CN114755285B - Method for predicting oxidizing capacity of sulfate radical to organic matters - Google Patents
Method for predicting oxidizing capacity of sulfate radical to organic matters Download PDFInfo
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- CN114755285B CN114755285B CN202210485009.0A CN202210485009A CN114755285B CN 114755285 B CN114755285 B CN 114755285B CN 202210485009 A CN202210485009 A CN 202210485009A CN 114755285 B CN114755285 B CN 114755285B
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Abstract
The invention discloses a method for predicting the oxidation capability of sulfate radical to organic matters, which collects the prior artThe second-order reaction rate constant of the sulfate radical and the organic matter, which is experimentally measured in the research; according to the oxygen consumption of the organic matters in the historical test and the second-level reaction rate constant of the organic matters, carrying out statistical analysis to obtain a relation model of sulfate radical and the second-level reaction rate constant of the organic matters; substituting oxygen consumption of the organic matter to be predicted into the relation model to obtain a predicted value of a second-order reaction rate constant of sulfate radical and the organic matter, wherein the predicted value is equal to the existing k SO4·– Compared with the value measuring method, the method has the advantages of simple and quick detection process and high accuracy; the measurement does not depend on large-scale instruments and equipment, organic structures, chemistry and other characteristics, and effectively reduces the test cost and the influence of insufficient reaction conditions and substance information on a prediction result.
Description
Technical Field
The invention relates to the field of predictive evaluation of reaction rate constants, in particular to a method for predicting the oxidation capability of sulfate radical to organic matters.
Background
Advanced Oxidation Processes (AOPs) are emerging technologies in the field of water treatment, and have very broad application prospects in the field of treatment of refractory organic wastewater. Which mainly comprises Fenton technology, ozone oxidation technology, persulfate activation technology and the like. These AOPs are mainly produced by hydroxyl radical (HO) · ) And sulfate radical (SO) 4 ·- ) Species with equal high redox potential are used for oxidizing and treating refractory organic pollutants. Wherein SO is based on 4 ·- Is the most promising in situ repair technique today: with HO with · A considerably even higher oxidizing capacity; with specific HO · A broader pH application range; with specific HO · Higher half-life and stability; and is less affected by competing components such as natural organic matters in the water body.
SO 4 ·- Second order reaction rate constant with organic matter
Is to characterize SO 4 ·- The intrinsic parameters of the reactivity with organic matters have important scientific and practical significance. In the scientific research aspect, determine->
Not only for research based on SO 4 ·- The degradation dynamics and degradation mechanism of the organic matters in the AOPs are important, the construction of a dynamic model in the reaction process is facilitated, and the degradation efficiency of different process systems is also convenient to compare. In practical use, the->
Organic matters with large values are easy to be subjected to SO in practice 4 ·- Degradation, which can be used to evaluate the organic matter in SO 4 ·- Degradation efficiency in AOPs treatment, optimization of reaction time and oxidant dosing and evaluation based on SO 4 ·- Whether the AOPs are suitable for treating the organic wastewater; furthermore, use is made of->
Value size screening for SO tolerance 4 ·- Is used for helping the establishment of a risk list and a priority control list.
Disclosure of Invention
Based on the method, the method for predicting the oxidizing capability of sulfate radicals on the organic matters is provided, and the influence of test cost, reaction conditions and insufficient material information on a prediction result is effectively reduced.
According to one aspect of the invention, a method of predicting the oxidizing ability of sulfate radicals to organic matter comprises:
measuring the dissolved oxygen concentration of an aqueous solution with a preset pH value as a blank initial value of the oxygen concentration of the aqueous solution;
adding a bisulphite solution and a permanganate solution into the aqueous solution, and measuring blank oxygen consumption of sulfate radical after oxidizing the aqueous solution according to the blank initial value;
dissolving an organic matter in the aqueous solution to obtain a liquid to be tested;
the pH value of the liquid to be measured is adjusted to the preset pH value, so that the liquid to be measured after adjustment is obtained;
measuring the initial value of a sample of the concentration of the dissolved oxygen in the liquid to be measured after the adjustment;
measuring the oxygen consumption of a sample after oxidizing the organic matters in the adjusted liquid to be measured by the sulfate radical by adding the bisulphite solution and the permanganate solution into the adjusted liquid to be measured;
obtaining the organic oxygen consumption of the organic matters in the liquid to be detected by calculating the difference value of the sample oxygen consumption and the blank oxygen consumption;
inputting the oxygen consumption of the organic matters into a relation model of sulfate radical and organic matters secondary reaction rate constant, and outputting predicted values of the sulfate radical and organic matters secondary reaction rate constant;
and determining the oxidizing ability of the sulfate radical to the organic matter based on the predicted value.
