CN114835241B - Real-time monitoring and ozone intelligent adding control method for refractory organic matters in sewage - Google Patents

Abstract

The invention relates to the fields of advanced sewage treatment and regenerated water production, and provides a method for real-time monitoring of refractory organic matter in sewage and an intelligent ozone dosing control method, which includes the steps of establishing a model of the relationship between absorbance and concentration of refractory organic matter; using a spectral scanning mechanism to acquire refractory organic matter in real time The absorbance of organic matter in the ultraviolet-visible light spectrum range, and the steps of using the model to monitor the concentration of the corresponding refractory organic matter in real time; calculate the ozone dosage according to the real-time monitoring concentration of the refractory organic matter, and establish the steps of an ozone intelligent dosing system. The process of the invention is simple, and the detection interval is short, and high-frequency online monitoring can be realized; the ozone intelligent dosing control system established based on the concentration monitoring method can determine the ozone dosing amount according to the measured concentration of refractory organic matter, and then control the ozone concentration. The aeration system adds ozone; the invention greatly saves the dosage of ozone and saves operating costs for sewage treatment plants.

Description

Real-time monitoring of refractory organic matter in sewage and intelligent ozone dosing control method

technical field

The invention relates to the fields of advanced sewage treatment and regenerated water production, in particular to a method for real-time monitoring of refractory organic matter in sewage and an intelligent ozone dosing control method.

Background technique

Refractory organic matter generally refers to organic chemical substances that are difficult to be degraded by biological action under natural conditions. They will continue to accumulate in natural environments such as water bodies and soils, and then enter organisms through the food chain and gradually enrich. It not only endangers the health of organisms, but also endangers the entire ecosystem, and finally enters the human body, endangering human health. Therefore, it is of great significance to realize the effective degradation and real-time monitoring of refractory organic matter in sewage.

The detection techniques for refractory organics in water mainly include liquid chromatography, liquid chromatography and tandem mass spectrometry, radioimmunoassay primary screening detection method, enzyme-linked immunosorbent assay, immunosensor, gas chromatography example trap mass spectrometry, capillary electrophoresis Detection technology, etc. Although the above method has high detection accuracy and can be used for the detection of trace amounts of refractory organics, the pretreatment operation is complicated, the detection equipment requirements are high, and real-time detection cannot be performed. Based on the above status quo, UV-Vis spectroscopy has become one of the important research directions for real-time monitoring of refractory organic matter in sewage. Using the principle of characteristic absorption of different types of refractory organics in the ultraviolet-visible region, construct a data-driven model, and further make a real-time online monitoring sensor for refractory organics in water based on the photoelectric principle, and combine it with a programmable logic controller to form ozone dosing Control system, so as to realize real-time online monitoring of refractory organic matter in sewage.

Contents of the invention

In order to solve the problem that the concentration of refractory organic matter in sewage is difficult to monitor online and cannot be effectively degraded by biological treatment, the present invention proposes a real-time monitoring method for refractory organic matter in sewage and an intelligent ozone dosing control method, which includes:

Step S1 of establishing a relationship model between the absorbance of the refractory organic matter and the corresponding chemical oxygen demand (COD) concentration;

Step S2 of obtaining the absorbance of the refractory organic matter in the ultraviolet-visible spectral range in real time by using the spectral scanning mechanism, and using the model of step S1 to monitor the corresponding concentration of the refractory organic matter in real time;

Calculate the ozone dosage according to the real-time monitoring concentration of refractory organic matter obtained in step S2, and establish step S3 of an ozone intelligent dosage system. The specific process of step S1 includes:

Step 1. Configure a standard solution of refractory organic substances with a concentration gradient, and sequentially use a spectral scanning mechanism to measure its absorbance in the ultraviolet-visible spectral range;

Step 2, draw the ultraviolet-visible light absorption spectrum diagram of the refractory organic substance at different concentrations, and find the wavelength where the characteristic absorption peak exists;

Step 3: Fitting the absorbance values at different concentrations at the wavelength of the characteristic absorption peak to the equation, and establishing a relationship model between the absorbance of the refractory organic matter and the COD concentration.

