CN108395003B - Numerical simulation method for directly coupling and degrading antibiotic wastewater through photocatalysis-biodegradation and application thereof - Google Patents

Numerical simulation method for directly coupling and degrading antibiotic wastewater through photocatalysis-biodegradation and application thereof Download PDF

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CN108395003B
CN108395003B CN201810290919.7A CN201810290919A CN108395003B CN 108395003 B CN108395003 B CN 108395003B CN 201810290919 A CN201810290919 A CN 201810290919A CN 108395003 B CN108395003 B CN 108395003B
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周丹丹
马跃
董双石
付亮
崔晓春
布鲁斯·里特曼
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Abstract

The invention provides a numerical simulation method for directly coupling and degrading antibiotic wastewater through photocatalysis-biodegradation, which belongs to the technical field of antibiotic wastewater treatment, wherein a kinetic model shown in a formula (11) is used for simulating the concentration of antibiotic at any moment in the process of directly coupling and degrading antibiotic wastewater through photocatalysis-biodegradation, the data simulated by the numerical simulation method and experimental data provided by the invention have high applicability and small relative error, and the correlation (R) of degradation simulation of tetracycline is recorded according to the embodiment2) Over 95%, the relative error is less than 2.1%; correlation of degradation simulation on amoxicillin (R)2) Above 93%, the relative error is less than 1.8%.
Figure DDA0001617484770000011
Wherein the content of the first and second substances,

Description

Numerical simulation method for directly coupling and degrading antibiotic wastewater through photocatalysis-biodegradation and application thereof
Technical Field
The invention belongs to the technical field of antibiotic wastewater treatment, and particularly relates to a numerical simulation method for degrading antibiotic wastewater by a photocatalysis-biodegradation direct coupling process and application thereof.
Background
In 2008, the group of subjects of professor Rittmann, the american academy of engineering, presented for the first time the concept of photocatalytic oxidation biodegradation direct coupling technology (ICPB). The photocatalyst is supported on the outer surface of the porous carrier, and the biofilm is distributed in the inner pores of the carrier. Under the excitation of ultraviolet light/visible light, the catalyst on the outer surface of the porous carrier can generate photocatalytic reaction, and the internal biological membrane can generate biodegradation under the aeration condition. The photocatalytic reaction and the biodegradation are carried out synchronously in time and space in a direct coupling reaction system. At present, the ICPB technology has been successfully applied to the degradation of biologically inhibitory pollutants such as phenol, chlorophenol, pyridine, dye wastewater, nitrobenzene, tetracycline and the like. Compared with the prior art, the method solves the problems of low mineralization efficiency of pollutants by single photocatalytic reaction, poor tolerance of single biodegradation to toxic and inhibitory pollutants, high energy consumption, excessive oxidation and the like of the photocatalysis and biodegradation process, and has remarkable advantages.
Kinetic models are crucial for large-scale and practical application of this new technology ICPB. In particular, the kinetic model can be used to: (1) analyzing key factors of pollutant degradation; (2) deeply elucidating complex reaction mechanisms; (3) providing a theoretical basis for the amplification of a reaction system; (4) and reasonably predicting the processing time so as to predict the running cost. Therefore, constructing a reasonable kinetic model is crucial for the optimization and control of ICPB.
Presently, ICPB systems have been reported to numerically simulate using the traditional mathematical model Aiba, i.e., simply quantifying the degradation of contaminants by a substrate inhibition model. The Aiba biological growth model is:
Figure BDA0001617484760000011
mu is the growth rate of the organism, mumaxFor maximum specific growth rate of the organism, CSIs the concentration of the contaminant, KSIs Aiba half maximum Rate concentration, KSIIs Aiba inhibitory concentration.
The biodegradation rate model of the contaminants in the reactor was also fitted using the Aiba biodegradation model:
Figure BDA0001617484760000021
r is the rate of contaminant degradation, rmaxThe maximum degradation rate.
