KR101894834B1 - Method for optimizing process control variable of advanced oxidation process (aop) using radical index determining apparatus with multi-channel continuous flow reactor - Google Patents

Abstract

Automated sequential injection analysis in water treatment system using Advanced Oxidation Process (AOP) and optical fiber equipped with spectrophotometer automatically measure the radical index representing the water quality of raw water, It can be used for process diagnosis and control of oxidant chemicals through the measurement of radical index, and it can calculate the optimized value of ultraviolet irradiation dose and hydrogen peroxide injection amount. Also, it is possible to measure the radical index of the sequential injection analysis with a multi- By using the process simulation program including the energy optimization analysis model, it is possible to perform the process diagnosis to predict the removal ability of harmful substances in the water, and also to control the process of the high oxidation process by calculating the ultraviolet radiation amount and the hydrogen peroxide injection amount that minimize the energy Energy saving and driving Process control of an advanced oxidation process using a radical index measuring apparatus equipped with a multi-channel continuous flow reactor capable of real time process diagnosis and process control by a radical index measuring apparatus having a multi-channel continuous flow reactor Variable optimization methods are provided.

Description

METHOD FOR OPTIMIZING PROCESS CONTROL VARIABLE OF ADVANCED OXIDATION PROCESS (AOP) USING RADICAL INDEX DETERMINATION APPARATUS WITH MULTI-CHANNEL CONTINUOUS FLOW REACTOR FIELD OF THE INVENTION [0001]

The present invention relates to an apparatus for measuring a radical index of a high oxidation process, and more particularly, to an optical oxidation process using an automated sequential injection analysis technique and an ultraviolet spectrophotometer in a water treatment system using an Advanced Oxidation Process (AOP) An apparatus and method for measuring the degree of oxidation of a radical using a radical index measuring apparatus equipped with a multi-channel continuous flow reactor capable of automatically measuring a radical index representing the water quality of raw water and calculating an optimized value of ultraviolet radiation dose and hydrogen peroxide injection amount according to the measured radical index And a method for optimizing process control parameters of an oxidation process.

Most of the domestic water treatment plants use river water as the water source. Recently, due to various pollutants, pollution of the water source is getting worse. Therefore, water treatment technology is needed to supply safe water.

Conventional water treatment methods commonly use sand filtration and chlorine disinfection methods after coagulation sedimentation. However, the conventional water treatment method is a method in which a microorganism such as a new medicinal substance (representative substances: carbamazepine, caffeine, ibuprofen) and a taste odor inducing substance (representative substance: geosmin, 2-methylisoborneol Since there is a limit to the efficient treatment of a drinking water source containing a substance, various oxidation treatment methods are being studied.

Among these oxidation treatment methods, the advanced oxidation process (AOP) maximizes the hydroxyl radical (OH), which is a reaction intermediate product, by using ozone, ultraviolet rays, hydrogen peroxide, and the like to remove the hardly decomposable organic substances in water. Here, the OH radical has the highest oxidizing power and is expected to have an important role in the chemical oxidation treatment. Ozone / high pH using ozone, ultraviolet rays / ozone using ozone / hydrogen peroxide and ultraviolet rays, ultraviolet rays / hydrogen peroxide, and the like are processes for removing harmful substances using such OH radicals. Quot;

For example, when ozone is applied to water treatment, if there are many substances highly reactive with ozone molecules in the treated water, the oxidation process is controlled so that the reaction proceeds by the direct path, and the reaction of the pollutant and ozone is relatively , It is effective to control the oxidation process so as to increase the production of OH radical by taking advantage of the characteristics of the indirect path.

As a method for compensating for the disadvantage of ozone using the oxidizing power of OH radicals, it is possible to improve the removal rate of harmful substances by mixing artificial ozone with hydrogen peroxide and UV. In addition, even when ozone alone is used, the OH radical yield is changed according to the change of the pH, so that the effect of the high oxidation process (AOP) can be obtained with only ozone. The common feature of this advanced oxidation process (AOP) is that it relies on the indirect oxidation of the OH radicals generated from the intermediates rather than expecting treatment effects from the directly injected oxidants. Ultimately, this advanced oxidation process (AOP) maximizes the production of OH radicals to maximize the oxidation effect.

In addition, ultraviolet technology is performed on the same principle as ozone technology and maximizes OH radical by reacting with oxidizing agent such as hydrogen peroxide rather than ultraviolet energy itself. Theoretically, two moles of OH radicals are produced which are produced by the decomposition of one mole of hydrogen peroxide by UV energy. At this time, although the oxidizing power of the OH radical is strong, the OH radical disappears as soon as it is formed in a few milliseconds to a few seconds, and is also highly influenced by a background material (e.g., natural organic matter and alkalinity) Therefore, it is known that the quantification of OH radicals generated in the oxidation reaction at high altitudes is very difficult.

For the quantitative analysis of such high-level oxidation reactions, process diagnosis based on this quantitative analysis and control of oxidant chemicals, it is essential to measure the radical index representing the complex water quality of raw water. In particular, the radical index is affected by the concentration of total organic carbon in the water, alkalinity, pH, and chromaticity. Quantitative analysis of radicals is indispensable in order to analyze the removal ability of organic substances in water in the advanced oxidation process using ozone and the ultraviolet oxidation process using ultraviolet rays, or to determine the injection conditions such as ozone, ultraviolet radiation dose and hydrogen peroxide.

To control the AOP, precise process control can be achieved by predicting the change of the radical index derived from the change of these factors. For this approach, various studies using various process simulation models have been tried.

However, these process simulation models do not correspond to each other and show different patterns. Even when the accurate process simulation model is completed, the pH, temperature, and organic concentration must always be measured for accurate process control. It is very complicated and difficult.

In addition, since the energy used in the process increases proportionally to the amount of ultraviolet irradiation and the amount of oxidizing agent such as hydrogen peroxide, the operating parameters should be adjusted and optimized considering the treatment level of the target material and the energy cost available in the process. In this case, the model predictive control is a control technique using a control input obtained by predicting a future output value by using a process model and optimizing the output value. The closed loop open loop optimal control input is controlled by a closed loop control . In order to approach these complex water quality characteristics and control variables of the process model in a practical way, it is necessary to determine the characteristics of complex water by measuring the radical index in water for application of the advanced oxidation process, The method of doing is useful.