In step S2, the spectrum scanning mechanism includes an ultraviolet-visible light full-wavelength scanner, an opaque PVC pipe, a signal transmission line, an integrated server, and a computer; the ultraviolet-visible light full-wavelength scanner includes an LED light source emitting element, and a light separation device , optical path emission window, optical path receiving window, measuring beam, cleaning nozzle, reference beam, optical signal conversion electrical signal element, signal collection element, electrical signal array detector; among them: LED light source emitting element is used to generate high-intensity penetrable The ultraviolet light and visible light of the liquid to be tested; the composite light generated by the LED light source emitting element is decomposed into the monochromatic light of the required wavelength at the light separation device; the monochromatic light passes through the liquid to be tested through the optical path emission window and enters the optical path to receive Window; the optical path receiving window is designed as a slidable element for changing the length of the optical path; a vibrating linear motor and an air cleaning nozzle are installed on the optical path emitting window and the optical path receiving window for effective cleaning of the measurement window; The electrical signal element is converted into a corresponding electrical signal, and finally the signal collection element and the electrical signal array detector transmit the signal to the integrated server through the signal transmission line, and the integrated server is used to realize data visualization and data storage.

The specific process of step one includes:

P1: Record the relative molecular mass of the refractory organic matter, and calculate the COD value corresponding to the unit mass concentration;

P2: Use a balance to weigh a certain amount of preferred refractory organic matter, dissolve it in a beaker, transfer it to a volumetric flask for constant volume, select a concentration range of 0-30mg/L COD, and prepare different concentrations of refractory organic matter according to the gradient standard solution;

P3: Use an opaque PVC tube as the container of the liquid to be tested, transfer the prepared refractory organic solution into the PVC tube, and put it into a UV-visible full-wavelength scanner for data collection.

Preferably, the scanning wavelength range of the ultraviolet-visible light full-wavelength scanner is 200-735nm, the scanning interval is 1nm, and the shortest measurement interval is 1min.

In step S3, according to the real-time monitoring concentration of refractory organic matter, the formula 1 for calculating the basis of ozone dosage is as follows:

y ₃ =n*Q*β

In the formula:

y ₃ is the dosage of ozone, the unit is mg/s;

n is the concentration of organic matter to be degraded in the water sample, in mg/L;

Q is the water flow rate, the unit is L/s;

β is the adjustment coefficient obtained according to the experimental data;

The concrete process of step S3 comprises:

Step 1: Use a cylindrical reactor as the reactor for ozone and water samples, and take the effluent from the secondary sedimentation tank of the sewage treatment plant as the experimental water. The reactor uses a titanium aeration head installed at the bottom for ozone dosing;

Step 2: Add a certain amount of water sample to the flow cell, put it into the UV-Vis full-wavelength scanner, use the water pump to make the water sample circulate in the flow cell and the reactor, and monitor the concentration of refractory organic matter in real time;

Step 3: Use an ozone generator to generate ozone and connect the aeration head;

Step 4: The data of the ultraviolet-visible light full-wavelength scanner is transmitted to the control system. The control system calculates the ozone dosage in real time according to formula 1 and controls the ozone dosage of the ozone generator to realize intelligent dosage.

The beneficial effects achieved by the present invention are:

First, the present invention provides a method and system for online monitoring of refractory organic matter concentration and controlling ozone dosing to degrade refractory organic matter; The principle of the characteristic absorption peak only needs to extract the absorbance value at a specific wavelength from the range of 200-750nm, and then substitute the absorbance value into the established corresponding model to obtain the corresponding concentration of refractory organic matter; the process of this method is simple, And the detection interval is short, and high-frequency online monitoring can be realized; the ozone intelligent dosing control system established based on this concentration monitoring method can determine the amount of ozone dosing according to the measured concentration of refractory organic matter, and then control the ozone aeration system to achieve ozone Dosing; the system greatly saves the dosage of ozone, and saves the operating cost for the sewage treatment plant; the inventive device applies the principle of ultraviolet-visible light spectrometry, and upgrades the traditional spectrophotometer. It can be applied to in-situ monitoring in actual engineering; in the water environment, many water quality indicators that have attracted much attention, such as chemical oxygen demand, nitrate nitrogen, nitrite nitrogen, turbidity, etc., will be in the range of ultraviolet and visible light Absorption peaks are generated inside, which means that the device can be used to realize online monitoring of multiple water quality indicators;

