A method for evaluating the contribution of active species to pollutant degradation in advanced oxidation processes

Abstract

The present invention provides a method for evaluating the contribution rate of active species to the degradation of pollutants in an advanced oxidation process, so as to achieve accurate evaluation of the degradation contribution rate of typical active species, derive and calculate correction coefficients of typical active species and target pollutants through homogeneous experiments, quantify the correlation between active species and target pollutants by using correction coefficients, comprehensively consider the reaction between active species and target pollutants, aim to introduce correction coefficients into the formula for calculating contribution rate, improve the accuracy of evaluating the contribution rate of active species to the degradation of pollutants in wastewater, and provide a reference for the targeted design of catalysts and the effective removal of pollutants.

Description

Technical Field

[0001] The invention belongs to the field of advanced sewage treatment, and in particular relates to a method for evaluating the contribution rate of active species to pollutant degradation in an advanced oxidation process. Background Art

[0002] Advanced wastewater treatment is an important water treatment process to ensure safe discharge of wastewater. Among them, advanced oxidation technology has received extensive attention and application as an efficient treatment process. Advanced oxidation technology, also known as deep oxidation technology, is characterized by the production of free radicals with strong oxidizing ability. Under the reaction conditions of high temperature and high pressure, electricity, sound, light radiation, catalysts, etc., it oxidizes large molecular refractory organic matter into low-toxic or non-toxic small molecular substances. Transition metal catalysts can activate peroxymonosulfate (PMS) to produce free radicals (such as hydroxyl radicals (·OH), sulfate radicals (SO4 ·- ), superoxide radicals (·O2 - ) and non-radical reactive species (singlet oxygen ( 1 O2), high-valent metal oxo species, etc.), both types of active species exist in actual reaction systems and contribute to the removal of pollutants together. Therefore, it is crucial to accurately evaluate the contribution of typical active species to pollutant degradation.

[0003] In most cases, the traditional method for evaluating the contribution rate of active species is to calculate the steady-state concentration of active species measured by probe compounds and the secondary reaction rate constants between pollutants and each active species. However, due to the neglect of important factors such as the molecular structure of pollutants, the effective reaction time of various active species with pollutants, etc., the calculation results may have certain deviations. The structure of a specific type of pollutant, especially its common or basic parent structure, will affect the effective reaction time with active species and the secondary reaction rate constant, and ultimately affect the contribution of each active species in the degradation process. For example, phenolic pollutants and sulfonamide antibiotics are easily 1 O2 attack, resulting in the reaction 1 O2 should be the dominant active species. However, conventional calculation methods show that OH and SO4 ·- The contribution rate is higher than 1 O2, because the second-order reaction rate constant (k BPA,·OH =6.9×10 9 M -1 s -1 , Much higher than 1 O2 and Therefore, it is necessary to revise the contribution rate of active species to pollutant degradation. Studies have shown that in complex systems, the introduction of correction coefficients to comprehensively consider multiple factors can effectively reduce the difference between simulated values ​​and actual values. Therefore, we introduce correction coefficients into the formula of the traditional method for calculating contribution rates. The correction coefficients can comprehensively consider the reaction between specific active species and pollutants and accurately evaluate the contribution of active species to pollutant degradation. Summary of the invention

[0004] The purpose of the present invention is to provide a method for evaluating the contribution of active species to pollutant degradation in an advanced oxidation process, wherein a correction coefficient is introduced to quantify the correlation between active species and pollutants, and the reaction between active species and pollutants is comprehensively considered, thereby promoting the understanding of the reaction between active species and pollutants and providing valuable predictions for the targeted design of catalysts and the effective removal of pollutants.

[0005] The object of the present invention is achieved through the following technical solutions.