According to an embodiment of the present invention, the above-mentioned relationship model is obtained by:
obtaining a second-level reaction rate constant of the sulfate radical and the organic matters through a historical test;
measuring oxygen consumption of the organic matter in the history test;
and obtaining a relation model of the second-order reaction rate constant of the sulfate radical and the organic matter through the oxygen consumption of the organic matter and the second-order reaction rate constant of the organic matter in the historical test.
According to an embodiment of the present invention, the pH value ranges from 5.0 to 9.0.
According to an embodiment of the present invention, the bisulphite includes one or two of sodium bisulphite and potassium bisulphite.
According to an embodiment of the present invention, the permanganate includes one or two of potassium permanganate and sodium permanganate.
According to an embodiment of the invention, the concentration ratio of the bisulphite to the permanganate is 5:1-10:1.
According to an embodiment of the present invention, the method for measuring oxygen consumption of the liquid to be measured or the aqueous solution includes an electrode polarography method or a fluorescence method.
According to an embodiment of the present invention, the method for measuring a blank oxygen consumption after oxidizing the aqueous solution with sulfate radicals according to the blank initial value by adding a bisulfite solution and a permanganate solution to the aqueous solution includes:
obtaining a blank minimum value of the aqueous solution by adding a bisulfite solution and a permanganate solution to the aqueous solution;
and calculating the difference between the blank initial value and the blank minimum value to obtain the blank oxygen consumption of the aqueous solution.
According to an embodiment of the present invention, the measuring of the oxygen consumption of the sample after oxidizing the organic matter in the adjusted test solution by the sulfate radical by adding the bisulfite solution and the permanganate solution to the adjusted test solution includes:
adding a bisulphite solution and a permanganate solution into the adjusted liquid to be measured to obtain the lowest value of the sample of the adjusted liquid to be measured;
and calculating the difference between the initial value of the sample and the minimum value of the sample to obtain the sample oxygen consumption of the adjusted liquid to be measured.
According to an embodiment of the present invention, in the measurement process of the blank initial value and the sample initial value, the aqueous solution or the solution to be measured is saturated with dissolved oxygen by stirring or oxygen injection.
From the technical scheme, the method for predicting the oxidizing capability of sulfate radicals to organic matters has the following beneficial effects:
compared with the prior art
Compared with the value measuring method, the method for predicting the oxidizing capability of sulfate radical to organic matters has the advantages of simple and quick detection process and high accuracy; the measurement is independent of large instruments (such as spectrum and chromatography) and is independent of the presence ofThe characteristics of the structure, chemistry and the like of the organism effectively reduce the test cost and the influence of insufficient reaction conditions and substance information on the prediction result; the model has good fitting capability and high prediction capability (& lt, & gt)>
And->
Substantially the same); the method has important scientific and practical significance in researching the water chemistry mechanism of the sulfate radical, evaluating the degradation efficiency of pollutants based on the sulfate radical advanced oxidation technology in the actual water environment, screening sulfate radical-resistant organic matters, establishing a risk list and preferentially controlling the list.
Drawings
FIG. 1 shows oxygen consumption of phenol solution at different addition ratios of sodium bisulfite and potassium permanganate in the embodiment of the invention;
FIG. 2 shows oxygen consumption (C, μM) and organic solution at different pH values according to an embodiment of the present invention
Is a relationship diagram of (1);
FIG. 3 shows an embodiment of the present invention
And->
Is a graph of the relationship of (1).