The present invention establishes a prediction model of refractory organic matter by measuring standard solutions, and finally realizes the real-time monitoring of the concentration of refractory organic matter in the water environment by relying on the high-frequency measurement characteristics of the ultraviolet-visible light full-wavelength scanner;

Second, the detection limit of the present invention can reach the microgram level for certain types of refractory organic substances, and the detection limit can be further reduced by changing the optical path, and not only can detect water bodies containing a single refractory organic substance, but also Detect water bodies containing a variety of refractory organic compounds;

Third, the present invention uses the LED light source as the emission light source of ultraviolet light and light, compared with the traditional tungsten lamp and deuterium light source, the LED light source can produce stronger light energy; the present invention designs the detection window as a vibrating The component cleans the detection window through the vibration effect, which has a better cleaning effect than the traditional air cleaning nozzle; the effective optical path of the present invention can be adjusted freely, so that the device has higher sensitivity and lower detection limit The detection interval of the present invention can be as low as 1 minute, which can monitor the dynamic changes of some indicators in the water environment in real time, and provide guidance for the governance of the water environment; the scanning range of the present invention is 200-750nm, and can detect simultaneously within this range A variety of water quality indicators can effectively reduce the use of traditional water quality monitoring instruments.

Description of drawings

Fig. 1 is the schematic diagram of the device for real-time monitoring of the concentration of refractory organic matter in the water environment of the present invention;

Fig. 2 is that the method of the present invention measures the UV-Vis spectrogram of different concentrations of refractory organic matter (tetracycline);

Fig. 3 is the refractory organic matter (tetracycline) standard curve that method of the present invention obtains;

Fig. 4 carries out partition partial least square analysis figure for refractory organic matter (chloramphenicol);

Fig. 5 is carried out partial least squares modeling result figure to chloramphenicol concentration in 245-265nm band;

Figure 6 is a diagram of the ozone intelligent dosing system.

In the picture:

LED light source emitting element 1, optical separation device 2, optical path emitting window 3, optical path receiving window 4, measuring beam 5, cleaning nozzle 6, reference beam 7, optical signal conversion electrical signal element 8, signal collecting element 9, electrical signal array Detector 10, signal transmission line 11, integrated server 12, computer 13.

Ozone generator 901, titanium aeration head 902, reactor 903, ultraviolet-visible light full-wavelength scanner 904, flow cell 905, water pump 906, control system 907.

Detailed ways

In order to make it easier for those skilled in the art to understand the present invention, the specific implementation manners of the present invention will be described below with reference to the accompanying drawings.

Example 1

The present invention provides a device for realizing the above-mentioned real-time monitoring method for the concentration of refractory organic matter, as shown in Figure 1, comprising a UV-visible full-wavelength scanner, which includes an LED light source emitting element 1. Optical separation device 2, optical path emission window 3, optical path receiving window 4, measuring beam 5, cleaning nozzle 6, reference beam 7, optical signal conversion electrical signal element 8, signal collection element 9, electrical signal array detector 10. It also includes a signal transmission line 11, an integrated server 12 and a computer 13. Among them: the LED light source emitting element 1 can generate sufficiently high-intensity ultraviolet light and visible light, so that the equipment can better pass the light through the liquid to be tested; For color light, the scanning interval of the device is 1nm, that is, the value of the sample is taken every 1nm. Furthermore, the light beam passes through the liquid to be measured through the optical path emission window 3 and then enters the optical path receiving window 4 . The optical path receiving window 4 is designed as a slidable element. By sliding the position of the optical path receiving window 4, the purpose of changing the length of the optical path is achieved, thereby enabling the device to have a lower detection limit. In addition, a vibrating linear motor is installed on the optical path emission window 3 and the optical path receiving window 4, and cooperates with the air cleaning nozzle 6 to achieve effective cleaning of the measurement window and ensure the accuracy of measurement. The light beam is converted into a corresponding electrical signal at the optical signal conversion electrical signal element 8, and finally the signal collection element 9 and the electrical signal array detector 10 transmit the signal to the integrated server 12 through the signal transmission line 11, in the integrated server 12 Data visualization and data storage can be realized.

