CN114835241B - Real-time monitoring and ozone intelligent adding control method for refractory organic matters in sewage - Google Patents
Real-time monitoring and ozone intelligent adding control method for refractory organic matters in sewage Download PDFInfo
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Abstract
The invention relates to the field of advanced sewage treatment and reclaimed water production, and provides a real-time monitoring and intelligent ozone adding control method for refractory organics in sewage, which comprises the steps of establishing an absorbance and concentration relation model of refractory organics; acquiring absorbance of the refractory organic matters in an ultraviolet-visible light spectrum range in real time by utilizing a spectrum scanning mechanism, and monitoring the concentration of the corresponding refractory organic matters in real time by utilizing a model; and calculating the ozone adding amount according to the concentration of the refractory organic matters monitored in real time, and establishing an intelligent ozone adding system. The invention has simple flow and short detection interval, and can realize high-frequency on-line monitoring; the intelligent ozone adding control system established based on the concentration monitoring method can determine the ozone adding amount according to the measured concentration of the refractory organic matters, and further control the ozone aeration system to carry out ozone adding; the invention greatly saves the ozone adding amount and saves the running cost for sewage treatment plants.
Description
Technical Field
The invention relates to the field of advanced sewage treatment and reclaimed water production, in particular to a real-time monitoring and ozone intelligent adding control method for refractory organic matters in sewage.
Background
Refractory organics generally refer to organic chemicals that are difficult to degrade by biological action under natural conditions. They accumulate in natural environments such as water, soil, etc., and then enter organisms through the food chain and become gradually enriched. Not only the health of the living beings is endangered, but also the whole ecological system is endangered, and finally the living beings can enter the human body, so that the health of the human beings is endangered. Therefore, the method has great significance in realizing effective degradation and real-time monitoring of the refractory organic matters in the sewage.
The detection technology of the hardly degradable organic matters in water mainly comprises a liquid chromatography method, a liquid chromatography and tandem mass spectrometry combined method, a radioimmunoassay primary screening detection method, an enzyme-linked immunosorbent assay method, an immunosensor, a gas chromatography example trap mass spectrometry, a capillary electrophoresis detection technology and the like, and the method has high detection precision and can be used for detecting trace hardly degradable organic matters, but has complex pretreatment operation, high detection equipment requirement and cannot detect the trace hardly degradable organic matters in real time. Based on the current situation, an ultraviolet-visible light spectroscopic method becomes one of important research directions for real-time monitoring of refractory organic matters in sewage. The principle that different kinds of refractory organic matters generate characteristic absorption in an ultraviolet-visible light region is utilized to construct a data driving model, a real-time on-line monitoring sensor for refractory organic matters in water is further manufactured based on a photoelectric principle, and the real-time on-line monitoring sensor and a programmable logic controller are combined to form an ozone adding control system, so that real-time on-line monitoring for refractory organic matters in sewage is realized.
Disclosure of Invention
In order to solve the problems that the concentration of the refractory organic matters in the sewage is difficult to monitor on line and cannot be effectively degraded by biological treatment, the invention provides a real-time monitoring and ozone intelligent adding control method for the refractory organic matters in the sewage, which comprises the following steps:
step S1, establishing a relation model of absorbance and corresponding Chemical Oxygen Demand (COD) concentration of refractory organic matters;
a step S2 of acquiring absorbance of the refractory organic matters in an ultraviolet-visible light spectrum range in real time by utilizing a spectrum scanning mechanism and monitoring the concentration of the corresponding refractory organic matters in real time by utilizing the model of the step S1;
and step S3, calculating the ozone adding amount according to the concentration of the refractory organic matters obtained in the step S2 and monitored in real time, and establishing an intelligent ozone adding system. The specific process of step S1 includes:
step one, preparing a standard solution of a refractory organic matter with a concentration gradient, and sequentially measuring the absorbance of the standard solution in an ultraviolet-visible light spectrum range by using a spectrum scanning mechanism;
drawing ultraviolet-visible light absorption spectrograms of the refractory organic matters at different concentrations, and finding out the wavelength of the characteristic absorption peak;
and thirdly, fitting an equation of absorbance values at different concentrations of the wavelength of the characteristic absorption peak, and establishing a relation model of absorbance and COD concentration of the refractory organic matters.
