KR102602624B1 - Chemiluminescence analysis device for evaluating the behavior of reactive oxygen species and chemiluminescence analysis method using the same - Google Patents

Abstract

The present invention discloses a chemiluminescence analysis device for evaluating the behavior of reactive oxygen species. A chemiluminescence analysis device according to an embodiment of the present invention includes a chamber part for accommodating an analysis object containing reactive oxygen species, a luminol injection part for injecting a luminol solution into the analysis object in the chamber, the reactive oxygen species of the analysis object and the An optical fiber unit that transmits a wavelength of light generated by chemiluminescence of luminol in a luminol solution, a detection unit that detects the wavelength of light transmitted from the optical fiber unit and converts it into an electrical signal, and the electrical signal converted from the detection unit. It is characterized by including a calculation device for storing and calculating.

Description

Chemiluminescence analysis device for evaluating the behavior of reactive oxygen species and chemiluminescence analysis method using the same

The present invention enables identification and quantitative evaluation of the behavior of reactive oxygen species generated in the photocatalytic reaction of the advanced oxidation process, measurement of light intensity from an optical perspective, observation of chemiluminescence through real-time measurement, and the use of luminol and an oxidizing agent capable of chemiluminescence. It relates to a chemiluminescence analysis method and device capable of measuring the intensity of chemiluminescence and the light energy emitted.

To date, wastewater containing various non-degradable organic pollutants has been treated using various advanced oxidation treatment research methods. Oxidation treatment has been used to decompose non-decomposable pollutants into water and CO ₂ using strong oxidizing agents such as ozone and H ₂ O ₂ , but this method is economically expensive and generates secondary pollutants. There were possible downsides. To solve these shortcomings, advanced oxidation treatment is being developed as a research method that decomposes organic pollutants by generating reactive oxygen species with strong oxidizing and reducing properties.

Research on various advanced oxidation treatments has been conducted to remove various non-degradable organic pollutants in the water system. The photocatalytic reaction, which has high oxidation power and rapid processing in advanced oxidation treatment, uses reactive oxygen species, a powerful oxidizing agent, to decompose non-decomposable pollutants into water and CO ₂ and has the advantage of not generating secondary pollutants. However, since reactive oxygen species are strong oxidizing agents, it is difficult to evaluate their behavior due to the fast oxidation reaction rate, and there is a lack of analytical methods for quantitatively measuring the amount produced. We attempted to improve applicability by solving these problems and presenting analysis methods as new guidelines. Research was conducted on device configuration and analysis methods that enable real-time and in-situ quantification of reactive oxygen species.

Japanese Published Patent P2006-520507 “Photocatalyst activity evaluation method and photocatalyst activity evaluation device”

The purpose of the present invention is to propose an analysis method and device for quantitatively measuring the amount of reactive oxygen species produced by solving the difficulties in evaluating the behavior due to the fast oxidation reaction rate and extinction rate of reactive oxygen species.

Specifically, The luminescence intensity of light is measured in real time using chemiluminescence analysis using chemical luminescence caused by the reaction between luminol and reactive oxygen species, and the luminescence intensity of light measured in real time is substituted into the formula to confirm the quantitative production of reactive oxygen species. It is possible to propose an analysis method and device that can evaluate the behavior of reactive oxygen species in situ due to changes in light emission intensity.

A chemiluminescence analysis device for evaluating the behavior of reactive oxygen species according to an embodiment of the present invention includes a chamber part for accommodating an analysis object containing reactive oxygen species, and a luminol injection for injecting a luminol solution into the analysis object in the chamber part. Part, an optical fiber part that transmits the wavelength of light generated by chemiluminescence of reactive oxygen species of the analyte and luminol of the luminol solution, detects the wavelength of the light transmitted from the light fiber part and generates an electric signal It includes a detection unit that converts the electrical signal into a signal, and a calculation device that stores and calculates the electrical signal converted from the detection unit.

The chamber unit of the chemiluminescence analysis device for evaluating the behavior of reactive oxygen species according to an embodiment of the present invention may further include a reactor for accommodating the analysis object, and a light irradiation unit for irradiating light to the analysis object accommodated in the reactor. You can.

The light irradiation unit of the chemiluminescence analysis device for evaluating the behavior of reactive oxygen species according to an embodiment of the present invention may be characterized by irradiating visible light or ultraviolet (UV) light.

The visible light of the chemiluminescence analysis device for evaluating the behavior of reactive oxygen species according to an embodiment of the present invention has a wavelength of 380 nm to 1100 nm, and the ultraviolet ray may be characterized by using a wavelength of 200 nm to less than 380 nm. .