On the other hand, Korean Patent Registration No. 10-1169877 discloses an invention entitled " Method for setting the operating condition of the advanced oxidation water treatment process "as prior art.

In the case of the method of setting the operating conditions of the highly oxidized water treatment process according to the prior art, the amount of the poorly decomposable harmful pollutants contained in the treated water in the UV / H ₂ O ₂ advanced oxidation water treatment process is extremely small, The concentration of p-chlorobenzoic acid (pCBA), which is an indicator of the reaction with OH radicals, was measured by using a highly oxidative water treatment process condition that can treat up to the target treatment concentration, Of the hazardous pollutants of the present invention.

However, in the case of the method of setting the operating conditions of the advanced oxidation water treatment process according to the prior art, a method of expelling the water quality of the raw water is a high performance liquid chromatography (HPLC) method using a chemical substance called pCBA (p-Chlorobenzoic acid) However, there is a problem that a response time for process control is long. In other words, it is impossible to quantify the reactivity of the OH radical interfering factor of the inflow water changing in real time in the case of the operating condition setting method of the advanced oxidation water treatment process according to the prior art, and the pCBA material itself is subjected to high performance liquid chromatography ), It is difficult to apply them as process control and diagnostic factors, and it is also difficult to perform real-time measurement for real-time process optimization.

On the other hand, as a prior art for solving the problem of the operating condition setting method of the advanced oxidation water treatment process disclosed in Korean Patent No. 10-1169877 mentioned above, 10-1306155 discloses an invention titled " Automatic control apparatus and method for an advanced oxidation process using radical inhibiting factors and radical reaction indices ", which will be described with reference to FIGS. 1 and 2. FIG.

FIG. 1 is a configuration diagram showing an automatic control apparatus for an advanced oxidation process using a hydroxyl radical scavenger and a radical reaction index according to a conventional technique, and FIG. 2 is a specific configuration diagram of the measurement unit shown in FIG.

Referring to FIG. 1, an automatic control apparatus for an advanced oxidation process using a radical scavenging factor and a radical reaction index according to the related art includes an altitude oxidation water treatment system for oxidizing the raw water by supplying ultraviolet rays and hydrogen peroxide to raw water The automatic control device for controlling the oxidation process includes a monitoring unit 10, a database 20, a measurement unit 30, a calculation unit 40, and a control unit 50.

The monitoring unit 10 is installed at one side of the raw water inlet to measure and monitor the water quality factor of the raw water including the UV254 absorbance.

The database 20 stores information including chemical reaction information on the contaminant to be removed and chemical reaction information on the indicator material.

The measurement unit 30 measures the OH radical generation inhibition response index taking into consideration the reactivity of a hydroxyl radical (OH) production inhibiting species using rhodamine-B as the indicator substance.

2, the measuring unit 30 includes an ultraviolet lamp 31, an ultraviolet light reactor 35, a hydrogen peroxide storage tank 36, a sample storage tank 33, an indicator material storage tank B), and a pipe 34 having a valve for connecting the storage tank and the photoreactor. An optical fiber 41 connected to the halogen light source supply device 39 and connected to the optical fiber 41 so as to fix the probe tip to the inner side of the reaction tank, and a reflection mirror installed under the tip through the fluid flowing between the probe tips of the reaction tank Is transmitted to the optical fiber 41 through the fluid and detected by the spectrophotometer 37, and the removal rate is continuously measured by measuring the permeability or the absorbance of the indicator substance rhodamine-B.

The measurement unit (30) is a measurement unit (30), in which a sample is filled in the photoreactor, and Rhodamine-B, which is maintained at a predetermined concentration, is injected as an indicator material and an ultraviolet lamp is operated without injecting hydrogen peroxide. (37) is used to measure the rate of decrease of rhodamine-B in the photoreactor, that is, the direct photodegradation rate, and then the hydrogen peroxide is added to measure the indirect photodegradation rate. At this time, Separately, the indirect photodegradation rate is measured three times or more.

The calculation unit 40 calculates the removal ability of the water treatment system for the contaminant to be removed contained in the raw water and calculates the ultraviolet ray irradiation amount and the hydrogen peroxide injection amount according to the target removal rate of the contaminant to be removed.

The control unit 50 corrects and controls the ultraviolet radiation amount and the hydrogen peroxide injection amount required in the advanced oxidation contact facility 60 according to the removal power, the ultraviolet radiation amount, and the hydrogen peroxide injection amount calculated by the calculation unit 40.

According to an automatic control apparatus for an advanced oxidation process using a hydroxyl radical inhibitor and a radical reaction index disclosed in Korean Patent No. 10-1306155, a radical reaction in consideration of the total reactivity of chemical species inhibiting the formation of hydroxyl radical (OH) It is possible to automatically control ultraviolet irradiation dose and hydrogen peroxide injection concentration according to the target removal rate of organic pollutants such as new medicinal substances and taste odor substances present in the target water.

However, in the case of the automatic control system for the advanced oxidation process using the OH radical inhibitor and the radical reaction index, the use of rhodamine-B as the indicator material is considered as an inhibitor of OH radical formation, considering the reactivity of the total chemical species inhibiting the generation of hydroxyl radicals There is a problem in that the irradiation intensity of the ultraviolet ray irradiation equipment can not be automatically controlled and thus the analysis can not be performed in real time under the continuous flow condition of the fluid and therefore it is inconvenient to directly measure the batch .

As a prior art for solving the problem of the operating condition setting method of the advanced oxidation water treatment process disclosed in Korean Patent No. 10-1306155 mentioned above, No. 10-1617822 discloses an invention titled " Apparatus and method for real-time measurement of the hydroxyl radical scavenging factor index of an advanced oxidation process ", which will be described with reference to Fig.

3 is a block diagram of an apparatus for real-time measurement of the hydroxyl radical scavenging factor of an advanced oxidation process according to the prior art.