However, this model only uses a pure biodegradation model to fit a section of the whole process of the direct coupling reaction of photocatalysis-biodegradation, which is only suitable for a certain stage of the reaction, and cannot simulate the whole process of the reaction as a whole, and ignores the direct coupling reaction between photolysis and biodegradation, so that the complex mechanism of the ICPB process cannot be reflected, which is the key mechanism of the ICPB reaction.
Disclosure of Invention
In view of the above, the present invention provides a numerical simulation method for simulating the direct coupling effect between photocatalysis and biodegradation, which can accurately display the complex mechanism of the ICPB process.
In order to achieve the above object, the present invention provides the following technical solutions: a numerical simulation method for directly coupling photocatalytic-biodegradation to degrade antibiotic wastewater comprises the following steps:
using antibiotic polluted wastewater as a treatment object, using porous sponge as a carrier, and adding Ag/TiO2A photocatalyst is loaded on the surface of the porous sponge, and a biological membrane is attached to the inside of the porous carrier to construct a photocatalytic-biodegradation directly-coupled antibiotic wastewater degradation system;
the dynamic model of the formula (11) is utilized to simulate the concentration of antibiotics in a system for directly coupling and degrading the antibiotics at any time in the photocatalytic-biodegradation direct coupling degradation antibiotic wastewater,
Figure BDA0001617484760000022
wherein the concentration of intermediate product int. at any instant is obtained by formula (12),
Figure BDA0001617484760000023
the abbreviations in formulae (11) and (12) have the corresponding meanings as follows: ANT antibiotic contaminants; ROS reactive oxygen species; TiO 22Titanium dioxide; int, intermediate; carrying out PC photocatalytic reaction; ICPB photocatalysis-biodegradation direct coupling; k is a radical of0The rate of reactive oxygen species generation; k is a radical of1Secondary reaction rates of antibiotic contaminants; k is a radical of2The secondary reaction rate of the intermediate product; t time; rmMaximum specific degradation rate of the intermediate product; ksA half-saturation constant; the biomass of X; [ ANT]The concentration of ANT; [ TiO 22]Represents the concentration of titanium dioxide; [ ROS]0Initial concentration of ROS; [ Int.]Intermediate product concentration; the [ Int.]Expressed by Chemical Oxygen Demand (COD); wherein the parameter k0、X、[TiO2]、[ROS]0、[ANT]、[Int.]Measured by experimental means, parameter k1、k2、Rm、KsTo be obtained by software fitting.
Preferably, the kinetic model of formula (11) is constructed as follows: the reaction process of ANT in direct coupling of photocatalysis-biodegradation is simplified as follows:
s1) catalyst TiO2The active species ROS with strong oxidizing property is generated by light excitation, as shown in formula (1),
Figure BDA0001617484760000031
s2) the active species ROS attacks the ANT to degrade the ANT into a biodegradable intermediate int, as shown in formula (2),
Figure BDA0001617484760000032
s3) a part of said intermediate product int. is attacked by reactive species ROS to produce products, as shown in formula (3),
Figure BDA0001617484760000033
s4) another part of the intermediate int. is biodegraded and eventually mineralized to carbon dioxide and water, as shown in formula (4),
Int.+biodegradation→CO2+H2O (4)
the ANT degradation in step S2) may be fitted using secondary reaction kinetics,
Figure BDA0001617484760000034
the rate of change of int. in step S3) is equal to the rate of photocatalytic generation minus the rate of consumption,
Figure BDA0001617484760000035
in the direct photocatalytic-biodegradation coupling process, the rate of change of int. is equal to the rate of production minus the rate of photocatalytic consumption and the rate of biodegradation,
Figure BDA0001617484760000036
the rate of change of the reactive species ROS is the rate of generation minus the rate of consumption,
Figure BDA0001617484760000041
the amount of the reactive species ROS at any one time obtained by integrating the rate of change of the reactive species ROS is,
Figure BDA0001617484760000046
the relationship between the reaction rates of the ANT and the int can be expressed in terms of competition kinetics:
k2＝Ak1(10)
wherein
Figure BDA0001617484760000042
The degradation reaction kinetic model of ANT was obtained by substituting the above formulae (9), (10) into the formulae (5) and (7):
Figure BDA0001617484760000043
wherein the content of the first and second substances,
Figure BDA0001617484760000044
the above model building process is based on the following assumptions: a, under a stable state, the biomass is constant in the direct coupling process of photocatalysis-biodegradation; b, biodegradation in the direct coupling process of photocatalysis-biodegradation can mineralize all intermediate products into carbon dioxide finally; c the amount of all active species produced photocatalytically is replaced by the amount of active species that plays the most dominant role.