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 comprises an LED light source emitting element, a light separation device, a light path emitting window, a light path receiving window, a measuring light beam, a cleaning nozzle, a reference light beam, a light signal conversion electric signal element, a signal collecting element and an electric signal array detector; wherein: the LED light source emitting element is used for generating high-intensity ultraviolet light and visible light which can pass through the liquid to be tested; the composite light generated by the LED light source emitting element is decomposed into monochromatic light with a required wavelength at the light separation device; monochromatic light passes through the light path emission window and enters the light path receiving window after passing through the liquid to be measured; the light path receiving window is designed as a slidable element for changing the light path length; a vibration linear motor and an air cleaning nozzle are arranged on the light path emission window and the light path receiving window and are used for effectively cleaning the measuring window; the light beam is converted into corresponding electric signals at the position of the electric signal conversion element, and finally the signal collection element and the electric signal array detector transmit the signals to the integrated server through the signal transmission line, and the integrated server is used for realizing the visualization of data and the storage of the data.
The specific process of the first step comprises the following steps:
p1: recording the relative molecular mass of the refractory organic matters, and calculating the COD value of the chemical oxygen demand corresponding to the concentration of the unit mass;
p2: weighing a certain amount of refractory organic matters with preferential levels by using a balance, dissolving the refractory organic matters in a beaker, transferring the dissolved refractory organic matters to a volumetric flask for constant volume, selecting a concentration range of 0-30mg/L COD, and preparing refractory organic matter standard solutions with different concentrations according to gradients;
p3: and (3) taking the light-tight PVC pipe as a container of liquid to be detected, transferring the prepared refractory organic matter solution into the PVC pipe, and placing the PVC pipe into an ultraviolet-visible light full-wavelength scanner for data acquisition.
Preferably, the scanning band range of the ultraviolet-visible light full-wavelength scanner is 200-735nm, the scanning interval is 1nm, and the shortest measuring interval is 1min.
In the step S3, the formula I for calculating the ozone addition amount according to the concentration of the refractory organic matters monitored in real time is as follows:
y 3 ＝n*Q*β
wherein:
y 3 the unit of the ozone is mg/s;
n is the concentration of the organic matters to be degraded in the water sample, and the unit is mg/L;
q is water inflow, and the unit is L/s;
beta is an adjustment coefficient obtained according to experimental data;
the specific process of step S3 includes:
step 1: taking a cylindrical reactor as a reactor of ozone and a water sample, taking effluent of a secondary sedimentation tank of a sewage treatment plant as experimental water, and adopting a titanium aeration head arranged at the bottom of the reactor for ozone addition;
step 2: adding a certain amount of water sample into the flow cell, placing the flow cell into an ultraviolet-visible light full-wavelength scanner, enabling the water sample to circulate in the flow cell and the reactor through a water pump, and monitoring the concentration of the refractory organic matters in real time;
step 3: ozone is generated by an ozone generator and is connected with an aeration head;
step 4: the data of the ultraviolet-visible light full-wavelength scanner is transmitted to a control system, and the control system calculates the ozone adding amount in real time according to a formula I and controls the ozone adding amount of the ozone generator to realize intelligent adding.