Before the equipment is put into use, the measurement window and the surface need to be completely cleaned and placed in ultrapure water for reference calibration of the equipment.

The shortest measurement interval is 1min, the detection window can be adjusted freely within the range of 0.5-50mm, and the scanning interval is 1nm. The final signal data can be opened on the PC in CSV file format, and the presentation form is to record the absorbance data every 1nm. When using the device in a complex water environment, it is necessary to install a protective net around the device to prevent large pollutants (such as flocs, etc.) from blocking the measurement window.

An ultraviolet-visible light full-wavelength scanner, the ultraviolet-visible light full-wavelength scanner includes a multi-parameter monitoring probe and an integrated server placed in the water environment to be tested.

The refractory organic matter concentration prediction model, the refractory organic matter data prediction model receives the data transmitted from the monitoring probe to the server, and inputs the data into the model to obtain the refractory organic matter concentration of the water body to be measured.

Ozone intelligent dosing system. The ozone intelligent dosing system establishes a formula through the corresponding ozone dosage of refractory organic matter, and determines the ozone dosage according to the real-time monitoring concentration of refractory organic matter in sewage to realize intelligent dosing.

Example 2

This embodiment provides a method for real-time monitoring and control of refractory organic matter in sewage, the method comprising the following steps:

1) Make an opaque PVC pipe as a container for the liquid to be tested to reduce the influence of external light on the measurement.

2) Before the measurement, the surface of the UV-Vis full-wavelength scanner is cleaned by rinsing with ultrapure water several times. Clean the measurement window 5 by rinsing with alcohol and wiping it with a soft object, and finally rinse it with ultrapure water several times.

3) Record the relative molecular mass of the refractory organic matter, and calculate the chemical oxygen demand (COD) value corresponding to the unit mass concentration. And according to the actual level of the concentration of refractory organic matter in the water environment, the concentration range of 0-30mg/L COD has been formulated.

4) Use a balance to weigh a certain amount of preferred refractory organic matter, dissolve it in a beaker, transfer it to a volumetric flask for constant volume, and prepare refractory organic matter solutions with different concentrations in this way.

5) Transfer the prepared refractory organic solution to a PVC tube, put it into an ultraviolet-visible light full-wavelength scanner, and perform an average operation on the PC side for the data of scanning the refractory organic solution 5 times, so as to reduce Measurement error.

6) Measure the prepared refractory organic solution sequentially in step 5, and upload the data to the PC for subsequent data processing.

7) Analyze the position of the characteristic absorption peak and the change of absorbance of the same refractory organic substance at different concentrations, and build a concentration prediction model for refractory organic substances according to the change of absorbance at the characteristic absorption wavelength due to different concentrations, so as to realize the detection of refractory organic substances. Real-time monitoring of the concentration of degraded organic matter.

Filling 1L of water into the opaque PVC pipe can meet the measurement requirements of the UV-Vis full-wavelength scanner.

The scanning range of the UV-Vis full-wavelength scanner is 200-735nm, the scanning interval is 1nm, the shortest measurement interval is 1min, and the measurement interval can be adjusted arbitrarily.