3, an apparatus 100 for real-time measurement of the radical scavenging factor of a high-level oxidation process according to the related art includes a sample unit 110, a reagent unit 120, an ultraviolet ray reaction unit 130, A material detecting unit 140 and a data analyzing unit 150.

The sample part 110 supplies the raw water to be water-treated on the continuous flow injection pipe 160.

The reagent part 120 supplies a reagent composed of Rhodamine-B 121, hydrogen peroxide 122 and distilled water 123, which are indicator materials, onto the continuous flow injection channel 160. At this time, Rhodamine-B is used as the indicator, and the rhodamine-B is adsorbed to the moving tube because it is a dye. Therefore, it is preferable to use a material which is less stained and easily accumulated and is less likely to be removed by the tube.

The ultraviolet ray reaction unit 130 includes a quartz cell 131 and an ultraviolet lamp 132. The ultraviolet ray reaction unit 130 includes a quartz cell 131 and an ultraviolet lamp 132. The sample unit 110 and the reagent unit 120 are connected to each other through a continuous flow injection channel 160 .

The indicator material detection unit 140 uses a spectrophotometer and measures the concentration of the indicator substance rhodamine-B after the reaction in the ultraviolet ray reaction unit 130.

The data analysis unit 150 includes a numerical calculation algorithm for data collection and signal processing.

In the case of the apparatus for real-time measurement of the hydroxyl radical scavenging factor index in the advanced oxidation process disclosed in Korean Patent No. 10-1617822, in the ultraviolet / hydrogen peroxide high-level oxidation process applied to treat harmful substances with the OH radical as a main mechanism, The concentration of hydrogen peroxide diluted with distilled water and Rhodamine-B, an indicator substance, can be measured in real time by changing the flow rate of the sample on the pipeline and applying a continuous flow injection method that keeps the ultraviolet intensity constant.

In the case of the apparatus for real-time measurement of the hydroxyl radical scavenging factor of the high-level oxidation process, the hydroxyl radical scavenging factor index is measured in the high-level oxidation process applied to remove trace organic pollutants in the water treatment or sewage effluent, / Quantitative elimination of harmful substances, ultraviolet radiation dose and hydrogen peroxide input amount can be accurately calculated through the hydrogen peroxide high-level oxidation process.

Also, in the case of the apparatus for real-time measurement of the radical scavenging factor of the high-level oxidation process, it is possible to real-time self-diagnosis and process optimization for the ultraviolet / hydrogen peroxide high-level oxidation process, and thus can be put to practical use as a technique for maximizing the hydroxyl radical.

Accordingly, in the case of the apparatus for real-time measurement of the hydroxyl radical scavenging factor of such an advanced oxidation process, a method and an apparatus for measuring an indicator substance called rhodamine-B by a continuous flow injection method are disclosed, The problem of using p-Chlorobenzoic acid (pCBA) proposed in the method of setting the operating conditions of the process is solved.

However, in the case of the apparatus for real-time measurement of the hydroxyl radical scavenging factor of the advanced oxidation process disclosed in Korean Patent No. 10-1617822, the shape of the continuous flow reactor is not specifically shown, and the reactor structure is a single reactor, There is a problem that they must be set differently from each other.

As another prior art, Korean Patent No. 10-1640416, filed and filed by the applicant and inventor of the present invention, discloses a chlorine-ultraviolet complex oxidation water treatment apparatus for removing harmful substances from algae Quot; chlorine injection amount and ultraviolet intensity variable control method ".

The Korean Patent No. 10-1640416 discloses a chlorine-ultraviolet complex oxidizing water treatment apparatus that removes noxious substances such as tastes, flavor-causing substances, A combined oxidation water treatment system that uses a two-stage ultraviolet oxidation process in which a hydrogen peroxide-ultraviolet process and a chlorine-UV process are sequentially combined to calculate ultraviolet radiation dose and hydrogen peroxide injection dose depending on the radical index .

However, in the case of such a chlorine-ultraviolet complex oxidation water treatment apparatus, there is a problem that a calculation model for obtaining the optimum solution of the process energy function model is not realized when calculating the ultraviolet irradiation dose and the hydrogen peroxide injection dose with the radical index.

Korean Patent No. 10-1617822 filed on November 14, 2014, entitled " Device and method for real-time measurement of hydroxyl radical scavenging factor index in advanced oxidation process " Korean Patent No. 10-1459376 filed on November 20, 2012, entitled "Advanced oxidation water treatment apparatus equipped with a control system and water treatment process using the same" Korean Patent No. 10-1306155 filed on June 14, 2012, entitled " Automatic Control Apparatus and Method for Advanced Oxidation Process Using Radical Inhibitor and Radical Reaction Index " Korean Patent No. 10-1169877 filed on Nov. 3, 2010, entitled "Method of setting operating conditions for advanced oxidation water treatment process" Korean Patent No. 10-1640416 filed on Apr. 23, 2014, entitled "Chlorine-ultraviolet complex oxidizing water treatment apparatus for removing algae-causing harmful substances and chlorine injection amount and ultraviolet intensity variable using the same Control method "

In order to solve the above-described problems, an object of the present invention is to provide a water treatment system using an Advanced Oxidation Process (AOP), an automated sequential injection analysis technique and an optical fiber equipped with a spectrophotometer, It can be used for process diagnosis and control of oxidant chemicals by measuring the radical index according to the water quality change by automatically measuring the radical index representing the water quality, and it is possible to calculate optimized values of ultraviolet radiation dose and hydrogen peroxide injection amount, And a method for optimizing process control parameters of a high-level oxidation process using a radical index measuring apparatus having a reactor.

A further object of the present invention is to provide a multi-channel continuous flow reactor capable of reducing energy and providing ease of operation by calculating ultraviolet radiation dose and hydrogen peroxide injection amount that minimize energy and performing process control of the advanced oxidation process And a method for optimizing process control parameters of a high-level oxidation process using the apparatus for measuring a radical index.