The beneficial effects achieved by the invention are as follows:
the invention provides a method and a system for on-line monitoring the concentration of refractory organics and controlling ozone addition to degrade refractory organics; the method is based on the principle that characteristic absorption peaks are generated at different positions of different types of refractory organic matters in ultraviolet and visible light ranges, and the concentration of the refractory organic matters can be obtained by extracting absorbance values at specific wavelengths from the range of 200-750nm and substituting the absorbance values into an established corresponding model; the method has simple flow and short detection interval, and can realize high-frequency online monitoring; the intelligent ozone adding control system established based on the concentration monitoring method can determine the ozone adding amount according to the measured concentration of the refractory organic matters, and further control the ozone aeration system to carry out ozone adding; the system greatly saves the ozone adding amount and saves the running cost for a sewage treatment plant; the device of the invention applies the principle of ultraviolet-visible light spectroscopy, and upgrades and reforms the traditional spectrophotometer, so that the device can be applied to in-situ monitoring in actual engineering; in water environment, a plurality of water quality indexes such as chemical oxygen demand, nitrate nitrogen, nitrite nitrogen, turbidity and the like which are paid attention to can generate absorption peaks in ultraviolet and visible light ranges, which means that the device can be used for realizing the on-line monitoring of a plurality of water quality indexes;
according to the method, a prediction model of the refractory organic matters is established by measuring the standard solution, and the real-time monitoring of the concentration of the refractory organic matters in the water environment is finally realized by means of the high-frequency measurement characteristic of an ultraviolet-visible light full-wavelength scanner;
secondly, the detection limit of the invention for some kinds of refractory organic matters can reach microgram level, and the detection limit can be further reduced by changing the optical path, and the invention can detect not only the water body containing single refractory organic matters, but also the water body containing various refractory organic matters;
thirdly, the LED light source is used as an ultraviolet light and light emitting light source, and compared with the traditional tungsten lamp and deuterium lamp light sources, the LED light source can generate stronger light energy; the detection window is designed to be a vibratable element, and is cleaned by a vibration effect, so that the air cleaning nozzle has a better cleaning effect compared with the traditional air cleaning nozzle; the effective optical path of the device can be freely adjusted, so that the device has higher sensitivity and lower detection limit; the detection interval of the invention can be as low as 1 minute, so that the dynamic change of certain indexes in the water environment can be monitored in real time, and guidance is provided for the treatment of the water environment; the scanning range of the invention is 200-750nm, and a plurality of water quality indexes can be detected simultaneously in the range, so that the use of the traditional water quality monitoring instrument can be effectively reduced.
Drawings
FIG. 1 is a schematic diagram of a device for monitoring the concentration of refractory organic matters in a water environment in real time;
FIG. 2 is a graph of the ultraviolet-visible spectrum of the method of the invention for measuring various concentrations of refractory organics (tetracyclines);
FIG. 3 is a standard curve of refractory organics (tetracyclines) obtained by the method of the invention;
FIG. 4 is a graph of a partitioned partial least squares analysis of refractory organics (chloramphenicol);
FIG. 5 is a graph showing the results of partial least squares modeling of chloramphenicol concentration in the 245-265nm band;
fig. 6 is a diagram of an intelligent ozone dosing system.
In the figure:
the device comprises an LED light source emitting element 1, a light separation device 2, a light path emitting window 3, a light path receiving window 4, a measuring light beam 5, a cleaning nozzle 6, a reference light beam 7, an optical signal conversion electric signal element 8, a signal collection element 9, an electric signal array detector 10, a signal transmission line 11, an integrated server 12 and a computer 13.
An ozone generator 901, a titanium aeration head 902, a reactor 903, an ultraviolet-visible full-wavelength scanner 904, a flow cell 905, a water pump 906, and a control system 907.
Detailed Description
In order to facilitate understanding of the invention by those skilled in the art, a specific embodiment of the invention is described below with reference to the accompanying drawings.