For refractory organic substances with only one characteristic absorption peak, the following model is used for modeling:

y ₁ =a*x+b

In the formula:

_y1 is the corresponding COD concentration of the refractory organic matter to be tested, in mg/L;

a is the slope of the established model;

x is the absorbance value of the refractory organic substance to be measured at the characteristic absorption wavelength, the unit is Abs;

b is the residual value of the established model.

For refractory organic substances with two or more characteristic absorption peaks, the following model is used for modeling (the formula contains three characteristic absorption peaks as an example):

y ₂ =a ₁ *x ₁ +b ₁ *x ₂ +c ₁ *x ₃ +d

In the formula:

_y2 is the corresponding COD concentration of the refractory organic matter to be tested, in mg/L;

a ₁ , b ₁ , c ₁ are the fitting parameters of the equation;

x ₁ , x ₂ , x ₃ are the absorbance values of the refractory organic matter to be measured at the wavelength of the characteristic absorption peak, and the unit is Abs;

d is the residual value of the established model.

In this example, four kinds of refractory organic substances are fitted. The four kinds of refractory organic substances correspond to characteristic absorption peaks at different quantities and wavelengths. The fitting results are shown in Table 1:

Table 1 Fitting results of four kinds of refractory organic compounds

The method is also extended to the case where multiple refractory organics are present in the solution at the same time. First, a variety of refractory organic compounds are mixed at different concentrations to configure multiple groups of samples to be tested. Each sample to be tested was measured 5 times one by one to take the average value, and the data was transferred to the PC terminal.

When modeling and predicting different refractory organic compounds in samples, different preprocessing methods (such as SG smoothing, first derivative, multiplicative scattering correction, etc.) are required to achieve the best prediction effect. The means of selecting the preprocessing method is to carry out partial least squares regression modeling on the data after various preprocessing methods, comprehensively compare the number of hidden variables, R ² , and the root mean square of the prediction error, and finally select the preprocessing with the best prediction performance method.

When predicting the concentration of different refractory organic substances, firstly, the best preprocessing method for the refractory organic substances is performed on the data, and then the partitioned partial least square method in the iToolbox toolbox is used in MATLAB2018b to select the predicted root mean square error The smallest interval, partial least squares regression in this interval can realize the effective prediction of the concentration of refractory organic substances to be measured in mixed samples.

Example 3

This embodiment provides an ozone intelligent dosing system for degrading refractory organic matter in sewage, comprising the following steps:

1) The cylindrical reactor 903 is used as the reactor for ozone and water samples, and the effluent from the secondary sedimentation tank of the sewage treatment plant is used as the experimental water. The reactor adopts a titanium aeration head 902 installed at the bottom for ozone dosing.

2) Add a certain amount of water sample to the flow cell 905, put it into the ultraviolet-visible light full-wavelength scanner 904, use the water pump 906 to make the water sample circulate in the flow cell and the reactor, and monitor the concentration of refractory organic matter in real time.

3) Use the ozone generator 901 to generate ozone, connect the aeration head, turn on the ozone generator and use a flow meter to control the dosage of ozone.

4) The data of the ultraviolet-visible light full-wavelength scanner is transmitted to the control system 907, and the following ozone dosing control formula is established according to the recorded data:

y ₃ =n*Q*β

In the formula:

y ₃ is the dosage of ozone, the unit is mg/s.

n is the concentration of organic matter to be degraded in the water sample, in mg/L.

Q is the water flow rate, the unit is L/s.

β is the correlation coefficient obtained from the experimental data.

5) Through the established formula, the amount of ozone generated by the ozone generator is controlled in real time to realize the intelligent dosing of ozone.

The value of the correlation coefficient β in the formula varies greatly, mainly depending on the change in the amount of ozone required for different types of refractory organic matter.

Example 4

This embodiment provides a method for real-time monitoring of the concentration of refractory organic matter in the water environment using the above-mentioned device, the method specifically includes the following steps:

1) Configure a standard solution of refractory organic matter with a concentration gradient of 0-30mg/LCOD (corresponding to COD concentration per unit mass concentration of refractory organic matter), and use an ultraviolet-visible light full-wavelength scanner to measure in sequence.