[0006] A method for evaluating the contribution of active species to pollutant degradation in an advanced oxidation process comprises the following steps:

[0007] Step 1: Quantify the correlation between active species and target pollutants using correction factors:

[0008] Firstly, based on the second-order reaction kinetics experiment between the probe compound and the active species, the steady-state concentration of each active species is calculated;

[0009] Then, through an experiment in which only the first active species is included in the reaction system, the correction coefficient between the first active species and the target pollutant is calculated. Specifically, the degradation contribution rate of the first active species is 1, and the correction coefficient of the first active species is equal to the pseudo-first-order rate constant of the target pollutant divided by the product of the second-order rate constant of the target pollutant and this active species and the steady-state concentration of this active species;

[0010] Then, through an experiment in which the reaction system only contains the first active species and the second active species, the correction coefficient between the second active species and the target pollutant is calculated, specifically: the degradation contribution rate of the first active species is equal to the product of the second-order rate constant of the target pollutant with this active species and the steady-state concentration divided by the pseudo-first-order rate constant of the target pollutant, multiplied by the correction coefficient of the first active species; the degradation contribution rate of the second active species is equal to 1 minus the degradation contribution rate of the first active species; the correction coefficient of the second target pollutant is equal to the degradation contribution rate of the second target pollutant multiplied by the pseudo-first-order rate constant of the target pollutant divided by the product of the second-order rate constant of the target pollutant with this active species and the steady-state concentration of this active species;

[0011] Then, through an experiment in which the reaction system only contains the first active species, the second active species and the third active species, the correction coefficient between the third active species and the target pollutant is calculated, specifically: the degradation contribution rate of the first active species is equal to the product of the second-order rate constant and the steady-state concentration of the target pollutant with this active species divided by the pseudo-first-order rate constant of the target pollutant, multiplied by the correction coefficient of the first active species; the degradation contribution rate of the second active species is equal to the product of the second-order rate constant and the steady-state concentration of the target pollutant with this active species divided by the pseudo-first-order rate constant of the target pollutant, multiplied by the correction coefficient of the first active species; the degradation contribution rate of the third active species is equal to 1 minus the degradation contribution rate of the first active species minus the degradation contribution rate of the second active species; the correction coefficient of the third target pollutant is equal to the degradation contribution rate of the third target pollutant multiplied by the pseudo-first-order rate constant of the target pollutant divided by the product of the second-order rate constant of the target pollutant with this active species and the steady-state concentration of this active species;

[0012] If there are four or more active species, the third species shall be taken as an example and so on.

[0013] Step 2: The calculation method of the degradation contribution rate of active species to target pollutants is as follows:

[0014] Detect and calculate the steady-state concentration of each active species in the advanced oxidation reaction system and the pseudo first-order rate constant of the target pollutant, and query the second-order rate constant of the target pollutant and each active species;

[0015] The product of the second-order rate constant of the target pollutant and this active species and the corresponding steady-state concentration of the active species is divided by the pseudo-first-order rate constant of the target pollutant to obtain the uncorrected degradation contribution rate. The uncorrected degradation contribution rate is multiplied by the correction coefficient between the corresponding active species and the target pollutant to obtain the accurate degradation contribution rate.

[0016] As a more optimal technical solution of the present invention, the active species are OH, SO4 ·- , 1 One or more of O2 and high-valent metal oxo species.

[0017] As a more preferred technical solution of the present invention, the first active species is OH, and the second active species is SO4 ·- , the third active species is 1 O2.

[0018] As a more preferred technical solution of the present invention, the probe compound is one or more of nitrobenzene (NB), benzoic acid (BA) and furfuryl alcohol (FFA).

[0019] As a more optimal technical solution of the present invention, the specific method for calculating the steady-state concentration of each active species based on the second-order reaction kinetics experiment of the probe compound and the active species is as follows: after adding the probe compound, a sample is taken out from the solution at a fixed time point during the reaction process, methanol is added to quench it, and the concentration of various pollutants is detected by HPLC after filtration. The steady-state concentration of OH and the pseudo-first-order rate constant of NB are calculated by the following formula:

[0020]

[0021]

[0022]

[0023] Then calculate SO4 by the following formula ·- Steady-state concentration and pseudo-first-order rate constant of BA:

[0024]

[0025]

[0026]

[0027] Then calculate it by the following formula 1 Pseudo-first-order rate constants for steady-state O2 concentration and FFA:

[0028]

[0029]

[0030]

[0031] Where [·OH] ss 、[SO4 ·- ] ss ,and[ 1 O2] ss They are OH, SO4 ·- and 1 Steady-state concentration of O2 (M), k NB，·OH , k BA，·OH , k FFA，·OH and are the second-order rate constants (M -1 s -1 ).