Example 1
The invention provides a device for realizing the real-time monitoring method of the concentration of the refractory organic matters, which is shown in fig. 1, and comprises an ultraviolet-visible light full-wavelength scanner, wherein the ultraviolet-visible light full-wavelength scanner comprises an LED light source emitting element 1, a light separation device 2, a light path emitting window 3, a light path receiving window 4, a measuring light beam 5, a cleaning nozzle 6, a reference light beam 7, an optical signal conversion electric signal element 8, a signal collecting element 9 and an electric signal array detector 10. The system also comprises a signal transmission line 11, an integrated server 12 and a computer 13. Wherein: the LED light source emitting element 1 can generate ultraviolet light and visible light with high enough intensity, so that the device can better pass light through the liquid to be detected; the generated composite light is decomposed into monochromatic light of a desired wavelength at the light separation device 2, and the scanning interval of the apparatus is 1nm, i.e., samples are valued every 1nm. And the light beam passes through the liquid to be measured through the light path emission window 3 and then enters the light path receiving window 4. The light path receiving window 4 is designed as a slidable element, and the purpose of changing the light path length is achieved by sliding the position of the light path receiving window 4, so that the device has a lower detection limit. And vibration linear motors are arranged on the light path emission window 3 and the light path receiving window 4 and are matched with an air cleaning nozzle 6, so that the measuring window is effectively cleaned, and the measuring accuracy is ensured. The light beam is converted into corresponding electric signals at the electric signal conversion element 8, and finally the signal collecting element 9 and the electric signal array detector 10 transmit the signals to the integrated server 12 through the signal transmission line 11, so that the visualization of data and the storage of data can be realized in the integrated server 12.
Before the device is put into use, the measurement window and the surface need to be completely cleaned and placed in ultrapure water to perform reference correction on the device.
The shortest measurement interval is 1min, the detection window can be freely adjusted within the range of 0.5-50mm, and the scanning interval is 1nm. The final signal data can be opened at the PC end in a CSV file format, and the form of the final signal data is that absorbance data is recorded once every 1nm. When the device is used in a complex water environment, a protective net is required to be installed around the device, so that large pollutants (such as floccules and the like) are prevented from blocking a measuring window.
The ultraviolet-visible light full-wavelength scanner comprises a multi-parameter monitoring probe and an integrated server, wherein the multi-parameter monitoring probe is placed in a water environment to be tested.
And the refractory organic matter concentration prediction model receives 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 detected.
The intelligent ozone adding system establishes a formula corresponding to the ozone adding amount through refractory organic matters, determines the ozone adding amount according to the concentration of the refractory organic matters in sewage monitored in real time, and realizes intelligent adding.
Example 2
The embodiment provides a real-time monitoring control method for refractory organic matters in sewage, which comprises the following steps:
1) An opaque PVC pipe is manufactured, and is used as a container for liquid to be measured, so that the influence of external illumination on measurement is reduced.
2) Before the measurement is performed, the surface of the ultraviolet-visible full-wavelength scanner is cleaned by multiple rinsing with ultrapure water. The measuring window 5 is cleaned by rinsing with alcohol and wiping with a soft object, and finally rinsing with ultra-pure water several times.
3) The relative molecular mass of the refractory organics was recorded and the Chemical Oxygen Demand (COD) value was calculated for the concentration per unit mass. And the concentration range of 0-30mg/L COD is formulated according to the actual concentration level of the refractory organic matters in the water environment.
4) And weighing a certain amount of refractory organics with a preferential level by using a balance, dissolving the refractory organics in a beaker, transferring the dissolved refractory organics to a volumetric flask for constant volume, and preparing refractory organics solutions with different concentrations by using the method.
5) Transferring the prepared refractory organic matter solution into a PVC pipe, placing the PVC pipe into an ultraviolet-visible light full-wavelength scanner, and carrying out averaging operation on data of scanning the refractory organic matter solution for 5 times at a PC end so as to reduce measurement errors.
6) And (5) sequentially measuring the prepared refractory organic matter solution in the step (5), uploading the data to a PC end, and carrying out subsequent data processing.
7) Analyzing the characteristic absorption peak position and the absorbance change of the same refractory organic matter at different concentrations, and constructing a refractory organic matter concentration prediction model according to the absorbance change caused by different concentrations at the characteristic absorption wavelength, so as to realize the real-time monitoring of the refractory organic matter concentration.
The light-tight PVC pipe is injected with 1L water, so that the measurement requirement of an ultraviolet-visible light full-wavelength scanner can be met.