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As a means for achieving the above technical object, there is provided a method for optimizing a process control parameter in an advanced oxidation process using a radical index measuring apparatus equipped with a multi-channel continuous flow reactor, comprising the steps of: A method for optimizing a process control parameter of an advanced oxidation process using a measuring device, comprising the steps of: a) setting a process energy according to a process energy optimization analysis model of an advanced oxidation process; b) measuring a radical index using a radical index measuring apparatus having a multi-channel continuous flow reactor, and setting a target removal rate for a harmful substance; c) calculating ultraviolet radiation dose, hydrogen peroxide injection amount, and total power energy consumption required for the harmful substance removal rate; d) deriving an optimal solution corresponding to the calculated ultraviolet radiation dose and hydrogen peroxide injection amount according to a Newton-optimized numerical model; e) determining whether the set process energy is greater than the calculated total power energy consumption; f) re-adjusting the target removal rate if the set process energy is not greater than the calculated total power energy consumption; g) determining whether the derived optimal solution is satisfactory; And h) monitoring the energy and controlling the process corresponding to the optimal solution if the derived optimal solution is a satisfactory level, wherein the radical index measuring device with the multi-channel continuous flow reactor of step b) The ultraviolet irradiation dose and the hydrogen peroxide injection dose are optimized for removing the target contaminants while minimizing the energy used in the advanced oxidation process by using the radical index measured by the method.

According to the present invention, in a water treatment system to which an advanced oxidation process using ultraviolet (AOP) is applied, a process simulating program including a radical index measuring apparatus for sequential injection analysis with a multi-channel continuous flow reactor and a process energy optimization analysis model It is possible to perform a process diagnosis that predicts the ability to remove harmful substances in the water.

According to the present invention, it is possible to reduce the energy and provide the convenience of operation by calculating the ultraviolet radiation dose and the hydrogen peroxide injection amount that minimize the energy and performing the process control of the advanced oxidation process.

According to the present invention, maximizing the hydroxyl radical (OH) to remove harmful organic contaminants can maximize the process performance while minimizing the process energy of the ultraviolet oxidation process using ultraviolet rays.

According to the present invention, it is possible to perform real-time process diagnosis and process control by means of a radical index measuring apparatus equipped with a multi-channel continuous flow reactor.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a block diagram showing an automatic control apparatus for an advanced oxidation process using a radical scavenger and a radical reaction index according to a conventional technique.
2 is a specific configuration diagram of the measurement unit shown in Fig.
3 is a block diagram of an apparatus for real-time measurement of the hydroxyl radical scavenging factor of an advanced oxidation process according to the prior art.
4 is a block diagram of an apparatus for measuring a radical index with a multi-channel continuous flow reactor according to an embodiment of the present invention.
5 is a view illustrating a quartz multi-channel continuous flow reactor shown in FIG.
6 is a photograph showing the quartz multi-channel continuous flow reactor shown in FIG.
FIG. 7 is a diagram illustrating finding an optimal solution according to a Newton-optimized numerical model applied to an apparatus for automatically measuring a radical index with a multi-channel continuous flow reactor according to an embodiment of the present invention.
FIG. 8 is a flowchart illustrating a method of optimizing a process control parameter of an advanced oxidation process using a radical index measuring apparatus having a multi-channel continuous flow reactor according to an embodiment of the present invention.
FIG. 9 is a diagram for explaining a process simulation program for an advanced oxidation process using ultraviolet rays, which is applied to a process control parameter optimization method for an advanced oxidation process according to an embodiment of the present invention.
10 is a diagram illustrating the calculation range of the optimized ultraviolet intensity and the hydrogen peroxide injection concentration calculated by the Newton-optimized numerical model in the process control parameter optimization method of the elevation oxidation process according to the embodiment of the present invention.
FIG. 11 is a graph illustrating an ultraviolet ray dose and an optimal amount of hydrogen peroxide injection according to the removal level of microcystin, which is an algae toxic substance, in the process control parameter optimization method of the elevated oxidation process according to the embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings, which will be readily apparent to those skilled in the art. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and similar parts are denoted by like reference characters throughout the specification.

Throughout the specification, when an element is referred to as "comprising ", it means that it can include other elements as well, without excluding other elements unless specifically stated otherwise. Also, the term "part" or the like, as described in the specification, means a unit for processing at least one function or operation, and may be implemented by hardware or software or a combination of hardware and software.

First, Korean Patent No. 10-1617822 filed and filed by the applicant and inventors of the present invention discloses an invention titled " Apparatus and method for real-time measurement of the hydroxyl radical scavenging factor index in the high oxidation process " , Which is incorporated herein by reference.

4 to 6, an apparatus for measuring a radical index with a multi-channel continuous flow reactor according to an embodiment of the present invention will be described with reference to FIGS. 7 to 11, A method for optimizing process control parameters of a high-level oxidation process using a radical index measuring apparatus equipped with a channel continuous flow reactor will be described.

[Radius index measuring apparatus (200) equipped with a multi-channel continuous flow reactor]

FIG. 4 is a schematic view of an apparatus for measuring a radical index with a multi-channel continuous flow reactor according to an embodiment of the present invention, FIG. 5 is a view illustrating a quartz multi-channel continuous flow reactor shown in FIG. 4, 6 is a photograph showing the quartz multi-channel continuous flow reactor shown in FIG.

Referring to FIG. 4, an apparatus 200 for measuring a radical index with a multi-channel continuous flow reactor according to an embodiment of the present invention is characterized in that, in a water treatment technique using an ultraviolet oxidation process using an ultraviolet ray, The ultraviolet reaction unit 230 includes a sample supply unit 210, a reagent supply unit 220, an ultraviolet ray reaction unit 230, a surface material detection unit 240, and a data analysis and process control unit 250. Channel continuous flow reactor 231, an automatic dispenser 232, a reactor cell 233, and an ultraviolet lamp 234. The multi-

The sample supply unit 210 supplies the raw water to be treated through the sample supply pump 271 onto the continuous flow injection channel 260.