[0032] As a better technical solution of the present invention: the correction coefficient between each active species and the target pollutant is calculated by taking the target pollutant as an example, as follows:

[0033] (1) Calculation of the correction factor of the first active species OH:

[0034] Determine the correction coefficient e1 between ·OH and the target pollutant. The experimental conditions are [FeSO4]0 = 0.1mM, [H2O2]0 = 1.5mM, [pollutant]0 = 20mg / L, T = 25℃. The correction coefficient e1 formula is as follows:

[0035]

[0036] Where [·OH] ss1 is the steady-state concentration of OH when the probe compound NB and the target pollutant coexist, calculated by the following formula

[0037]

[0038] (2) The second active species SO4 ·- Calculation of correction factor:

[0039] Determine SO4 ·- The correction coefficient e1 between the target pollutant and the target pollutant, the experimental conditions are [PDS]0 = 5.0mM, [pollutant]0 = 20mg / L, 5.0mM PDS is added to the mixture, T = 25℃, the correction coefficient e2 formula is as follows:

[0040]

[0041] Where [·OH] ss2 is the steady-state concentration of ·OH when the probe compound NB and the target pollutant coexist, [·SO4 ·- ] ss2 When the probe compound BA and the target pollutant exist at the same time, SO4 ·- The steady-state concentration is calculated as:

[0042]

[0043] Where R ·OH is the contribution rate of ·OH to the degradation of the target pollutant when the probe compound NB and the target pollutant coexist, When the probe compound BA and the target pollutant coexist, SO4 ·- The contribution rate to the degradation of target pollutants is calculated as follows:

[0044]

[0045]

[0046] (3) Calculation of correction factor for the third active species:

[0047] Sure 1 The correction coefficient e3 between O2 and the target pollutant, the experimental conditions are [Co(NO3)2]0=0.1mM, [PMS]0=0.5mM, [pollutant]0=20mg / L, T=25℃, the correction coefficient e3 formula is as follows:

[0048]

[0049] Where [·OH] ss3 is the steady-state concentration of ·OH when the probe compound NB and the target pollutant coexist, [·SO4 ·- ] ss3 When the probe compound BA and the target pollutant exist at the same time, SO4 ·- The steady-state concentration of 1 O2] ss3 When the probe compound FFA and the target pollutant coexist 1 The steady-state concentration of O2 is calculated as:

[0050]

[0051]

[0052]

[0053] Where R ·OH , and They are OH, SO4 ·- and 1 The contribution rate of O2 to the degradation of target pollutants is calculated as follows:

[0054]

[0055]

[0056]

[0057] Beneficial effects:

[0058] The present invention provides a method for evaluating the contribution rate of active species to pollutant degradation in an advanced oxidation process, which is used to accurately evaluate the contribution of typical active species to pollutant degradation in an advanced oxidation process. In the embodiment, bisphenol A (BPA) is taken as an example, and correction coefficients of typical active species and BPA are calculated and derived by homogeneous experiments. The correction coefficients are used to quantify the correlation between active species and pollutants, and the reaction between active species and pollutants is comprehensively considered, aiming to introduce these correction coefficients into the calculation formula of the traditional method, thereby improving the accuracy of calculating the contribution rate of active species. Taking the traditional method as a comparative example, the method has a comprehensive analysis, accurately evaluates the actual contribution of active species to pollutants in wastewater, provides a reference for the targeted design of catalysts and the effective removal of pollutants, and is innovative, practical and popularizable. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] Figure 1 The degradation kinetics result diagram of the probe compound and the target pollutant in Example 1 is shown in FIG.

[0060] (a) BPA and (b) NB through Fe 2+ / H2O2 degradation kinetics, (c) BPA, (d) NB and (e) BA degradation kinetics by PDS / UV, and (f) BPA, (g) NB, (h) BA and (i) FFA degradation kinetics by Co 2+ / PMS degradation kinetics results;

[0061] Experimental conditions: [NB]0 = [BA]0 = [FFA]0 = 0.05 mM; [Fe 2+ ]0=0.1mM; [H2O2]0=1.5mM; [PSD]0=3mM; [Co 2+ ]0=0.05mM; [PMS]0=0.5mM; [pH]0=7.3.