Preferably, the reaction kinetic model of chemical oxygen demand COD is represented by formula (17):
Figure BDA0001617484760000045
wherein [ COD ] is the concentration of Chemical Oxygen Demand (COD), k3 is the secondary reaction rate of the Chemical Oxygen Demand (COD), the [ COD ] is measured by an experimental means, and k3 is obtained by software fitting.
Preferably, the method for constructing the chemical oxygen demand COD reaction kinetic model is as follows: the degradation rate of the chemical oxygen demand COD is fitted with a second order reaction kinetics:
Figure BDA0001617484760000051
wherein [ ROS ] is obtained by the formula (14),
Figure BDA0001617484760000052
the photocatalytic degradation rate for obtaining the chemical oxygen demand COD in the formula (13) with the formula (14) is shown as a formula (15),
Figure BDA0001617484760000053
in the biodegradation process, the degradation rate of the chemical oxygen demand COD is shown as a formula (16),
Figure BDA0001617484760000054
integration (15) and formula (16) obtained a degradation rate reaction kinetic model of the chemical oxygen demand COD in a photocatalytic-biodegradation direct coupling process:
Figure BDA0001617484760000055
the invention also provides application of the numerical simulation method for directly coupling and degrading the antibiotic wastewater through photocatalysis-biodegradation in amplification, control and optimization of a system for directly coupling and degrading the antibiotic wastewater through photocatalysis-biodegradation.
Preferably, k is during said application0、X、TiO2The concentration, ROS concentration, ANT concentration, int concentration and COD concentration are measured by experiments, and k is1、k2、k3、Rm、KsObtained for software fitting.
The invention has the beneficial effects that: the numerical simulation method for directly coupling and degrading the antibiotic wastewater through photocatalysis-biodegradation provided by the invention takes an intermediate product as a bridge, combines a photocatalysis model with a biodegradation model, constructs a dynamic model of antibiotic concentration change in the whole process of directly coupling the photocatalysis-biodegradation, solves the problem that the traditional mathematical model is only suitable for a certain stage of directly coupling the photocatalysis-biodegradation, and can embody a reaction mechanism of directly coupling the photocatalysis and the biodegradation, namely, a large amount of photocatalytic products are degraded by organisms, so that active species generated by photocatalysis can attack target pollutants more, and the ROS concentration which is reacted with ANT on the model is increased. The data simulated by the numerical simulation method provided by the invention has high applicability and small relative error with experimental data, and the degradation simulation correlation (R) of the tetracycline is recorded according to the embodiment2) Over 95%, the relative error is less than 2.1%; correlation of degradation simulation on amoxicillin (R)2) Above 93%, the relative error is less than 1.8%.
Detailed Description
The invention provides a numerical simulation method for directly coupling and degrading antibiotic wastewater through photocatalysis-biodegradation. The photocatalytic-biodegradation direct coupling method comprises (ICPB): loading a photocatalyst on the outer surface of the porous carrier, and distributing the biological membrane in the pores inside the porous carrier; under the excitation of ultraviolet light/visible light, the catalyst on the outer surface of the porous carrier is excited to generate photocatalytic reaction, and the intermediate product generated by photocatalysis is directly utilized by the inner biomembrane and is subjected to biodegradation and mineralization.
Numerical simulation: the method includes the steps of constructing a mathematical model through reasonable hypothesis, carrying out mathematical derivation according to the mathematical model, fitting with experimental data, obtaining correlation and error analysis of the model, and obtaining applicability of the constructed model.