The reagent supply unit 220 is connected to the reagent supply pump 272 through the reagent supply pumps 272, 273 and 274 and is made up of indicator materials such as Rhodamine-B 221, hydrogen peroxide 222 and distilled water 223. The reagent is supplied on the continuous flow injection conduit (260). At this time, Rhodamine-B is used as the indicator, and Rhodamine-B is adsorbed to the moving tube because the sample is a dye.

The ultraviolet ray reactor 230 includes a multichannel continuous flow reactor 231, an automatic dispenser 232, a reactor cell 233 and an ultraviolet lamp 234. The sample supply unit 210 and the reagent supply unit 220 Is connected on a continuous flow injection conduit (260) connected in a continuous flow injection manner.

The surface material detection unit 240 uses a spectrophotometer implemented as an optical cable and measures the concentration of the indicator material Rhodamine-B 221 after the reaction in the ultraviolet ray reaction unit 230.

The data analysis and process control unit 250 may be implemented, for example, by a computer. The data analysis and process control unit 250 collects and analyzes data from the surface material detection unit 240, and uses the measured radical index to measure the process energy And the optimum values of the ultraviolet radiation dose and the hydrogen peroxide injection amount, which are control variables for removing the target contaminants, are calculated.

Specifically, the apparatus 200 for measuring a radical index with a multi-channel continuous flow reactor according to an embodiment of the present invention measures a radical index of a target raw material, such as Rhodamine-B (221) And the decrease rate of Rhodamine-B (221) is measured by a stepwise passive analysis several times over the conditions of ultraviolet irradiation intensity and concentration of hydrogen peroxide.

In the case of Korean Patent No. 10-1617822 mentioned above, it is necessary to carry out a stepwise measurement analysis by a manual method in order to measure a radical index. In particular, in order to fluctuate ultraviolet radiation dose, . This is because the ultraviolet irradiation dose (mJ / cm 2) is a factor calculated from the intensity (mW / cm 2) of the ultraviolet ray and the contact time (sec).

In order to solve the problem that the shape of the reactor is not specified in the case of the above-mentioned Korean Patent No. 10-1617822, in the apparatus 200 for measuring a radical index with a multi-channel continuous flow reactor according to the embodiment of the present invention, , The reactor structure is composed of a quartz multi-channel continuous flow reactor 231 as shown in Figs. 5 and 6. In addition, an automatic dispenser 232 is installed at one side of the multichannel continuous flow reactor 231 to change the flow direction automatically by the residence time so that the sample is automatically distributed according to the set time. At this time, By storing it in the reactor cell 233 of the vessel, it becomes a structure capable of measuring the radical index without any fluctuation of the flow rate. 5 shows an actual structure of the continuous flow reactor 231 of the multi-channel structure applied to the apparatus 200 for measuring a radical index. As shown in FIG. 4, the indicator material detector 240 implemented as an optical cable in the visible light region, for example, continuously measures Rhodamine-B 221 by a spectrophotometer, and the measured rhodamine- B (221), a radical index to be reflected in the water quality of raw water is automatically measured according to the following equation (5).

Specifically, the apparatus 200 for measuring a radical index with a multi-channel continuous flow reactor according to an embodiment of the present invention supplies a target raw water sample to a continuous flow injection conduit 260, B (221), which is an indicator substance, and transfers the mixture to the ultraviolet ray reaction unit (230) at a constant flow rate. Then, the reactivity of the indicator material, Rhodamine-B 221, is detected by the indicator material detector 240, which is a spectrophotometer, by optimizing ultraviolet irradiation dose and hydrogen peroxide injection amount without fluctuation of the flow rate of the indicator material mixed with the target raw water sample.

On the continuous flow pipe 260, a target raw water for obtaining a radical index, Rhodamine-B 221 as an index substance, hydrogen peroxide 222 as an oxidizing agent, and distilled water 223 are mixed. At this time, the Rhodamine-B 221 and the hydrogen peroxide 222 are injected into the target raw water at a predetermined concentration, and a sample supply pump 271 and reagent supply pumps 272, 273 and 274 are provided . At this time, the target raw water sample to be injected is set to be 95% or more of the total flow rate in order to minimize the error caused by the other reagents 221, 222, and 223 to be mixed.

Also, the Rhodamine-B 221 is injected so that the initial concentration remains constant at 1 uM while the apparatus 200 for measuring a radical index with a multi-channel continuous flow reactor according to the embodiment of the present invention is operated, About 2.5% or less of the total amount is introduced.

At this time, the concentration of the hydrogen peroxide 222 can be changed from a minimum of 0 mg / L to a maximum of 150 mg / L according to the concentration condition, and about 2.5% or less of the total flow rate is set to flow. In order to change the hydrogen peroxide concentration (H ₂ O ₂ ) while maintaining the total flow rate thus set, the concentration of hydrogen peroxide injected per condition is changed. At this time, the concentration of the hydrogen peroxide 222 to be injected is controlled by adjusting the injection ratio of the hydrogen peroxide concentrate 222 and the distilled water 223 at the high concentration during the hydrogen peroxide injection.

The ultraviolet ray reacting unit 230 is a section in which the chemical reaction of the hydroxyl radical (OH) generated by the physical reaction of the mixed sample with the ultraviolet ray irradiator occurs and the injected rhodamine-B 221 is irradiated with ultraviolet rays and OH radicals This is the section to be removed. In this case, the multi-channel continuous flow reactor 231 of the ultraviolet ray reactor 230 may be formed of a quartz material so as to transmit the ultraviolet rays emitted from the ultraviolet lamp 234.

Specifically, the ultraviolet lamp 234 is fixed on the upper portion of the multi-channel continuous flow reactor 231 to emit ultraviolet rays at a predetermined distance and intensity. Since the ultraviolet lamp 234 requires a certain time to irradiate ultraviolet rays of a certain intensity, the apparatus for measuring a radical index 200 having a multi-channel continuous flow reactor according to an embodiment of the present invention Stabilization time is required.