[0062] Figure 2 The contribution rate calculated by the modified method of Example 1 and the traditional method and the result diagram of the capture experiment;

[0063] Figure 3 The present invention is a flow chart of a method for evaluating the contribution of active species to pollutant degradation in an advanced oxidation process. DETAILED DESCRIPTION

[0064] The specific embodiments of the present invention are further described below in conjunction with the accompanying drawings. It should be noted that the description of these embodiments is used to help understand the present invention, but does not constitute a limitation of the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0065] The embodiments of the present invention are described in detail below. The embodiments described below are exemplary and are only used to explain the present invention, and should not be construed as limiting the present invention. If no specific techniques or conditions are specified in the embodiments, the techniques or conditions described in the literature in this area or the product specifications are used. The reagents or instruments used that do not specify the manufacturer are all conventional products that can be obtained commercially.

[0066] like Figure 3 As shown, the present invention provides a method for evaluating the contribution rate of active species to pollutant degradation in an advanced oxidation process, comprising the following steps:

[0067] Step 1: Quantify the correlation between active species and target pollutants using correction factors:

[0068] Firstly, based on the second-order reaction kinetics experiment between the probe compound and the active species, the steady-state concentration of each active species is calculated;

[0069] Then, through an experiment in which only the first active species is included in the reaction system, the correction coefficient between the first active species and the target pollutant is calculated. Specifically, the degradation contribution rate of the first active species is 1, and the correction coefficient of the first active species is equal to the pseudo-first-order rate constant of the target pollutant divided by the product of the second-order rate constant of the target pollutant and this active species and the steady-state concentration of this active species;

[0070] Then, through an experiment in which the reaction system only contains the first active species and the second active species, the correction coefficient between the second active species and the target pollutant is calculated, specifically: the degradation contribution rate of the first active species is equal to the product of the second-order rate constant of the target pollutant with this active species and the steady-state concentration divided by the pseudo-first-order rate constant of the target pollutant, multiplied by the correction coefficient of the first active species; the degradation contribution rate of the second active species is equal to 1 minus the degradation contribution rate of the first active species; the correction coefficient of the second target pollutant is equal to the degradation contribution rate of the second target pollutant multiplied by the pseudo-first-order rate constant of the target pollutant divided by the product of the second-order rate constant of the target pollutant with this active species and the steady-state concentration of this active species;

[0071] Then, through an experiment in which the reaction system only contains the first active species, the second active species and the third active species, the correction coefficient between the third active species and the target pollutant is calculated, specifically: the degradation contribution rate of the first active species is equal to the product of the second-order rate constant and the steady-state concentration of the target pollutant with this active species divided by the pseudo-first-order rate constant of the target pollutant, multiplied by the correction coefficient of the first active species; the degradation contribution rate of the second active species is equal to the product of the second-order rate constant and the steady-state concentration of the target pollutant with this active species divided by the pseudo-first-order rate constant of the target pollutant, multiplied by the correction coefficient of the first active species; the degradation contribution rate of the third active species is equal to 1 minus the degradation contribution rate of the first active species minus the degradation contribution rate of the second active species; the correction coefficient of the third target pollutant is equal to the degradation contribution rate of the third target pollutant multiplied by the pseudo-first-order rate constant of the target pollutant divided by the product of the second-order rate constant of the target pollutant with this active species and the steady-state concentration of this active species;

[0072] If there are four or more active species, the third species shall be taken as an example and so on.

[0073] Step 2: The calculation method of the degradation contribution rate of active species to target pollutants is as follows:

[0074] Detect and calculate the steady-state concentration of each active species in the advanced oxidation reaction system and the pseudo first-order rate constant of the target pollutant, and query the second-order rate constant of the target pollutant and each active species;

[0075] The product of the second-order rate constant of the target pollutant and this active species and the corresponding steady-state concentration of the active species is divided by the pseudo-first-order rate constant of the target pollutant to obtain the uncorrected degradation contribution rate. The uncorrected degradation contribution rate is multiplied by the correction coefficient between the corresponding active species and the target pollutant to obtain the accurate degradation contribution rate.

