazepine. After 8 minutes of reaction, the degradation rates of carbamazepine were 96.1% and 95.1%, respectively, which were lower than the degradation rate (99%) under non-aeration conditions. This indicates that the method provided by the present invention relies on an anaerobic pathway, can be carried out under natural conditions, and is more conducive to saving energy.

[0107] Figure 3 For different Cl in Example 3 - The degradation rate graph of carbamazepine at different concentrations is shown in the figure. Figure 3 It can be seen that, under the same reaction conditions, after 60 minutes of reaction, different Cl... - The degradation rate of carbamazepine in concentrated wastewater can reach over 90%. - When the concentration is greater than or equal to 1 mmol / L, the degradation rate of carbamazepine reaches more than 98%, indicating that the method provided by the present invention can make good use of the chloride ions inherent in the water and promote the free radical cycle.

[0108] Figure 4 This is a graph showing the degradation rate of carbamazepine under different amounts of bisulfite added in Example 4. Figure 4 It can be seen that the carbamazepine degradation rates at bisulfite concentrations of 50 μmol / L, 75 μmol / L, 100 μmol / L, 125 μmol / L, 150 μmol / L, and 250 μmol / L were 2.0%, 3.5%, 12.2%, 99%, 99%, and 99%, respectively. That is, under the same reaction conditions, the carbamazepine degradation rate gradually increases with the increase of bisulfite concentration, and the degradation rate can reach 99% when the bisulfite concentration is 125 μmol / L.

[0109] Figure 5 This is a graph showing the degradation rate of carbamazepine under different pH conditions in Example 5. Figure 5 It can be seen that after 12 minutes of reaction, the degradation rates of carbamazepine at pH values ​​of 3.0, 5.0, 7.0, 9.0, and 11.0 were 99.9%, 99.9%, 99.9%, 89%, and 3.8%, respectively. In addition, the degradation rate at pH = 1.0 also reached 99.9% after 12 minutes. This indicates that under different pH reaction conditions, the degradation effect of carbamazepine is better at pH = 1-7. The degradation rate is slightly reduced at pH values ​​greater than 7 and less than or equal to 9, reaching about 80%-90%. Degradation is inhibited at pH values ​​greater than 9.

[0110] Table 1 shows the degradation rate of carbamazepine at different redox reaction temperatures in Example 6. As can be seen from Table 1, the degradation rate of carbamazepine in the range of 10-50℃ shows a trend of first increasing and then decreasing, but it is always higher than 90%. When the temperature reaches 30℃, the degradation rate of carbamazepine can reach 99.9%, and when the temperature reaches 50℃, the degradation rate decreases slightly.

[0111] Table 1. Degradation rate of carbamazepine at different redox reaction temperatures in Example 5.

[0112] temperature 10℃ 20℃ 30℃ 40℃ 50℃ Degradation rate 94％ 95.5％ 99.9％ 99.9％ 99.8％

[0113] Table 2 shows the degradation effect of carbamazepine at different initial concentrations in Example 7. As can be seen from Table 2, under the same reaction conditions, the degradation rate of carbamazepine gradually decreases with the increase of its initial concentration. However, when its initial concentration is 10 μmol / L, the degradation rate can still reach 96.4% within 8 minutes.

[0114] Table 2. Degradation effects of carbamazepine at different initial concentrations in Example 7.

[0115] concentration 2μmol / L 4μmol / L 6μmol / L 8μmol / L 10 μmol / L Degradation rate 99.9％ 99.0％ 98.4％ 96.7％ 96.4％

[0116] Table 3 shows the degradation effects of carbamazepine and imipramine under different actual water conditions in Application Example 1. As can be seen from Table 3, in actual water bodies, the chloride ion content in near-shore waters is higher, which is more conducive to the rapid degradation of carbamazepine and imipramine. The degradation rates of carbamazepine and imipramine can reach 89.3% and 86.6% respectively after 1 minute of reaction.

[0117] Table 3 shows the degradation effects of carbamazepine and imipramine under different actual water conditions in Application Example 1.

[0118] Water body type Deionized water Lake water Nearshore waters Carbamazepine degradation rate 8.5％ 56.4％ 89.3％ Imipramine degradation rate 10.2％ 48.3％ 86.6％

Claims

1. An in-situ treatment method for dibenzo-p-ethylhexane in chlorinated water bodies The method for treating organic pollutants is characterized by, Includes the following steps: Hypochlorite and bisulfite are added to chlorinated water to carry out a redox reaction, thereby degrading the dibenzo-azophosphorus compounds. Organic pollutants.

2. The method according to claim 1, characterized in that, In the chlorinated water, Cl - The concentration is greater than or equal to 1 mmol / L.

3. The method according to claim 1, characterized in that, The pH of the chlorinated water is 1-11.

4. The method according to claim 1, characterized in that, In the chlorinated water body, dibenzo-p-ethyl The concentration of organic pollutants is 1-20 μmol / L.

5. The method according to claim 4, characterized in that, The dibenzoza Organic pollutants include at least one of carbamazepine, imipramine, and oxcarbazepine.

6. The method according to claim 4, characterized in that, The dosage of hypochlorite is 10-400 μmol / L.

7. The method according to claim 4, characterized in that, The dosage of the bisulfite is 100-400 μmol / L.

8. The method according to claim 6, characterized in that, The hypochlorite is selected from at least one of calcium hypochlorite and sodium hypochlorite.

9. The method according to claim 7, characterized in that, The bisulfite is selected from at least one of sodium bisulfite, potassium bisulfite, and sodium sulfite.

10. The method according to claim 1, characterized in that, The redox reaction is carried out at a temperature of 10-50℃ for a time of 60 min or more.

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