In the method of measuring a radical index having a multi-channel continuous flow reactor according to an embodiment of the present invention, first, an ultraviolet ray irradiation amount to be irradiated through the ultraviolet lamp 234 is set, B 221 and hydrogen peroxide 222 supplied from the reagent supply unit 220 are set. Next, the target raw water and Rhodamine-B 221 are injected and mixed on the continuous flow injection conduit 260, and the concentration of the hydrogen peroxide 222 is set to be applied to the continuous flow injection conduit 260 Inject.

Next, the index substance detection unit 240 measures the concentration of rhodamine-B 221, which is an index substance, and repeatedly performs the measurement according to the hydrogen peroxide concentration conditions.

Next, the above-described process is repeatedly performed according to ultraviolet irradiation dose conditions. When the index material detection unit 240 transmits the detected data to the data analysis and process control unit 250, the data analysis and process control unit 250 The received data is analyzed to derive the hydroxyl radical scavenger index.

As a result, according to the apparatus for measuring a radical index having a multi-channel continuous flow reactor according to an embodiment of the present invention, in a water treatment system to which an AOP is applied using ultraviolet rays, By using the process simulator program including the radical index measuring device and the process energy optimization analysis model, it is possible to perform the process diagnosis to predict the removal ability of harmful substances in the water. In addition, it is possible to perform real-time process diagnosis and process control by using a radical index measuring apparatus equipped with a multi-channel continuous flow reactor, and to maximize the hydroxyl radical (OH) so as to remove harmful organic pollutants, Maximizing process performance while minimizing process energy.

Meanwhile, by using the radical index measured by the apparatus 200 for measuring a radical index with a multi-channel continuous flow reactor according to an embodiment of the present invention, it is possible to minimize the process energy used in the high- Optimization values of ultraviolet irradiation dose and hydrogen peroxide injection amount, which are control variables for removal, should be calculated.

[Method for Optimizing Process Control Variables in Advanced Oxidation Process using Radical Index Measuring Apparatus]

7 is a diagram illustrating finding an optimal solution according to a Newton's optimization numerical model applied to an apparatus for automatically measuring a radical index with a multi-channel continuous flow reactor according to an embodiment of the present invention.

를 그려 그래프 상에 임의의

값을 지정하고, 이 값을

라 한다. 다음 단계로서,

에서 접선을 그린 후, 이러한 접선과

축이 만나는 점을

이라고 하며, 이때, 접선에 해당하는 식은 다음의 수학식 1과 같이 나타낼 수 있다. Referring to FIG. 7, the Newton-optimized numerical model is a very efficient method for finding an approximate value or an actual value of a general function. As shown in FIG. 7, a method of obtaining a root using the Newton-optimized numerical model is as follows.

On the graph.

Specify a value, and

. As a next step,

After drawing the tangent line,

The point where the axis meets

Here, the equation corresponding to the tangent can be expressed by the following equation (1).

The general model equation for this Newton-optimized numerical model is shown in Equation 2 below.

Equation (3) means ultraviolet radiation dose for removing the removal rate (R%) of harmful substances in water in the reactor and Equation (4) is used for the amount of hydrogen peroxide drug. However, the energy consumed in the high-level oxidation process (AOP) using ultraviolet rays is proportional to the dose of ultraviolet radiation and the amount of hydrogen peroxide injected as shown in Equation (5).

)에 필요한 자외선(UV) 조사량인

(단위는 mJ/㎠)는 다음의 수학식 3과 같이 구할 수 있다.Specifically, the harmful substance removal rate (

), Which is the ultraviolet (UV)

(Unit: mJ / cm < 2 >) can be obtained by the following equation (3).

는 자외선 강도(단위는 W/㎠)를 나타내고,

는 조사 시간(단위는 분(min))을 나타내며,

는 유해물질 제거율(단위는 %)을 나타내고,

및

는 각각 254㎚ 몰흡광계수(단위는 M^-1㎝^-1)를 나타내며,

및

는 각각 양자수득률(단위는 mol/einstein)을 나타내고,

는 254㎚ 자외선의 흡광도(단위는 ㎝^-1)를 나타내며,

는 분광광도계를 이용하여 254㎚에서 측정한 UV 흡수물질 측정값인 광에너지 단위변환상수(단위는 J/einstein^-1)를 나타내고,

는 과산화수소와 OH 라디칼의 이차반응속도상수(단위는 M^-1s^-1)를 나타내며,

는 과산화수소 주입량(단위는 ㎎/L)을 나타낸다.here,

(Unit: W / cm < 2 >),

Represents the irradiation time (unit: min)

Represents the removal rate of harmful substances (unit is%),

And

(Unit: M < ^-1 > cm <" ¹ &

And

Represents the quantum yield (unit: mol / einstein), respectively,

Represents the absorbance (unit: cm ^-1 ) of 254 nm ultraviolet light,

Represents a light energy unit conversion constant (unit: J / einstein ^-1 ), which is a UV absorbing material measurement value measured at 254 nm using a spectrophotometer,

Represents the secondary reaction rate constant (unit: M ^-1 s ^-1 ) of hydrogen peroxide and OH radical,

Represents the amount of hydrogen peroxide injected (unit: mg / L).

(단위는 ㎎/L)은 다음의 수학식 4와 같이 구할 수 있다.Next, the hydrogen peroxide injection amount

(Unit: mg / L) can be obtained by the following equation (4).

는 OH 라디칼지수(단위는 sec^-1)를 나타내며,

는 유해물질 제거율(단위는 %)을 나타내고, 또한,

는 254㎚ 자외선의 흡광도(단위는 ㎝^-1)를 각각 나타낸다.here,

Represents an OH radical index (unit: sec ^-1 )

Represents the removal rate of harmful substances (unit is%),

Represents the absorbance (unit: cm ^-1 ) of 254 nm ultraviolet light.

)는 다음의 수학식 5와 같이 구할 수 있다.At this time, the OH radical index (

) Can be obtained by the following equation (5).