The luminol injection unit of the chemiluminescence analysis device for evaluating the behavior of reactive oxygen species according to an embodiment of the present invention includes a luminol container section equipped with the luminol solution, a luminol injection device for delivering the luminol solution provided in the luminol container section, and It may be characterized by including a luminol injection port for injecting the luminol solution delivered from the luminol injection device into the analysis object of the chamber unit.

The optical fiber unit of the chemiluminescence analysis device for evaluating the behavior of reactive oxygen species according to an embodiment of the present invention uses multi-mode optical fiber (MMF), single-mode step index fiber (SMF), and dispersion. It may be one selected from the group consisting of Compensated Optical Fiber (DCF, Dispersion Compensated Fiber) and Low Water Peak Fiber (LWPF).

The detection unit of the chemiluminescence analysis device for evaluating the behavior of reactive oxygen species according to an embodiment of the present invention may be characterized as a spectrophotometer that detects and analyzes the wavelength of light and converts it into an electrical signal. .

The calculation device of the chemiluminescence analysis device for evaluating the behavior of reactive oxygen species according to an embodiment of the present invention is characterized by including a monitor that can calculate the electrical signal converted from the detection unit and then digitize or image it and transmit it. can do.

A chemiluminescence spectrometry method for evaluating the behavior of reactive oxygen species according to another embodiment of the present invention includes preparing an analysis object containing reactive oxygen species in the chamber portion of a chemiluminescence analysis device for evaluating the behavior of reactive oxygen species; Injecting a luminol solution into the object to be analyzed, chemically reacting with reactive oxygen species of the object to be analyzed and luminol in the luminol solution to emit light, transmitting the wavelength of light from the light emission to the detection unit by the optical fiber unit, the detection unit It includes detecting the wavelength of light and converting it into an electrical signal, and storing and calculating the value converted into the electrical signal in a calculation device.

The step of preparing an analyte containing the reactive oxygen species in the chemiluminescence spectrometry method for evaluating the behavior of reactive oxygen species according to another embodiment of the present invention occurs externally through advanced oxidation processes (AOPs). It is characterized by preparing an analysis object containing reactive oxygen species, or preparing an analysis object containing reactive oxygen species generated through a reaction step of reactants, photocatalysts, and light.

The photocatalyst used in chemiluminescence analysis for evaluating the behavior of reactive oxygen species according to another embodiment of the present invention includes titanium oxide (TiO ₂ ), zinc oxide (ZnO), cadmium sulfide (CdS), zirconium oxide (ZrO ₂ ), and metal. It is characterized by at least one selected from the group consisting of gC ₃ N ₄ -TiO ₂ (Graphitic carbon nitride titanium dioxide), which is an oxide semiconductor, and Fe-TNT (iron doped titanium nanotubes), which is a complex metal oxide.

The above calculation of the chemiluminescence spectrometry method for evaluating the behavior of reactive oxygen species according to another embodiment of the present invention is characterized in that it is calculated according to the following calculation formula 1.

[Calculation Formula 1]

Amount of reactive oxygen species produced (μM) = α Х Amount of luminol reaction (μM) = α´(μM/μW) Х Intensity of actual light generated (μW).

In the calculation formula 1 above, the intensity of the actually generated light (μW) = the intensity of the measured light (μW) Х e ^(k*d) ,

The α is the reaction constant (1≤α) between the amount of reactive oxygen species produced and the reaction amount during the luminol reaction,

The α´ is the reaction constant (α´≤1) between the amount of reactive oxygen species generated during luminol reaction and the actual luminescence intensity,

The k is the rate of decrease according to distance of the intensity of the actually generated light,

The d(cm) is the distance from the actual light generation location to the optical fiber.

In order to identify reactive oxygen species generated on the photocatalyst surface according to the chemiluminescence analysis device and chemiluminescence analysis method according to an embodiment of the present invention, the wavelength of light generated from chemiluminescence with luminol is measured and recorded in real time to evaluate behavior and quantitatively. There is an effect that can be measured.

In order to confirm the reactive oxygen species generated on the surface of the photocatalyst according to the chemiluminescence analysis device and chemiluminescence analysis method according to an embodiment of the present invention, the wavelength of light generated from chemiluminescence with luminol is measured and recorded in real time to determine the reactive oxygen species. Energy measurement has the effect of enabling effective control and prediction of decomposition when decomposing organic pollutants in water.