[0076] Example 1

[0077] In this example, BPA is used as the target pollutant, and NB, BA, and FFA are used as probe compounds. First, the steady-state concentrations of active species, ·OH, SO4 ·- of 1 The steady-state concentration of O2 was calculated by the following equations S1-S9. [NB], [BA] and [FFA] represent the concentrations of NB, BA and FFA at a given reaction time, respectively; [NB]0, [BA]0 and [FFA]0 are the initial concentrations of NB, BA and FFA, respectively, and the added concentration is 0.05 mM. [·OH] ss 、[SO4 ·- ] ss ,and[ 1 O2] ssThey are OH, SO4 ·- of 1 The steady-state concentration of O2 (M), where k NB，·OH , k BA，·OH , k FFA，·OH and represents the second-order rate constant (M) of the reaction between the probe compound and the active species. -1 s -1 During the reaction, 1.5 mL of sample was taken out from the solution at a fixed time point using a syringe, quenched by adding 100.0 μL of methanol and filtered through a 0.22 μm membrane, and added to a liquid injection bottle. The concentrations of various pollutants were detected by HPLC. All experiments were repeated three times.

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087] Then determine the correction factor for the reaction between active species and BPA, and convert e i Defined as a correction factor. The correction factor can be used to quantify the correlation between active species and pollutants, reflecting the impact of their reactions. 2+ It reacts with hydrogen peroxide (H2O2) to produce ·OH, and the contribution of ·OH is widely considered to be close to 100%. Based on this, the correction factor e1 between ·OH and pollutants is established, which is obtained by formula S10-11. For e2, when peroxydisulfate (PDS) is activated by ultraviolet (UV) photolysis, only ·OH and SO4 are generated. ·- Substituting e1 into the formula, the contribution of OH in PDS / UV can be calculated. SO4 can be determined by subtracting the contribution of OH from 1. ·- Then, SO4 ·- Substitute the contribution rate into formula S12 to derive the value of e2. 2+Activated PMS will produce SO4 ·- , OH and 1 O2. Using a similar derivation method as e2, determine 1 The correction coefficient e3 between O2 and pollutants is as follows:

[0088] Ⅰ. Determine the correction coefficient e1 between ·OH and BPA by calculating the formula S10-S11, experimental conditions: [FeSO4]0=0.1mM, [H2O2]0=1.5mM, [BPA]0=20mg / L, T=25℃.

[0089]

[0090]

[0091]

[0092] The contribution of OH in this experiment is widely believed to be close to 100%, R ·OH =1, S11 is R ·OH Substitute =1 into S10 and we get the result.

[0093] Ⅱ. Determine SO4 ·- The correction coefficient e2 between PDS and BPA is calculated by formula S12-S13. The experimental conditions are: [PDS]0 = 5.0 mM, [BPA]0 = 20 mg / L, 5.0 mM PDS is added to the mixture, and the UV intensity is 122.5 mW / cm 2 (Illuminated area = 3.34 cm 2 ), T = 25°C.

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100] III. Determination 1 The correction coefficient e3 between O2 and BPA is calculated by formula S14-S15, and the experimental conditions are: [Co(NO3)2]0=0.1mM, [PMS]0=0.5mM, [BPA]0=20mg / L, T=25℃.

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109] Calculated SO4 ·- , OH and 1 The correction coefficients of the reaction between O2 and BPA are 0.8236, 0.9859 and 20.7570 respectively.

[0110] The specific correction methods are as follows:

[0111] The contribution of active species to the degradation of BPA is calculated using formulas S16-S18, as follows:

[0112] R ·OH , and They are SO4 ·- , OH and 1 The contribution of O2 to BPA degradation is calculated as follows. BPA,·OH , and BPA and ·OH (6.9×10 9 M -1 s -1 )、SO4 ·- (1.6×10 9 M –1 s -1 )and 1 O2(3.0×10 5 M –1 s -1 ) is the second-order reaction rate constant; k obs，BPA is the pseudo first-order rate constant of BPA.

[0113]

[0114]

[0115]

[0116] like Figure 1 As shown in (a) BPA and (b) NB through Fe 2+ / H2O2 degradation kinetics, (c) BPA, (d) NB and (e) BA degradation kinetics by PDS / UV, and (f) BPA, (g) NB, (h) BA and (i) FFA and by Co 2+ / PMS degradation kinetics results; Experimental conditions: [NB]0 = [BA]0 = [FFA]0 = 0.05 mM; [Fe 2+ ]0=0.1mM; [H2O2]0=1.5mM; [PSD]0=3mM; [Co 2+ ]0=0.05mM; [PMS]0=0.5mM; [pH]0=7.3.