Detailed Description
The present invention will be further described in detail below with reference to specific embodiments and with reference to the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent.
Commonly used
The measurement method can be mainly classified into a direct method and an indirect method.
Wherein, the direct method mainly uses a laser flash photolyzer to directly measure SO 4 ·- Attenuation Rate (k) at its absorption maximum wavelength (i.e. 450 nm) obs ) K measured under different concentrations of organic matters obs The slope obtained by fitting the value and the concentration of the organic matters is the organic matters
Values. The method has high equipment dependence, and the generated SO due to extremely short reaction time 4 ·- The rate at which self-polymerization occurs tends to be non-negligible and the measurement error is large. Indirect methods mainly include competition kinetics and model methods based on quantitative structure-activity relationship (QSAR).
The competition kinetics method can obtain relatively accurate
Values, but measurement conditions were severe: not only require
Value and->
The difference of the values is not more than one order of magnitude, HO is added into the reaction system · Is a quencher of (2); in addition, the method also needs to rely on chromatographic detection, is complex in operation, is time-consuming and labor-consuming, and is high in cost. However, more than one hundred million chemicals (CAS number) are currently registered, more than 10 tens of thousands are used daily, and most of the activated substances are not evaluated.
In the face of such a huge and increasing number of chemicals, it is apparent that the conventional experimental methods alone cannot meet the requirements
The requirement of value measurement cannot be satisfied 4 ·- The parametric requirements of AOPs technology for treating real waste water, neitherCan meet the requirements of chemical risk management.
Although the empirical model based on QSAR can reduce test cost, sample testing time and make up for the known
The method has the defects of insufficient value quantity, but the modeling data set of the method has huge requirement, a plurality of influencing factors and poor model prediction capability (reported R 2 adj Most preferably less than 0.9), the predicted data is inaccurate.
According to one aspect of the invention, a method of predicting the oxidizing ability of sulfate radicals to organic matter comprises:
step one: measuring the dissolved oxygen concentration of an aqueous solution with a preset pH value as a blank initial value of the oxygen concentration of the aqueous solution;
step two: the blank oxygen consumption after the sulfate radical oxidation of the aqueous solution is measured according to the blank initial value by adding a bisulphite solution and a permanganate solution into the aqueous solution;
step three: the organic matter is dissolved in the aqueous solution to obtain a liquid to be tested;
step four: the pH value of the liquid to be measured is regulated to the preset pH value, so that the regulated liquid to be measured is obtained;
step five: measuring the initial value of a sample of the concentration of dissolved oxygen in the liquid to be measured after adjustment;
step six: the method comprises the steps of adding a bisulphite solution and a permanganate solution into an adjusted liquid to be measured, and measuring the oxygen consumption of a sample after organic matters in the adjusted liquid to be measured are oxidized by sulfate radicals;
step seven: obtaining the organic oxygen consumption of the organic matters in the liquid to be detected by calculating the difference value of the sample oxygen consumption and the blank oxygen consumption;
step eight: inputting oxygen consumption of the organic matters into a relation model of sulfate radical and organic matters secondary reaction rate constant, and outputting predicted values of the sulfate radical and organic matters secondary reaction rate constant;
step nine: and determining the oxidizing capacity of sulfate radical to organic matters according to the predicted value.
Compared with the prior art
Compared with the value measuring method, the method for predicting the oxidizing capability of sulfate radical to organic matters has the advantages of simple and quick detection process and high accuracy; the measurement does not depend on large instruments (such as spectrum and chromatograph) and organic structures, chemistry and other characteristics, so that the influence of test cost, reaction conditions and insufficient material information on a prediction result is effectively reduced; the model has good fitting capability and high prediction capability (& lt, & gt)>
And->
Substantially the same); the method has important scientific and practical significance in researching the water chemistry mechanism of the sulfate radical, evaluating the degradation efficiency of pollutants based on the sulfate radical advanced oxidation technology in the actual water environment, screening sulfate radical-resistant organic matters, establishing a risk list and preferentially controlling the list.