The invention provides a numerical simulation method for directly coupling and degrading antibiotic wastewater through photocatalysis-biodegradation, which comprises the following steps of:
using antibiotic polluted wastewater as a treatment object, using porous sponge as a carrier, and adding Ag/TiO2A photocatalyst is loaded on the surface of the porous sponge, and a biological membrane is attached to the inside of the porous carrier to construct a photocatalytic-biodegradation directly-coupled antibiotic wastewater degradation system;
the dynamic model of the formula (11) is utilized to simulate the concentration of antibiotics in a system for directly coupling and degrading the antibiotics at any time in the photocatalytic-biodegradation direct coupling degradation antibiotic wastewater,
Figure BDA0001617484760000061
wherein the concentration of intermediate product int. at any instant is obtained by formula (12),
Figure BDA0001617484760000071
the abbreviations in formulae (11) and (12) have the corresponding meanings as follows: ANT antibiotic contaminants; ROS reactive oxygen species; TiO 22Oxidation of hydrogen dioxideTitanium; int, intermediate; carrying out PC photocatalytic reaction; ICPB photocatalysis-biodegradation direct coupling; k is a radical of0The rate of reactive oxygen species generation; k is a radical of1Secondary reaction rates of antibiotic contaminants; k is a radical of2The secondary reaction rate of the intermediate product; t time; rmMaximum specific degradation rate of the intermediate product; ksA half-saturation constant; the biomass of X; [ ANT]The concentration of ANT; [ TiO 22]Represents the concentration of titanium dioxide; [ ROS]0Initial concentration of ROS; [ Int.]Intermediate product concentration; the [ Int.]Expressed by Chemical Oxygen Demand (COD); wherein the parameter k0、X、[TiO2]、[ROS]0、[ANT]、[Int.]Measured by experimental means, k0The concentration of the ROS is the intercept of the plot of the ROS generation amount and the time, and the concentrations of the ANT and int are measured by adopting an ultra-high performance liquid chromatography and a COD determinator. Parameter k1、k2、Rm、KsTo be obtained by software fitting.
In the present invention, the method for constructing the kinetic model described in formula (11) is as follows: the reaction process of ANT in direct coupling of photocatalysis-biodegradation is simplified as follows:
s1) catalyst TiO2Excited by light to generate reactive species ROS with strong oxidizing property,
Figure BDA0001617484760000072
s2) the reactive species ROS attacks the ANT degrading the ANT to biodegradable int,
Figure BDA0001617484760000073
s3) a part of said int. is attacked by reactive species ROS to produce products,
Figure BDA0001617484760000074
s4) additional portions of the int. are biodegraded and eventually mineralized into carbon dioxide and water,
Int.+biodegradation→CO2+H2O (4)
the ANT degradation in step S2) may be fitted using secondary reaction kinetics,
Figure BDA0001617484760000075
the rate of change of int. in step S3) is equal to the rate of photocatalytic generation minus the rate of consumption,
Figure BDA0001617484760000081
in the direct photocatalytic-biodegradation coupling process, the rate of change of int. is equal to the rate of production minus the rate of photocatalytic consumption and the rate of biodegradation,
Figure BDA0001617484760000082
the rate of change of the reactive species ROS is the rate of generation minus the rate of consumption,
Figure BDA0001617484760000083
the amount of the reactive species ROS at any one time obtained by integrating the rate of change of the reactive species ROS is,
Figure BDA0001617484760000087
the relationship between the reaction rates of the ANT and the int can be expressed in terms of competition kinetics:
k2＝Ak1(10)
wherein
Figure BDA0001617484760000084
The degradation reaction kinetic model of ANT was obtained by substituting the above formulae (9), (10) into the formulae (5) and (7):
Figure BDA0001617484760000085
wherein the content of the first and second substances,
Figure BDA0001617484760000086
preferably, the reaction kinetic model of chemical oxygen demand COD is represented by formula (17):
Figure BDA0001617484760000091
in the invention, the construction of the dynamic model for directly coupling and degrading the antibiotic wastewater by photocatalysis-biodegradation is based on the following assumptions: (1) in a stable state, the dropped biological membrane and the newly grown biological membrane keep balance, and the biomass is constant. (2) Biodegradation can eventually mineralize all intermediates to carbon dioxide. (3) The amount of intermediate products produced by the photocatalytic reaction and the aerobic biodegradation is expressed by Chemical Oxygen Demand (COD). (4) The amount of all active species produced by photocatalysis is replaced by the amount of active species that plays the most dominant role.