[0117] Cobalt-zinc composite catalyst 20CZO-V o and 20CZO as examples. The capture experimental results confirmed that ·OH, SO4 ·- , 1 Effects of O2 and high-valent cobalt oxide species (Co(IV)=O) on 20CZO-V o Degradation of BPA in / PMS / vis and 20CZO / PMS / vis systems.

[0118] The contribution rate of each active species to the degradation of BPA is calculated as follows:

[0119] First, calculate the steady-state concentration of active species, OH, SO4 ·- of 1 The steady-state concentration of O2 was calculated by equations S1-S9. o / PMS / vis and 20CZO / PMS / vis, respectively, produced about 2.21×10 -13 M and 2.07×10 -13 M's [·OH] ss 4.85×10 -13 M and 9.75×10 -13 M[SO4 ·- ] ss , 1.15×10 -12 M and 2.45×10 -12 M 1 O2]ss. Using the traditional contribution rate calculation method S10-S13, we get: R of 20CZO / PMS / vis ·OH , and R Co(IV)＝O81.6%, 89.0%, 0.42% and -71.0% respectively, 20CZO-V o / PMS / vis R ·OH , and R Co(IV)＝O are 47.5%, 24.2%, 0.11% and 28.2% respectively; using the correction method, we get: R of 20CZO / PMS / vis ·OH , and R Co(IV)＝O They are 22.4%, 52.7%, 2.9% and 22.0% respectively, 20CZO-V o / PMS / vis R ·OH , and R Co(IV)＝O The contribution rates of active species in the two systems obtained by the correction method are basically consistent with the trend of the capture experimental results, while the traditional method has a large error ( Figure 2 ). In the 20CZO / PMS / vis system, the contribution rate of the traditional method to high-valent cobalt oxide species (Co(IV)=O) is -71.0%, while the modified method can accurately evaluate the contribution rate of Co(IV)=O. The above results verify that the modified method can more accurately evaluate the contribution rate of active species to pollutant degradation than the traditional method.

[0120]

[0121]

[0122]

[0123]

[0124] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A method for evaluating the contribution of active species to pollutant degradation in an advanced oxidation process, characterized in that: The steps include: Step 1: Quantify the correlation between active species and target pollutants using correction factors: Firstly, based on the second-order reaction kinetics experiment between the probe compound and the active species, the steady-state concentration of each active species is calculated; Then, through an experiment in which only the first active species is included in the reaction system, the correction coefficient between the first active species and the target pollutant is calculated. Specifically, the degradation contribution rate of the first active species is 1, and the correction coefficient of the first active species is equal to the pseudo-first-order rate constant of the target pollutant divided by the product of the second-order rate constant of the target pollutant and this active species and the steady-state concentration of this active species; Then, through an experiment in which the reaction system only contains the first active species and the second active species, the correction coefficient between the second active species and the target pollutant is calculated, specifically: the degradation contribution rate of the first active species is equal to the product of the second-order rate constant of the target pollutant with this active species and the steady-state concentration divided by the pseudo-first-order rate constant of the target pollutant, multiplied by the correction coefficient of the first active species; the degradation contribution rate of the second active species is equal to 1 minus the degradation contribution rate of the first active species; the correction coefficient of the second target pollutant is equal to the degradation contribution rate of the second target pollutant multiplied by the pseudo-first-order rate constant of the target pollutant divided by the product of the second-order rate constant of the target pollutant with this active species and the steady-state concentration of this active species; Then, through an experiment in which the reaction system only contains the first active species, the second active species and the third active species, the correction coefficient between the third active species and the target pollutant is calculated, specifically: the degradation contribution rate of the first active species is equal to the product of the second-order rate constant and the steady-state concentration of the target pollutant with this active species divided by the pseudo-first-order rate constant of the target pollutant, multiplied by the correction coefficient of the first active species; the degradation contribution rate of the second active species is equal to the product of the second-order rate constant and the steady-state concentration of the target pollutant with this active species divided by the pseudo-first-order rate constant of the target pollutant, multiplied by the correction coefficient of the first active species; the degradation contribution rate of the third active species is equal to 1 minus the degradation contribution rate of the first active species minus the degradation contribution rate of the second active species; the correction coefficient of the third target pollutant is equal to the degradation contribution rate of the third target pollutant multiplied by the pseudo-first-order rate constant of the target pollutant divided by the product of the second-order rate constant of the target pollutant with this active species and the steady-state concentration of this active species; If there are four or more active substances, the third one shall be taken as an example and so on; Step 2: The calculation method of the degradation contribution rate of active species to target pollutants is as follows: Detect and calculate the steady-state concentration of each active species in the advanced oxidation reaction system and the pseudo first-order rate constant of the target pollutant, and query the second-order rate constant of the target pollutant and each active species; The product of the second-order rate constant of the target pollutant and the active species and the corresponding steady-state concentration of the active species is divided by the pseudo-first-order rate constant of the target pollutant to obtain the uncorrected degradation contribution rate, and the uncorrected degradation contribution rate is multiplied by the correction coefficient between the corresponding active species and the target pollutant to obtain the accurate degradation contribution rate; The first active species is OH, and the second active species is SO4 ·- , the third active species is 1 O 2； The probe compound is one or more of NB, BA and FFA; The specific method for calculating the steady-state concentration of each active species based on the secondary reaction kinetics experiment of the probe compound and the active species is as follows: After adding the probe compound, samples were taken from the solution at fixed time points during the reaction, quenched with methanol, and filtered and then the concentrations of various pollutants were detected by HPLC. The steady-state concentration of ·OH and the pseudo-first-order rate constant of NB were calculated by the following formula: Then calculate SO4 by the following formula ·- Steady-state concentration and pseudo-first-order rate constant of BA: Then calculate it by the following formula 1 Pseudo-first-order rate constants for steady-state O2 concentration and FFA: Where [·OH] ss 、[SO4 ·- ] ss ,and[ 1 O2] ss They are OH, SO4 ·- and 1 The steady-state concentration of O2, k NB,·OH , k BA,·OH , k FFA,·OH and represent the second-order rate constants of the probe compound and the active species, respectively.