2) Import the measurement data into the computer 13, draw the ultraviolet-visible light absorption spectrum diagrams of the refractory organics at different concentrations, and find the wavelengths of the characteristic absorption peaks (see Figure 2).

3) Fit the absorbance values at different concentrations at this wavelength to the equation (see Figure 3), and calculate the goodness of fit to determine whether the model is feasible, and calculate the minimum detection of refractory organic substances by this method limit.

4) Substitute the absorbance of the liquid to be measured at a specific wavelength into the model to obtain the concentration of refractory organic matter.

The present invention has carried out the measurement of detection limit to tetracycline, ofloxacin, chloramphenicol, streptomycin, and the results are as shown in table 2:

Table 2 Calculation parameters of device detection limits for four kinds of refractory organic substances

Example 5:

In this embodiment, the water body containing ofloxacin, tetracycline, and chloramphenicol is carried out real-time monitoring of the concentration of refractory organic matter, and the steps are as follows:

1) Configure 70 samples of three refractory organic compounds freely combined at random concentrations, scan all samples in the 200-420nm band with an ultraviolet-visible light full-wavelength scanner, and transfer the data of the final 70 samples to the computer.

2) Select the optimal preprocessing method. The 70 samples were preprocessed by SG smoothing, moving average method, first derivative and second derivative respectively, and then the concentration of each refractory organic compound was used as the dependent variable, and the original data including the unpreprocessed The five groups of sample data are used as independent variables, and the modeling of partial least squares regression is carried out. The number of latent variables (LVs), root mean square of prediction error (RMSEP), and goodness of fit (R2) of the model were used as evaluation indicators to comprehensively evaluate the most helpful pretreatment method for the prediction of the concentration of each refractory organic compound. The results are shown in Table 3.

3) After the optimal pretreatment of each refractory organic compound, the 200-420nm wave band is divided into 10 sub-sections, and partitioned partial least squares are performed to obtain the prediction average value of each refractory organic compound in which wave band range. The square root error is the smallest. Establishing a model in this band can effectively predict the concentration of refractory organic matter.

The results show that taking chloramphenicol as an example, the best pretreatment method for chloramphenicol is the moving average method. After preprocessing, the partitioned partial least squares analysis was carried out on the data, and the predicted root mean square error of chloramphenicol reached the minimum value in the range of 245-267.5nm (see Figure 4), and the partial minimum in this area The quadratic method is used for modeling, and a good fitting effect is obtained (see Figure 5), which proves that the method is accurate and feasible.

Table 3 Comparison of pretreatment methods for different types of refractory organic matter

The above embodiments of the present invention are not intended to limit the protection scope of the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principle of the present invention shall be included in the protection scope of the claims of the present invention.

Claims (3)