The scanning wave band range of the ultraviolet-visible light full-wave scanner is 200-735nm, the scanning interval is 1nm, the shortest measuring interval is 1min, and the measuring interval can be adjusted arbitrarily.
When modeling refractory organics that have only one site that produces a characteristic absorption peak, the following model is used:
y 1 ＝a*x+b
wherein:
y 1 the unit is mg/L for the corresponding COD concentration of the refractory organic matter to be detected;
a is the slope of the model established;
x is the absorbance value of the to-be-detected refractory organic matter at the characteristic absorption wavelength, and the unit is Abs;
b is the residual value of the model built.
When modeling refractory organic matter having two or more characteristic absorption peaks, the following model is adopted (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
wherein:
y 2 the unit is mg/L for the corresponding COD concentration of the refractory organic matter to be detected;
a 1 、b 1 、c 1 fitting parameters for the equation;
x 1 、x 2 、x 3 the unit is Abs for the absorbance value of the nondegradable organic matter to be measured at the wavelength generating the characteristic absorption peak;
d is the residual value of the model built.
In this example, four refractory organics were fitted, and the four refractory organics correspond to characteristic absorption peaks at different numbers and wavelengths, respectively, and the fitting results are shown in table 1:
TABLE 1 fitting results for four refractory organics
The method also expands the condition that a plurality of refractory organic matters exist in the solution at the same time. Firstly, mixing a plurality of refractory organic matters at different concentrations to prepare a plurality of groups of samples to be tested. And measuring each sample to be measured for 5 times one by one, taking an average value, and transferring the data to a PC end.
When modeling and predicting different refractory organics in a sample, different pretreatment methods (such as SG smoothing, first derivative, multiplicative scattering correction and the like) are needed to achieve the best prediction effect. The method for selecting the preprocessing method is to model partial least squares regression of the data after a plurality of preprocessing methods, and comprehensively compare the hidden variable number and R 2 And finally, selecting a preprocessing method with the best prediction performance.
When the concentration of different refractory organics is predicted, firstly, the optimal pretreatment method which is most suitable for the refractory organics is carried out on the data, then, the partial least square method of the partition in the itolbox tool box is used in MATLAB2018b, the interval with the minimum root mean square error of the prediction is selected, and the partial least square regression is carried out on the interval, so that the effective prediction of the concentration of the refractory organics to be detected in the mixed sample can be realized.
Example 3
The embodiment provides an intelligent ozone adding system for degrading refractory organic matters in sewage, which comprises the following steps:
1) The cylindrical reactor 903 is taken as a reactor of ozone and water samples, secondary sedimentation tank effluent of a sewage treatment plant is taken as experimental water, and the reactor adopts a titanium aeration head 902 arranged at the bottom for ozone addition.
2) A certain amount of water sample is added into a flow cell 905, an ultraviolet-visible light full-wavelength scanner 904 is arranged, the water sample circulates in the flow cell and the reactor through a water pump 906, and the concentration of the refractory organic matters is monitored in real time.
3) Ozone is generated by using an ozone generator 901, and is connected with an aeration head, the ozone generator is started, and the adding amount of the ozone is controlled by using a flowmeter.
4) The data of the ultraviolet-visible full-wavelength scanner is transmitted to a control system 907, and the following ozone addition control formula is established according to the recorded data:
y 3 ＝n*Q*β
wherein:
y 3 the unit of the ozone is mg/s.
n is the concentration of the organic matter to be degraded in the water sample, and the unit is mg/L.
Q is water inflow rate, and the unit is L/s.
Beta is a correlation coefficient obtained from experimental data.
5) The amount of ozone generated by the ozone generator is controlled in real time through the established formula, so that intelligent ozone adding is realized.
The value of the correlation coefficient beta in the formula has larger change, and mainly depends on the change of the ozone amount required by different kinds of refractory organic matters.