In the invention, the construction method of the reaction kinetic model of the chemical oxygen demand COD is as follows: the degradation rate of the chemical oxygen demand COD is fitted with a second order reaction kinetics:
Figure BDA0001617484760000092
wherein [ ROS ] is obtained by the formula (14),
Figure BDA0001617484760000093
the photocatalytic degradation rate for obtaining the chemical oxygen demand COD in the formula (13) with the formula (14) is shown as a formula (15),
Figure BDA0001617484760000094
in the biodegradation process, the degradation rate of the chemical oxygen demand COD is shown as a formula (16),
Figure BDA0001617484760000095
integration (15) and formula (16) obtained a degradation rate reaction kinetic model of the chemical oxygen demand COD in a photocatalytic-biodegradation direct coupling process:
Figure BDA0001617484760000096
the invention also provides application of the numerical simulation method for directly coupling and degrading the antibiotic wastewater through photocatalysis-biodegradation in amplification, control and optimization of a system for directly coupling and degrading the antibiotic wastewater through photocatalysis-biodegradation. In the invention, the numerical simulation method for directly coupling and degrading the antibiotic wastewater by photocatalysis-biodegradation can simulate the concentration of antibiotic at any moment in the direct coupling process of photocatalysis-biodegradation, analyze key factors of pollutant degradation, and further deeply clarify a complex reaction mechanism, namely, a large amount of photocatalytic products are degraded by organisms, so that active species generated by photocatalysis attack target pollutants more, and the concentration of ROS (reactive oxygen species) reacting with ANT is increased on a model; providing a theoretical basis for the amplification of a reaction system; and reasonably predicting the processing time so as to predict the running cost.
The following examples are provided to illustrate the method for numerical simulation of directly coupling and degrading antibiotic wastewater by photocatalytic-biodegradation and its application, but they should not be construed as limiting the scope of the present invention.
Example 1
Case of applying established model to ICPB system for treating Tetracycline (TCH) wastewater
At 20mg/L saltAcid Tetracycline (TCH) is used as a target pollutant, porous sponge is used as a carrier, and Ag/TiO is added2The photocatalyst is loaded on the surface of the porous sponge, and the biomembrane is attached to the inside of the porous carrier to construct an ICPB system. The TCH degradation and mineralization numerical simulation result is experimentally verified by adopting the formulas (11) and (17), wherein k is0、X、TiO2The concentration, ROS concentration, TCH concentration, int. concentration and COD concentration are measured by experiments and directly substituted into formula k0The concentration of the ROS is the intercept of the plot of the ROS generation amount and the time, and the concentrations of the ANT and int are measured by adopting an ultra-high performance liquid chromatography and a COD determinator. And parameter k1、k2、k3、Rm、KsFor the First Optimization fitting by software. TCH degradation rate constant k of ICPB system when TCH initial concentration is 20mg/L1Improved by 12% compared with single photocatalysis (R)2) Are all over 95 percent, and the relative error is less than 2.1 percent. In addition, the COD degradation rate constant of the ICPB system is improved by about 38% compared with that of the ICPB system by single photocatalysis, the correlation between the numerical result of model simulation and the numerical result obtained by experiment is more than 92%, and the relative error is not more than 0.9%.