1. A method for real-time monitoring of refractory organic matter in sewage and intelligent ozone dosing control method, characterized in that it includes: Step S1 of establishing a relationship model between the absorbance of the refractory organic matter and the corresponding chemical oxygen demand (COD) concentration; Step S2 of obtaining the absorbance of the refractory organic matter in the ultraviolet-visible spectral range in real time by using the spectral scanning mechanism, and monitoring the corresponding concentration of the refractory organic matter in real time using the model of step S1; Calculate the ozone dosage according to the real-time monitoring concentration of the refractory organic matter obtained in step S2, and establish the step S3 of the ozone intelligent dosage system; The specific process of step S1 includes: Step 1. Configure a standard solution of refractory organic substances with a concentration gradient, and sequentially use a spectral scanning mechanism to measure its absorbance in the ultraviolet-visible spectral range; Step 2, draw the ultraviolet-visible light absorption spectrum diagram of the refractory organic substance at different concentrations, find the wavelength of the characteristic absorption peak, and the absorption peak may exist in one or more places; Step 3. Fitting the absorbance values at different concentrations at the wavelength of the characteristic absorption peak to the equation, and establishing a relationship model between the absorbance of the refractory organic matter and the corresponding COD concentration; In step S2, the spectrum scanning mechanism includes an ultraviolet-visible light full-wavelength scanner, an opaque PVC pipe, a signal transmission line, an integrated server, and a computer; the ultraviolet-visible light full-wavelength scanner includes an LED light source emitting element, and a light separation device , optical path emission window, optical path receiving window, measuring beam, cleaning nozzle, reference beam, optical signal conversion electrical signal element, signal collection element, electrical signal array detector; among them: LED light source emitting element is used to generate high-intensity penetrable The ultraviolet light and visible light of the liquid to be tested; the composite light generated by the LED light source emitting element is decomposed into the monochromatic light of the required wavelength at the light separation device; the monochromatic light passes through the liquid to be tested through the optical path emission window and enters the optical path to receive Window; the optical path receiving window is designed as a slidable element for changing the length of the optical path; a vibrating linear motor and an air cleaning nozzle are installed on the optical path emitting window and the optical path receiving window for effective cleaning of the measurement window; The electrical signal element is converted into a corresponding electrical signal, and finally the signal collection element and the electrical signal array detector transmit the signal to the integrated server through the signal transmission line, and the integrated server is used to realize data visualization and data storage; The specific process of step one includes: P1: Record the relative molecular mass of refractory organic matter, and calculate the COD value corresponding to the unit mass concentration; P2: Use a balance to weigh a certain amount of preferred refractory organic matter, dissolve it in a beaker, transfer it to a volumetric flask for constant volume, select a concentration range of 0-30mg/L COD, and prepare different concentrations of refractory organic matter according to the gradient standard solution; P3: Use an opaque PVC tube as the container of the liquid to be tested, transfer the prepared refractory organic solution into the PVC tube, and put it into a UV-visible light full-wavelength scanner for data collection; The scanning range of the ultraviolet-visible light full-wavelength scanner is 200-735nm, the scanning interval is 1nm, and the shortest measurement interval is 1min. 2. The method for real-time monitoring of refractory organic matter in sewage according to claim 1 and intelligent ozone dosing control method, characterized in that: for only one refractory organic matter that produces a characteristic absorption peak, the following model is used for fitting: y ₁ =a*x+b In the formula: _y1 is the corresponding COD concentration of the refractory organic matter to be tested, in mg/L; a is the slope of the established model; x is the absorbance value of the refractory organic substance to be measured at the characteristic absorption wavelength; b is the residual value of the established model; For refractory organic substances with two or more characteristic absorption peaks, the following model is used for fitting. The formula takes three characteristic absorption peaks as an example: y ₂ =a ₁ *x ₁ +b ₁ *x ₂ +c ₁ *x ₃ +d In the formula: _y2 is the corresponding COD concentration of the refractory organic matter to be tested, in mg/L; a ₁ , b ₁ , c ₁ are the fitting parameters of the equation; x ₁ , x ₂ , and x ₃ are the absorbance values of the refractory organic matter to be measured at the wavelength at which the characteristic absorption peak occurs; d is the residual value of the established model. 3. The method for real-time monitoring of refractory organic matter in sewage and smart ozone dosing control method according to claim 1, characterized in that: the specific process of step S3 comprises: Step 1: Use a cylindrical reactor as the reactor for ozone and water samples, and take the effluent from the secondary sedimentation tank of the sewage treatment plant as the experimental water. The reactor uses a titanium aeration head installed at the bottom for ozone dosing; Step 2: Add a certain amount of water sample to the flow cell, put it into the UV-Vis full-wavelength scanner, use the water pump to make the water sample circulate in the flow cell and the reactor, and monitor the concentration of refractory organic matter in real time; Step 3: Use an ozone generator to generate ozone and connect the aeration head; Step 4: The data of the ultraviolet-visible light full-wavelength scanner is transmitted to the control system. The control system calculates the ozone dosage in real time according to formula 1 and controls the ozone dosage of the ozone generator to realize intelligent dosage.