Example 4
The embodiment provides a method for monitoring the concentration of refractory organic matters in a water environment in real time by utilizing the device, which specifically comprises the following steps:
1) Preparing 0-30mg/LCOD concentration gradient refractory organic matter standard solution (corresponding to COD concentration meter by unit mass concentration refractory organic matter), and sequentially measuring by using ultraviolet-visible light full-wavelength scanner.
2) The measured data are led into a computer 13, ultraviolet-visible light absorption spectrograms of the refractory organic matters under different concentrations are drawn, and the wavelengths of the characteristic absorption peaks are found (see figure 2).
3) And (3) carrying out equation fitting on absorbance values at different concentrations at the wavelength (see figure 3), calculating the goodness of fit, determining whether the model has feasibility, and calculating the lowest detection limit of the method on the refractory organic matters.
4) Substituting the absorbance of the liquid to be detected under the specific wavelength into the model to obtain the concentration of the refractory organic matters.
The detection limit of the tetracycline, ofloxacin, chloramphenicol and streptomycin is measured, and the results are shown in Table 2:
TABLE 2 detection limit calculation parameters for four refractory organics
Example 5:
the method for monitoring the concentration of the refractory organic matters in the water body containing ofloxacin, tetracycline and chloramphenicol in real time comprises the following steps:
1) 70 samples of three refractory organic matters which are freely combined in random concentration are configured, all samples are scanned in a wave band of 200-420nm by using an ultraviolet-visible light full-wave band scanner, and data of the final 70 samples are transmitted to a computer.
2) An optimal pretreatment method is selected. And carrying out SG smoothing, moving average, first derivative pretreatment and second derivative pretreatment on 70 samples, and then carrying out partial least squares regression modeling by taking the concentration of each refractory organic substance as a dependent variable and five groups of sample data including raw data which are not pretreated as independent variables. The number of potential variables (LVs), the root mean square of prediction error (RMSEP) and the goodness of fit (R2) of the model are taken as evaluation indexes, and comprehensive judgment is performed on the preprocessing method which is most helpful to the concentration prediction of each refractory organic matter. The results are shown in Table 3.
3) After the optimal pretreatment of each refractory organic matter, the wave band of 200-420nm is divided into 10 small segments, and the partial least square is carried out to obtain the predicted root mean square error of each refractory organic matter in the wave band range. The concentration of the refractory organic matters can be effectively predicted by establishing a model in the wave band.
As a result, chloramphenicol was used as an example, and the optimum pretreatment method for chloramphenicol was a moving average method. After pretreatment, the data is subjected to partitioned partial least square analysis to obtain that the predicted root mean square error of chloramphenicol reaches the minimum value within the range of 245-267.5nm (see fig. 4), and modeling is carried out on the area by a partial least square method to obtain a good fitting effect (see fig. 5), so that the method is proved to be accurate and feasible.
TABLE 3 comparison of pretreatment methods for different kinds of refractory organics
The above embodiments of the present invention do not limit the scope of the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the scope of the present invention as set forth in the appended claims.