According to an embodiment of the present invention, in the second step, by adding a bisulphite solution and a permanganate solution to the aqueous solution, a blank oxygen consumption amount after sulfate radical oxidation of the aqueous solution is determined according to a blank initial value, specifically including:
obtaining a blank minimum value of the aqueous solution by adding a bisulfite solution and a permanganate solution to the aqueous solution;
and obtaining the blank oxygen consumption of the aqueous solution by calculating the difference value between the blank initial value and the blank minimum value.
According to an embodiment of the present invention, in the step six, the oxygen consumption of the sample after the organic matter in the solution to be measured after the sulfate radical oxidation adjustment is measured by adding the bisulphite solution and the permanganate solution to the solution to be measured after the adjustment, specifically including:
adding a bisulphite solution and a permanganate solution into the adjusted liquid to be measured to obtain the minimum value of the sample of the adjusted liquid to be measured;
and obtaining the sample oxygen consumption of the liquid to be measured after adjustment by calculating the difference value between the initial value of the sample and the minimum value of the sample.
Sulfate radical (SO) 4 ·- ) Is a major active species of the permanganate/bisulphite system, which generates and SO 3 ·- With O 2 Is related to the rapid reaction of (a). Since the reactivity of sulfate radicals with organics in the permanganate/bisulfite system is closely related to oxygen consumption.
According to the embodiment of the invention, in the measuring process of the blank initial value and the sample initial value, the water solution or the liquid to be measured is saturated with dissolved oxygen by stirring or oxygen injection.
By making it saturated with dissolved oxygen, measurement errors can be effectively reduced.
According to an embodiment of the invention, the relationship model is obtained by:
obtaining a second-level reaction rate constant of sulfate radical and organic matters through a historical test;
measuring oxygen consumption of organic matters in a historical test;
and obtaining a relation model of the second-order reaction rate constant of sulfate radical and organic matters through the oxygen consumption of the organic matters and the second-order reaction rate constant of the organic matters in the historical test.
According to the embodiment of the invention, the second-order reaction rate constant of sulfate radical and the organic matter, which are experimentally measured in the prior study, is collected
/>
According to the oxygen consumption of the organic matters and the second-level reaction rate constant of the organic matters, carrying out statistical analysis to obtain a relation model of sulfate radical and the second-level reaction rate constant of the organic matters;
substituting oxygen consumption of the organic matter to be predicted into the relation model to obtain a predicted value of the second-order reaction rate constant of sulfate radical and the organic matter
According to the examples of the present invention, the experimentally measured sulfate radical was reacted with the organic compound at a second rate constant
Predicted value of the second order reaction rate constant with sulfate radical and the organic matter +.>
Fitting was performed.
Correction determining coefficient R obtained by fitting 2 adj =0.96, indicating that the fitting ability of the present relationship model is good;
and->
The slope obtained by fitting is 1.0, and the correction decision coefficient R 2 adj =0.98, model predictive power is high.
According to an embodiment of the invention, the pH value is in the range of 5.0 to 9.0.
According to an embodiment of the invention, the pH value may be 5.0,6.0,7.0,8.0,9.0, for example.
According to an embodiment of the invention, wherein the bisulphite comprises one or both of sodium bisulphite and potassium bisulphite.
According to an embodiment of the invention, wherein the permanganate comprises one or both of potassium permanganate and sodium permanganate. According to an embodiment of the invention, the concentration ratio of bisulphite to permanganate is 5:1-10:1.
According to embodiments of the invention, the concentration ratio of bisulphite to permanganate may be 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, etc., with 5:1 being preferred.
Sulfate radical (SO) 4 ·- ) Is permanganate/sulfurous acidA major active species of hydrogen salt system, which generates and generates SO 3 ·- With O 2 Is related to the rapid reaction of (a). Since the reactivity of the sulfate radical and the organic matter in the permanganate/bisulphite system is closely related to the oxygen consumption, the second-order reaction rate constant of the sulfate radical and the organic matter can be obtained by detecting and judging the oxygen consumption in the permanganate/bisulphite system
Thus, the reactivity of the sulfate radical to such an organic compound can be judged.