는 OH 라디칼과 과산화수소의 이차반응속도상수를 나타내며,

은 채널별 측정된 로다민-B 감소속도 함수의 기울기를 나타내고,

는 채널별로 측정된 로다민-B 함수의 절편을 나타내며,

는 OH 라디칼과 로다민-B의 이차반응 속도상수를 나타내고,

는 로다민-B의 초기농도를 나타낸다.here,

Represents the secondary reaction rate constant of the OH radical and hydrogen peroxide,

Represents the slope of the measured rhodamine-B decay rate function for each channel,

Represents a segment of a rhodamine-B function measured for each channel,

Represents the secondary reaction rate constant of the OH radical and rhodamine-B,

Indicates the initial concentration of rhodamine-B.

On the other hand, the ultraviolet irradiation dose and hydrogen peroxide injection amount are the main energy used in the process in the ultraviolet oxidation technique. Therefore, it is necessary to calculate the optimized values of the ultraviolet irradiation dose and the hydrogen peroxide injection amount, which are control variables for removing the target contaminants while minimizing the energy used in the process. Therefore, the energy used in the process is proportional to the dose of ultraviolet radiation and the dose of hydrogen peroxide drug as shown in Equation (6) below.

(단위는 ㎾h/㎥)는 다음의 수학식 6과 같이 구할 수 있다.That is, the total power energy consumption

(Unit: kWh / m < 3 >) can be obtained by the following Equation (6).

는 자외선(UV)에 의한 전력 소비량(단위는 ㎾h/㎥)을 나타내고,

는 과산화수소(

)에 의한 전력 소비량(단위는 ㎾h/㎥)을 나타내며,

는 대상원수 시료에 적용된 UV 조사량(단위는 J/㎡)을 나타내고,

는 반응기 광조사 길이(단위는 m)를 나타내며,

는 자외선램프 효율(단위는 %)을 나타내고,

는 과산화수소(

) 주입농도(단위는 ㎏/㎥)를 각각 나타낸다.here,

(Unit: kWh / m < 3 >) by ultraviolet (UV)

Hydrogen peroxide

(Unit: kWh / m < 3 >),

(Unit: J / m < 2 >) applied to the target raw water sample,

(Unit: m) of the reactor,

Represents the ultraviolet lamp efficiency (unit:%)

Hydrogen peroxide

) Injection concentration (unit: kg / m < 3 >).

함수값을 최적화(최소화)시키는 공정제어변수의 조합을 찾아야 한다. 이때, 상기 최적화된 공정제어변수의 조합인 자외선 조사량과 과산화수소 주입량의 조합은 전술한 뉴턴(Newton) 최적화 수치모델이 구현된 공정모사 프로그램으로 최적화된 공정제어변수를 도출할 수 있다.In other words, in Equation (6), which takes Equations (3) and (4)

You should find a combination of process control variables that optimize (minimize) the function value. At this time, the combination of the ultraviolet radiation dose and the hydrogen peroxide injection dose, which is a combination of the optimized process control variables, can obtain an optimized process control variable by the process simulation program implementing the Newton optimization numerical model described above.

Meanwhile, FIG. 8 is a flowchart illustrating a method of optimizing a process control parameter in a high-level oxidation process using a radical index measuring apparatus having a multi-channel continuous flow reactor according to an embodiment of the present invention.

Referring to FIG. 8, a method for optimizing process control parameters of a high-level oxidation process using a radical index measuring apparatus having a multi-channel continuous flow reactor according to an embodiment of the present invention includes: Then, the process energy is set (S201). Here, the process energy optimization analysis model of the advanced oxidation process is embedded in the data analysis and process control unit 250 as described above.

Next, a radical index is measured using a radical index measuring apparatus equipped with a multi-channel continuous flow reactor according to an embodiment of the present invention, and a target removal rate for harmful substances is set (S202).

Next, the ultraviolet radiation dose is calculated by the above-described equation (3), the hydrogen peroxide injection amount is calculated by the equation (4), and the total power energy consumption is calculated by the equation (6) (S203).

Next, an optimal solution corresponding to the ultraviolet radiation amount and the hydrogen peroxide injection amount is derived according to the Newton-optimized numerical model according to the above-described Equations 1 and 2 (S204).

Next, it is determined whether the set process energy is greater than the calculated total power energy consumption (S205).

Next, if the set process energy is not greater than the calculated total power energy consumption, the target removal rate is readjusted (S206). At this time, when the set process energy is larger than the calculated total power energy consumption, the process corresponding to the derived optimal solution is controlled.

Next, it is determined whether the derived optimal solution is satisfactory (S207). At this time, if the derived optimal solution is not satisfactory, the target removal rate is readjusted until the derived optimal solution reaches a satisfactory level.

Next, if the derived optimal solution is satisfactory, the energy is monitored (S208) and the process corresponding to the optimal solution is controlled (S209).

Therefore, according to the method of optimizing the process control parameters of the advanced oxidation process using the apparatus for measuring a radical index with a multi-channel continuous flow reactor according to the embodiment of the present invention, in the water treatment technique using the ultraviolet oxidation technique, And the combination of the ultraviolet radiation dose and the hydrogen peroxide injection amount that minimizes the radical processing energy can be calculated.

FIG. 9 is a diagram for explaining a process simulation program for an advanced oxidation process using ultraviolet rays, which is applied to a process control parameter optimization method for an advanced oxidation process according to an embodiment of the present invention.

As shown in FIG. 9, the process simulation program of the ultraviolet oxidation process using ultraviolet rays, which is applied to the process control variable optimization method of the advanced oxidation process according to the embodiment of the present invention, The optimum solution corresponding to the ultraviolet irradiation dose and the hydrogen peroxide injection dose can be derived.

10 is a diagram illustrating the calculation range of the optimized ultraviolet intensity and the hydrogen peroxide injection concentration calculated by the Newton-optimized numerical model in the process control parameter optimization method of the altitude oxidation process according to the embodiment of the present invention.

As shown in FIG. 10, the optimum operating conditions are shown by dotted lines according to the calculated range of the ultraviolet intensity and the hydrogen peroxide injection concentration calculated by the Newton-optimized numerical model for the contaminants to be removed.

FIG. 11 is a graph illustrating an ultraviolet irradiation amount and an optimal amount of hydrogen peroxide injection according to the removal level of microcystin, which is an alga toxic substance, in the process control parameter optimization method of the elevation oxidation process according to the embodiment of the present invention.