Claims (3)
1. The method for real-time monitoring of refractory organic matters in sewage and intelligent ozone adding control is characterized by comprising the following steps:
step S1, establishing a relation model of absorbance and corresponding Chemical Oxygen Demand (COD) concentration of refractory organic matters;
a step S2 of acquiring absorbance of the refractory organic matters in an ultraviolet-visible light spectrum range in real time by utilizing a spectrum scanning mechanism and monitoring the concentration of the corresponding refractory organic matters in real time by utilizing the model of the step S1;
step S3 of calculating the ozone adding amount according to the concentration of the refractory organic matters obtained in the step S2 and monitored in real time and establishing an intelligent ozone adding system;
the specific process of step S1 includes:
step one, preparing a standard solution of a refractory organic matter with a concentration gradient, and sequentially measuring the absorbance of the standard solution in an ultraviolet-visible light spectrum range by using a spectrum scanning mechanism;
drawing ultraviolet-visible light absorption spectrograms of the refractory organic matters at different concentrations, and finding out the wavelengths of characteristic absorption peaks, wherein the wavelengths may be one or more of the absorption peaks;
fitting an equation of absorbance values at different concentrations of wavelengths of the characteristic absorption peaks, and establishing a relation model of absorbance and corresponding COD concentration of the refractory organic matters;
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 comprises an LED light source emitting element, a light separation device, a light path emitting window, a light path receiving window, a measuring light beam, a cleaning nozzle, a reference light beam, a light signal conversion electric signal element, a signal collecting element and an electric signal array detector; wherein: the LED light source emitting element is used for generating high-intensity ultraviolet light and visible light which can pass through the liquid to be tested; the composite light generated by the LED light source emitting element is decomposed into monochromatic light with a required wavelength at the light separation device; monochromatic light passes through the light path emission window and enters the light path receiving window after passing through the liquid to be measured; the light path receiving window is designed as a slidable element for changing the light path length; a vibration linear motor and an air cleaning nozzle are arranged on the light path emission window and the light path receiving window and are used for effectively cleaning the measuring window; the light beam is converted into corresponding electric signals at the position of the optical signal conversion electric signal element, and finally the signal collection element and the electric signal array detector transmit the signals to the integrated server through the signal transmission line, and the integrated server is used for realizing the visualization of data and the storage of the data;
the specific process of the first step comprises the following steps:
p1: recording the relative molecular mass of the refractory organic matters, and calculating the COD value corresponding to the concentration of the unit mass;
p2: weighing a certain amount of refractory organic matters with preferential levels by using a balance, dissolving the refractory organic matters in a beaker, transferring the dissolved refractory organic matters to a volumetric flask for constant volume, selecting a concentration range of 0-30mg/L COD, and preparing refractory organic matter standard solutions with different concentrations according to gradients;
p3: the method comprises the steps of using an opaque PVC pipe as a container of liquid to be detected, transferring a prepared refractory organic solution into the PVC pipe, and placing the PVC pipe into an ultraviolet-visible light full-wavelength scanner for data acquisition;
the scanning wave band range of the ultraviolet-visible light full-wave scanner is 200-735nm, the scanning interval is 1nm, and the shortest measuring interval is 1min.
2. The method for monitoring refractory organic matters in sewage and intelligently adding and controlling ozone in real time according to claim 1, which is characterized in that: for refractory organics with only one point generating characteristic absorption peaks, the following model was used for fitting:
y 1 ＝a*x+b
wherein:
y 1 the unit is mg/L for the corresponding COD concentration of the refractory organic matter to be detected;
a is the slope of the model established;
x is the absorbance value of the to-be-detected refractory organic matter at the characteristic absorption wavelength;
b is the residual value of the established model;
for refractory organic matters with two or more characteristic absorption peaks, the following model is adopted for fitting, and 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
wherein:
y 2 the unit is mg/L for the corresponding COD concentration of the refractory organic matter to be detected;
a 1 、b 1 、c 1 fitting parameters for the equation;
x 1 、x 2 、x 3 the absorbance value of the to-be-detected refractory organic matter at the wavelength generating the characteristic absorption peak;
d is the residual value of the model built.
3. The method for monitoring refractory organic matters in sewage and intelligently adding and controlling ozone in real time according to claim 1, which is characterized in that: the specific process of step S3 includes:
step 1: taking a cylindrical reactor as a reactor of ozone and a water sample, taking effluent of a secondary sedimentation tank of a sewage treatment plant as experimental water, and adopting a titanium aeration head arranged at the bottom of the reactor for ozone addition;
step 2: adding a certain amount of water sample into the flow cell, placing the flow cell into an ultraviolet-visible light full-wavelength scanner, enabling the water sample to circulate in the flow cell and the reactor through a water pump, and monitoring the concentration of the refractory organic matters in real time;
step 3: ozone is generated by an ozone generator and is connected with an aeration head;
step 4: the data of the ultraviolet-visible light full-wavelength scanner is transmitted to a control system, and the control system calculates the ozone adding amount in real time according to a formula I and controls the ozone adding amount of the ozone generator to realize intelligent adding.
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