According to the embodiment of the invention, the organic matters are one or more of phenols, alcohols, aldehydes, ketones, acids, medicines, personal care products, endocrine disruptors, pesticides and other organic pollutants.
According to the embodiment of the invention, the method for measuring the oxygen consumption of the liquid or the aqueous solution to be measured comprises an electrode polarography method or a fluorescence method.
According to the embodiment of the invention, the oxygen consumption of the liquid or the aqueous solution to be measured can be measured by adopting a probe for preventing dissolved oxygen in the liquid or the aqueous solution to be measured, and the oxygen consumption can be monitored in real time.
The following detailed description of the present invention is given by way of example only, and not by way of limitation.
Example 1: the oxygen consumption relation between different addition ratios of sodium bisulfite and potassium permanganate and phenol solution is explored.
FIG. 1 shows oxygen consumption of phenol solutions at different addition ratios of sodium bisulfite and potassium permanganate in an embodiment of the invention.
Detecting oxygen consumption of a phenol solution under different addition ratios of sodium bisulphite and potassium permanganate, wherein the concentration of the phenol solution is 10 mu M, the pH of the solution is 8.0, and the specific experimental steps are as follows:
(1) Respectively placing 50mL of ultrapure water in 5 blue cap bottles, and adjusting the pH value of the aqueous solution to 8.0 by using 0.1mM dilute sulfuric acid and 0.1mM sodium hydroxide solution to obtain solution O 1 ～O 5 ；
(2) Placing dissolved oxygen probes in the solution O respectively 1 ～O 5 Continuously stirring, and recording initial value M of dissolved oxygen concentration after instrument indication is stable 1 ～M 5 ；
(3) Preparation of reaction solutions with different addition ratios of sodium bisulfite and potassium permanganate, 25mM sodium bisulfite solution (0.05, 0.1, 0.2, 0.5 and 1.0mL respectively) and 10mM potassium permanganate solution (0.5 mL) were sequentially added to solution O under stirring 1 ～O 5 Respectively obtain solution B 1 ～B 5 ；
(4) Recording solution B every 3s within 20-25 s after adding potassium permanganate solution 1 ～B 5 The concentration value of the dissolved oxygen is obtained to obtain the lowest value N of the concentration of the dissolved oxygen 1 ～N 5 ；
(5) An initial value M of the dissolved oxygen concentration 1 ～M 5 And the lowest value N of the corresponding dissolved oxygen concentration 1 ～N 5 The difference value of (a) is the oxygen consumption A of the blank group 1 ～A 5 ；
(6) Respectively adding 50mL of ultrapure water into 5 blue cap bottles, and adding 0.1mL of 5mM phenol solution into the water solution to obtain mixed solution P 1 ～P 5 The pH value of the mixed solution is adjusted to be the same as the initial pH value of the blank group, and the same steps as the blank group are carried out to obtain the oxygen consumption B of the experimental group 1 ～B 5 ；
(7) Calculate oxygen consumption B 1 ～B 5 With corresponding A 1 ～A 5 Obtaining oxygen consumption C of phenol from the difference 1 ～C 5 ；
(8) The oxygen consumption of the obtained phenol is plotted as an ordinate, and the addition ratio of sodium bisulphite and potassium permanganate is plotted as an abscissa, so that the graph 1 is obtained.
As shown in fig. 1, the oxygen consumption of the phenol solution is different under different sodium bisulfite and potassium permanganate addition ratios, when the sodium bisulfite and potassium permanganate addition ratios are 5:1 and 10:1, the positive oxygen consumption of the phenol solution can be obviously measured, wherein when the sodium bisulfite and potassium permanganate addition ratios are 5:1, the oxygen consumption of the phenol solution is most obvious, so that the concentration ratio of the preferable bisulfite to the permanganate is 5:1.
Example 2: exploring oxygen consumption (C, mu M) and concentration of organic solution at different pH values
Is a relationship of (3).
FIG. 2 shows oxygen consumption (C, μM) and organic solution at different pH values according to an embodiment of the present invention
Is a graph of the relationship of (1).