2. A method for evaluating the contribution of active species to pollutant degradation in an advanced oxidation process according to claim 1, characterized in that: The calculation of the correction factor between each active species and the target pollutant, taking the target pollutant as an example, is as follows: (1) Calculation of the correction factor of the first active species OH: Determine the correction coefficient e1 between ·OH and the target pollutant. The experimental conditions are [FeSO4]0 = 0.1mM, [H2O2]0 = 1.5mM, [pollutant]0 = 20mg / L, T = 25℃. The correction coefficient e1 formula is as follows: Where [·OH] ss1 is the steady-state concentration of OH when the probe compound NB and the target pollutant coexist, calculated by the following formula (2) The second active species SO4 ·- Calculation of correction factor: Determine SO4 ·- The correction coefficient e1 between the target pollutant and the target pollutant, the experimental conditions are [PDS]0 = 5.0mM, [pollutant]0 = 20mg / L, 5.0mM PDS is added to the mixture, T = 25℃, the correction coefficient e2 formula is as follows: Where [·OH] ss2 is the steady-state concentration of OH when the probe compound NB and the target pollutant coexist, [SO4 ·- ] ss2 When the probe compound BA and the target pollutant coexist, SO4 ·- The steady-state concentration is calculated as: Where R ·OH is the contribution rate of ·OH to the degradation of the target pollutant when the probe compound NB and the target pollutant coexist, When the probe compound BA and the target pollutant coexist, SO4 ·- The contribution rate to the degradation of target pollutants is calculated as follows: (3) Calculation of correction factor for the third active species: Sure 1 The correction coefficient e3 between O2 and the target pollutant, the experimental conditions are [Co(NO3)2]0=0.1mM, [PMS]0=0.5mM, [pollutant]0=20mg / L, T=25℃, the correction coefficient e3 formula is as follows: Where [·OH] ss3 is the steady-state concentration of ·OH when the probe compound NB and the target pollutant coexist, [·SO4 ·- ] ss3 When the probe compound BA and the target pollutant exist at the same time, SO4 ·- The steady-state concentration of 1 O2] ss3 When the probe compound FFA and the target pollutant coexist 1 The steady-state concentration of O2 is calculated as: Where R ·OH , and They are OH, SO4 ·- and 1 The contribution rate of O2 to the degradation of target pollutants is calculated as follows: 。

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