When the initial concentration of TCH is 40mg/L, the TCH degradation rate constant of the ICPB system is improved by 9% compared with that of single photocatalysis, and the correlation between the numerical result of model simulation and the numerical result obtained by the experiment is more than 96%. In addition, the COD degradation rate constant of the ICPB system is improved by about 43 percent compared with that of the ICPB system by single photocatalysis, and the correlations are all more than 94 percent.
Example 2
Case of applying constructed model to ICPB system for treating Amoxicillin (AMO) wastewater
Taking 20mg/L Amoxicillin (AMO) as a target pollutant, taking porous sponge as a carrier, and taking Ag/TiO2The photocatalyst is loaded on the surface of the porous sponge, and the biomembrane is attached to the inside of the porous carrier to construct an ICPB system. The AMO degradation and mineralization numerical simulation result is actually carried out by adopting the formulas (11) and (17)Verification of where k0、X、TiO2The concentration, ROS concentration, AMO concentration, int concentration and COD concentration are measured by experiments and directly substituted into the formula, and the parameter k1、k2、k3、Rm、KsFor fitting by software FirstOptimization. k is a radical of0The concentration of the ROS is the intercept of the plot of the ROS generation amount and the time, and the concentrations of the ANT and int are measured by adopting an ultra-high performance liquid chromatography and a COD determinator. Compared with single photocatalysis, the AMO degradation rate constant of the ICPB system is improved by 13.4%, the correlation between the numerical result of model simulation and the numerical result obtained by the test is more than 93%, and the relative error is less than 1.8%. In addition, the COD degradation rate constant of the ICPB system is improved by about 35% compared with that of the ICPB system by single photocatalysis, the correlations are all over 90%, and the relative error is not more than 2.7%.
When the AMO initial concentration is 40mg/L, the AMO degradation rate constant of the ICPB system is improved by 11.6% compared with that of single photocatalysis, and the correlation between the numerical result of model simulation and the numerical result obtained by the test is more than 95%. In addition, the COD degradation rate constant of the ICPB system is improved by about 40% compared with that of the ICPB system by single photocatalysis, and the correlations are all more than 92%.
The embodiments show that the data simulated by the numerical simulation method provided by the invention and the experimental data have high applicability and small relative error.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (5)

1. A numerical simulation method for directly coupling photocatalytic degradation and biodegradation to degrade antibiotic wastewater is characterized by comprising the following steps:
takes antibiotic polluted wastewater as a treatment object and takes porous sponge as a carrierA body of Ag/TiO2A photocatalyst is loaded on the surface of the porous sponge, and a biological membrane is attached to the inside of the porous carrier to construct a photocatalytic-biodegradation directly-coupled antibiotic wastewater degradation system;
the dynamic model of the formula (11) is utilized to simulate the direct coupling degradation of the concentration of the antibiotic at any time in the antibiotic wastewater system through photocatalysis-biodegradation,
Figure FDA0002372927340000011
wherein the concentration of intermediate product int. at any instant is obtained by formula (12),
Figure FDA0002372927340000012
the abbreviations in formulae (11) and (12) have the corresponding meanings as follows: ANT antibiotic contaminants; ROS reactive oxygen species; TiO 22Titanium dioxide; int, intermediate; carrying out PC photocatalytic reaction; ICPB photocatalysis-biodegradation direct coupling; k is a radical of0The rate of reactive oxygen species generation; k is a radical of1Secondary reaction rates of antibiotic contaminants; k is a radical of2The secondary reaction rate of the intermediate product; t time; rmMaximum specific degradation rate of the intermediate product; ksA half-saturation constant; the biomass of X; [ ANT]Represents the concentration of ANT; [ TiO 22]Represents the concentration of titanium dioxide; [ ROS]0Represents the initial concentration of ROS; [ Int.]Represents the intermediate product concentration; the [ Int.]Expressed by Chemical Oxygen Demand (COD); wherein, in formula (12)
Figure FDA0002372927340000013
Wherein the parameter k0、X、[TiO2]、[ROS]0、[ANT]、[Int.]Measured by experimental means, parameter k1、k2、Rm、KsTo be obtained by software fitting.