Detecting oxygen consumption (C, mu M) and of solutions of different organic matters (dimetimidazole, metronidazole, sugar alcohol, benzoic acid, gemfibrozil and methyl phenyl sulfoxide) at different pH values
Wherein the concentration of sodium bisulphite is 250. Mu.M, the concentration of potassium permanganate is 50. Mu.M, and the concentration of the organic matter solution is 10. Mu.M, the specific experimental procedure is as follows:
(1) Respectively placing 50mL of ultrapure water in 6 blue cap bottles, and adjusting the pH value of the aqueous solution to 8.0 by using 0.1mM dilute sulfuric acid and 0.1mM sodium hydroxide solution to obtain solution O 1 ～O 6 ；
(2) Placing dissolved oxygen probes in the solution O respectively 1 ～O 6 Continuously stirring, and recording initial value M of dissolved oxygen concentration after instrument indication is stable 1 ～M 6 ；
(3) Sequentially adding 0.5mL of 25mM sodium hydrogen sulfite solution and 0.5mL of 10mM potassium permanganate solution to the solution O under stirring 1 ～O 6 Respectively obtain solution B 1 ～B 6 ；
(4) Recording the solution every 3s within 20-25 s after adding the potassium permanganate solutionB 1 ～B 6 The concentration value of the dissolved oxygen is obtained to obtain the lowest value N of the concentration of the dissolved oxygen 1 ～N 6 ；
(5) An initial value M of the dissolved oxygen concentration 1 ～M 6 And the lowest value N of the corresponding dissolved oxygen concentration 1 ～N 6 The difference value of (a) is the oxygen consumption A of the blank group 1 ～A 6 ；
(6) Respectively taking 50mL of ultrapure water into 6 blue cap bottles, adding the stock solution of the dimethylnitroimidazole, the metronidazole, the sugar alcohol, the benzoic acid, the gemfibrozil and the methyl phenyl sulfoxide into the aqueous solution to obtain a mixed solution P 1 ～P 6 Wherein the concentration of each organic matter is 10 mu M, the pH value of the mixed solution is adjusted to be the same as the initial pH value of the blank group, and the same steps as the blank group are carried out to obtain the oxygen consumption B of the experimental group 1 ～B 6 ；
(7) Calculate oxygen consumption B 1 ～B 6 With corresponding A 1 ～A 6 Obtain the oxygen consumption C of each organic matter 1 ～C 6 ；
(8) The oxygen consumption of each organic material at other pH values (i.e., 5.0,6.0,7.0 and 9.0) was obtained in the same manner as in the above-described steps. Among them, the oxygen consumption of the blank group at different pH values is shown in Table 1, and it is found that the initial solution pH value has substantially no influence on the oxygen consumption measurement of the blank group without adding the organic matter.
TABLE 1 oxygen consumption of blank groups at different pH values
(9) The second-level reaction rate constants of sulfate radical, dimetimidazole, metronidazole, sugar alcohol, benzoic acid, gemfibrozil and methyl phenyl sulfoxide, which are experimentally measured in the existing research, are collected
(10) Taking the oxygen consumption of each organic matter as an ordinate,
FIG. 2 is made as a horizontal sitting plot and is related to oxygen consumption of different organic matters>
And carrying out statistical analysis on the data to obtain a relation model of sulfate radical and organic matter secondary reaction rate constant.
As shown in FIG. 2, the oxygen consumption of each organic matter is equal to that of the organic matter in the pH range of 5.0-9.0
Linear correlation. The comparison shows that the slope obtained at pH 8.0 is maximum (6.36X 10 –9 ) Indicating->
The same level of change, obvious change of dissolved oxygen, obtained +.>
Possibly more precisely. Therefore, the oxygen consumption and +.A.of each organic matter at pH 8.0 was selected>
As a model for predicting the relationship between sulfate radical and the second-order reaction rate constant of the organic matter.
FIG. 3 shows an embodiment of the present invention
And->
Is a graph of the relationship of (1).