As shown in FIG. 11, when the concentration of microcystin in water is 100 μg / L, the ultraviolet radiation dose optimized to a treatment water concentration of 4 μg / L is 885 mJ / cm 2 to remove 99% microcystin , The amount of hydrogen peroxide injection was calculated to be about 2 mg / L, the ultraviolet radiation dose optimized to 40 μg / L of treatment water concentration to remove 90% of microcystin was 575 mJ / cm 2, and the amount of hydrogen peroxide injection was about 1 mg / .

As a result, according to the method for optimizing the process control parameters of the advanced oxidation process using the apparatus for measuring radical index with a multi-channel continuous flow reactor according to an embodiment of the present invention, the ultraviolet radiation dose and the hydrogen peroxide injection amount, (OH) to maximize the removal of harmful organic pollutants, thereby minimizing the process energy of the high-level oxidation process using ultraviolet rays, and improving the process performance Can be maximized.

It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims rather than the detailed description and all changes or modifications derived from the meaning and scope of the claims and their equivalents are to be construed as being included within the scope of the present invention do.

200: Measuring instrument of radical index
210:
220: reagent supply unit
230: ultraviolet ray reaction part
240:
250: Data analysis and process control unit
260: continuous flow injection pipe
221: Rhodamine-B
222: hydrogen peroxide
223: distilled water
231: Multi-channel continuous flow reactor
232: Automatic dispenser
233: reactor cell
234: ultraviolet lamp
271: Sample supply pump
272, 273, 274: Reagent supply pump

Claims (13)

delete delete delete delete delete A method for optimizing process control parameters of a high-level oxidation process using a radical index measuring apparatus having a multi-channel continuous flow reactor,
a) setting the process energy according to a process energy optimization analysis model of the high-level oxidation process;
b) measuring a radical index using a radical index measuring apparatus (200) equipped with a multi-channel continuous flow reactor, and setting a target removal rate for a harmful substance;
c) Removal rate of harmful substances (

), A hydrogen peroxide injection amount, and a total power energy consumption;
d) deriving an optimal solution corresponding to the calculated ultraviolet radiation dose and hydrogen peroxide injection amount according to a Newton-optimized numerical model;
e) determining whether the set process energy is greater than the calculated total power energy consumption;
f) re-adjusting the target removal rate if the set process energy is not greater than the calculated total power energy consumption;
g) determining whether the derived optimal solution is satisfactory; And
h) monitoring the energy and controlling the process corresponding to the optimal solution if the derived optimal solution is at a satisfactory level
, ≪ / RTI &
The radical index measured by the radical index measuring apparatus 200 having the multi-channel continuous flow reactor of the step b) is used to minimize the energy used in the high-level oxidation process, Wherein the optimum value of the irradiation dose and the hydrogen peroxide injection amount is calculated. The method of optimizing the process control parameters of the advanced oxidation process using the apparatus for measuring a radical index with a multi-channel continuous flow reactor. The method according to claim 6,
In the step b), the radical index measured by the apparatus for measuring a radical index (200) having the multi-channel continuous flow reactor

),

Lt; / RTI >

Represents the secondary reaction rate constant of the OH radical and hydrogen peroxide,

Represents the slope of the measured rhodamine-B decay rate function for each channel,

Represents a segment of a rhodamine-B function measured for each channel,

Represents the secondary reaction rate constant of the OH radical and rhodamine-B,

Characterized in that the initial concentration of rhodamine-B is the initial concentration of rhodamine-B. The method according to claim 6,
In order to minimize the energy to remove the harmful substances at a desired target removal rate level in the step c), the total power energy consumption amount (

) As an objective function,

Channel continuous flow reactor, characterized in that the combination of ultraviolet radiation dose and hydrogen peroxide injection dose that minimizes the function value is calculated, and the process diagnosis is performed by predicting the removal rate of toxic substances by a process simulation program implementing the Newton-optimized numerical model A Method for Optimizing Process Control Variables for Advanced Oxidation Processes Using a Radical Index Measuring Device. The method according to claim 6,
In step c), the removal rate of harmful substances

) Required for ultraviolet irradiation (

)silver,

Lt; / RTI >

Indicates ultraviolet light intensity,

Represents the irradiation time,

Represents the removal rate of harmful substances,

And

Respectively, exhibit a molar extinction coefficient of 254 nm,

And

Respectively represent the quantum yield,

Represents the absorbance of ultraviolet light of 254 nm,

Represents a light energy unit conversion constant, which is a UV absorbing material measurement value measured at 254 nm using a spectrophotometer,

Represents the secondary reaction rate constant of hydrogen peroxide and OH radical,

Characterized in that the concentration of hydrogen peroxide is expressed as the amount of hydrogen peroxide injected. 10. The method of claim 9,
The amount of hydrogen peroxide injected in step c)

)silver,

Lt; / RTI >

Represents an OH radical index,

Represents the removal rate of harmful substances,

And the absorbance of ultraviolet ray of 254 nm, respectively, in a high-frequency oxidation process. The method according to claim 6,
The total power energy consumption in step c)

),

Lt; / RTI >

Represents the power consumption by ultraviolet (UV) light,

Represents the power consumption by hydrogen peroxide,

Represents the UV irradiation amount applied to the target raw water sample,

Lt; / RTI > represents the reactor light irradiation length,

Represents the ultraviolet lamp efficiency,

Wherein the concentration of hydrogen peroxide is expressed as a concentration of hydrogen peroxide. The method according to claim 6,
Wherein in the step (f), when the set process energy is greater than the calculated total power energy consumption, the process corresponding to the derived optimal solution is controlled. A Method for Optimizing Process Control Variables for Advanced Oxidation Processes. The method according to claim 6,
Wherein the target removal rate is readjusted until the derived optimal solution becomes a satisfactory level, when the derived optimal solution is not satisfactory in step g). ≪ RTI ID = 0.0 > A Method for Optimizing Process Control Variables in Advanced Oxidation Process using Measuring Device.

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