2. The numerical simulation method according to claim 1, wherein the kinetic model of equation (11) is constructed as follows: the reaction process of ANT in direct coupling of photocatalysis-biodegradation is simplified as follows:
s1) catalyst TiO2Generating reactive species ROS with strong oxidizing property by light excitation, as shown in formula (1)
Figure FDA0002372927340000021
S2) the active species ROS attack the ANT, degrading the ANT into a biodegradable intermediate int, as shown in formula (2),
Figure FDA0002372927340000022
s3) a part of said intermediate product int. is attacked by reactive species ROS to produce products, as shown in formula (3),
Figure FDA0002372927340000023
s4) the remainder of the intermediate int. is biodegraded and eventually mineralized to carbon dioxide and water, as shown in equation (4),
Int.+biodegradation→CO2+H2O (4)
performing secondary reaction kinetic fitting on ANT degradation in the step S2), wherein the secondary reaction kinetic fitting is shown as a formula (5)
Figure FDA0002372927340000024
The change rate of int in step S3) is equal to the photocatalytic generation rate minus the consumption rate, as shown in equation (6)
Figure FDA0002372927340000025
In the direct coupling process of photocatalysis-biodegradation, the change rate of int is equal to the generation rate minus the photocatalysis consumption rate and the biodegradation rate, as shown in formula (7)
Figure FDA0002372927340000031
The rate of change of the reactive species ROS is the rate of production minus the rate of consumption, as shown in equation (8)
Figure FDA0002372927340000032
Integrating the change rate of the ROS to obtain the amount of the ROS at any moment, as shown in a formula (9),
Figure FDA0002372927340000033
the relationship between the reaction rates of said ANT and said int. is expressed by competition kinetics, as shown in equation (10):
k2＝Ak1(10)
wherein
Figure FDA0002372927340000034
Substituting the above formulas (9) and (10) into the formulas (5) and (7) to obtain a kinetic model formula (11) of the ANT degradation reaction:
Figure FDA0002372927340000035
wherein the concentration of the intermediate product int. at any time is obtained by formula (12),
Figure FDA0002372927340000036
the above model building process is based on the following assumptions: a, under a stable state, the biomass is constant in the direct coupling process of photocatalysis-biodegradation; b, biodegradation in the direct coupling process of photocatalysis-biodegradation mineralizes all intermediate products into carbon dioxide finally; c the amount of all active species produced photocatalytically is replaced by the amount of active species that plays the most dominant role.
3. The numerical simulation method according to claim 1, wherein the chemical oxygen demand COD reaction kinetic model is represented by formula (17):
Figure FDA0002372927340000041
wherein [ COD ]]Is the concentration of chemical oxygen demand COD, k3The second order reaction rate of Chemical Oxygen Demand (COD) [ COD]Measured by experimental means, k3Obtained by software fitting.
4. The numerical simulation method according to claim 3, wherein the Chemical Oxygen Demand (COD) reaction kinetic model is constructed by: the degradation rate of the chemical oxygen demand COD is fitted by using second-order reaction kinetics, and is shown as a formula (13):
Figure FDA0002372927340000042
wherein [ ROS ] is obtained by the formula (14),
Figure FDA0002372927340000043
the photocatalytic degradation rate for obtaining the chemical oxygen demand COD in the formula (13) with the formula (14) is shown as a formula (15),
Figure FDA0002372927340000044
in the biodegradation process, the degradation rate of the chemical oxygen demand COD is shown as a formula (16),
Figure FDA0002372927340000045
integration (15) and formula (16) obtained a degradation rate reaction kinetic model of the chemical oxygen demand COD in a photocatalytic-biodegradation direct coupling process:
Figure FDA0002372927340000051
5. the application of the numerical simulation method for directly coupling and degrading the antibiotic wastewater through photocatalysis-biodegradation according to any one of claims 1 to 4 in amplification of a system for directly coupling and degrading the antibiotic wastewater through photocatalysis-biodegradation, control and optimization of system parameters.
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