Detecting the 6 organic matters
And->
Fitting degree of (a) in a specific experimental procedure such asThe following steps:
(1) Oxygen consumption C of dimetimidazole, metronidazole, sugar alcohol, benzoic acid, gemfibrozil and methyl phenyl sulfoxide 1 ～C 6 Substituting into the relation model to obtain the predicted value of the second-order reaction rate constant of sulfate radical and the organic matter
(3) Will be
As ordinate, ++>
Fig. 3 is made as a abscissa plot and correlation analysis is performed.
As can be seen from the figure 3 of the drawings,
and->
Substantially the same, the slope obtained by fitting was 1.0, R 2 adj =0.98, indicating that the model predictive power is high.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the invention thereto, but to limit the invention thereto, and any modifications, equivalents, improvements and equivalents thereof may be made without departing from the spirit and principles of the invention.
Claims (8)
1. A method of predicting the oxidizing ability of sulfate radicals to organics comprising:
measuring the dissolved oxygen concentration of an aqueous solution with a preset pH value as a blank initial value of the oxygen concentration of the aqueous solution;
adding a bisulphite solution and a permanganate solution into the aqueous solution, and determining blank oxygen consumption after sulfate radical oxidation of the aqueous solution according to the blank initial value;
dissolving an organic matter in the aqueous solution to obtain a liquid to be tested;
the pH value of the liquid to be measured is regulated to the preset pH value, so that the regulated liquid to be measured is obtained;
measuring the initial value of a sample of the concentration of the dissolved oxygen in the adjusted liquid to be measured;
measuring the oxygen consumption of a sample after oxidizing the organic matters in the regulated liquid to be measured by the sulfate radical by adding the bisulphite solution and the permanganate solution into the regulated liquid to be measured;
obtaining the organic oxygen consumption of the organic matters in the liquid to be detected by calculating the difference value of the sample oxygen consumption and the blank oxygen consumption;
inputting the oxygen consumption of the organic matters into a relation model of sulfate radical and organic matters secondary reaction rate constant, and outputting predicted values of the sulfate radical and organic matters secondary reaction rate constant;
determining the oxidizing capacity of the sulfate radical to the organic matter according to the predicted value;
in the measuring process of the blank initial value and the sample initial value, the water solution or the liquid to be measured is saturated with dissolved oxygen by stirring or oxygen injection;
wherein, the relation model is obtained by the following steps:
obtaining a second-level reaction rate constant of the sulfate radical and the organic matters through a historical test;
determining oxygen consumption of the organic matter in the historical test;
and obtaining a relation model of the sulfate radical and the second-order reaction rate constant of the organic matters through the oxygen consumption of the organic matters and the second-order reaction rate constant of the organic matters in the historical test.
2. The method of claim 1, wherein the pH is in the range of 5.0 to 9.0.
3. The method of claim 1, wherein the bisulphite salt comprises one or both of sodium bisulphite, potassium bisulphite.
4. The method of claim 1, wherein the permanganate comprises one or both of potassium permanganate and sodium permanganate.
5. The method of claim 1, wherein the concentration ratio of the bisulphite salt to the permanganate salt is 5:1-10:1.
6. The method according to claim 1, wherein the method for measuring oxygen consumption of the liquid to be measured or the aqueous solution comprises an electrode polarography method or a fluorescence method.
7. The method of claim 1, wherein said determining a blank oxygen consumption after sulfate radical oxidation of said aqueous solution from said blank initial value by adding a bisulfite solution and a permanganate solution to said aqueous solution comprises:
obtaining a blank minimum value of the aqueous solution by adding a bisulfite solution and a permanganate solution to the aqueous solution;
and obtaining the blank oxygen consumption of the aqueous solution by calculating the difference value between the blank initial value and the blank minimum value.
8. The method of claim 1, wherein said determining the oxygen consumption of the sample after oxidizing the organics in the conditioned test solution via the sulfate radicals by adding the bisulfite solution and the permanganate solution to the conditioned test solution comprises:
obtaining the lowest value of a sample of the adjusted liquid to be measured by adding a bisulphite solution and a permanganate solution into the adjusted liquid to be measured;
and obtaining the sample oxygen consumption of the adjusted liquid to be measured by calculating the difference between the initial value of the sample and the minimum value of the sample.
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