According to the chemiluminescence analysis device and chemiluminescence analysis method according to an embodiment of the present invention, the energy of reactive oxygen species present in the analysis object can be confirmed, quantitative measurement is possible, and the resulting organic pollutant decomposition can be effectively controlled. There is.

According to the chemiluminescence analysis device and chemiluminescence analysis method according to an embodiment of the present invention, it is possible to demonstrate the photocatalytic reaction and increase the possibility of developing an advanced oxidation treatment process.

Figure 1 shows the configuration of a chemiluminescence analysis device for evaluating the behavior of reactive oxygen species according to an embodiment of the present invention (Figure 1a) and an image of an example of the same (Figure 1b).
Figure 2 shows a step diagram for a chemiluminescence spectrometry method for evaluating the behavior of reactive oxygen species according to another embodiment of the present invention.
Figure 3 shows a portable configuration diagram of a chemiluminescence analysis device for evaluating the behavior of reactive oxygen species according to an embodiment of the present invention.
Figure 4 is a blank test using chemiluminescence analysis to evaluate the behavior of reactive oxygen species according to another embodiment of the present invention, and a graph of performance evaluation results to confirm the luminescence phenomenon of reactive oxygen species and luminol.
Figure 5 is a graph showing the results of checking the chemiluminescence intensity of reactive oxygen species and luminol using chemiluminescence analysis to evaluate the behavior of reactive oxygen species according to another embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings and the contents described in the accompanying drawings, but the present invention is not limited or limited by the embodiments.

The terminology used herein is for describing embodiments and is not intended to limit the invention. As used herein, singular forms also include plural forms, unless specifically stated otherwise in the context. As used herein, “comprises” and/or “comprising” refers to the presence of one or more other components, steps, operations and/or elements. or does not rule out addition.

As used herein, “embodiment,” “example,” “aspect,” “example,” etc. should be construed to mean that any aspect or design described is better or advantageous than other aspects or designs. It's not like that.

Additionally, the term 'or' means an inclusive OR 'inclusive or' rather than an exclusive OR 'exclusive or'. That is, unless otherwise stated or clear from the context, the expression 'x uses a or b' means any of the natural inclusive permutations.

Additionally, as used in this specification and claims, the singular expressions “a” or “an” generally mean “one or more,” unless otherwise indicated or it is clear from the context that the singular refers to singular forms. It should be interpreted as

Additionally, a part of an act, layer, area, component request, etc., is said to be "on" or "on" another part, not only when it is directly on top of the other part, but also when there are other acts, layers, areas, or components in between. Also includes cases where etc. are included.

Hereinafter, a chemiluminescence analysis device for evaluating the behavior of reactive oxygen species according to an embodiment of the present invention will be described with reference to the attached drawings.

Figure 1a shows a schematic diagram of a chemiluminescence analysis device for evaluating the behavior of reactive oxygen species according to an embodiment of the present invention.

Referring to FIG. 1A, the chemiluminescence analysis device 100 for evaluating the behavior of reactive oxygen species includes a chamber part 110 that accommodates an analysis object containing reactive oxygen species, and a luminol solution to the analysis object in the chamber part 110. A luminol injection unit 120 that automatically injects, an optical fiber unit 130 that transmits the wavelength of light generated by chemiluminescence of reactive oxygen species of the analyte and luminol of the luminol solution, transmitted from the optical fiber unit 130. It includes a detection unit 140 that detects the received wavelength of light and converts it into an electrical signal, and a calculation device 150 that stores and calculates the electrical signal converted from the detection unit.

The chemiluminescence analysis device 100 according to an embodiment of the present invention is in a bench-scale form.

The chamber unit 110 may further include a reactor 112 for accommodating the analysis object, and a light irradiation unit 114 for irradiating light to the analysis object accommodated in the reactor 112.

The chamber portion 110 has a hexahedral shape that does not allow light to enter, and has a structure that allows one side to be opened and closed.

Accordingly, by opening one side, the analysis object can be prepared by continuously supplying it to the reactor 112 through a small pump, or the reactor 110 in which the analysis object is prepared in a batch manner can be accommodated in the chamber portion 110.

The reactor 112 containing the analysis object may be a reactor made of glass or ceramics, and the shape of the reactor is a flat reactor capable of containing the analysis object, and its shape is not limited.

However, the preferred shape for the reactor may be a cylindrical or polygonal flat column shape and may be made of glass. Preferably, it may be a Petri Dish.

The reactor 112 may further include a stirrer, and the stirrer may be a magnetic bar.

The magnetic rod rotates to promote and homogenize the chemical reaction by stirring the analyte.

The light irradiation unit 114 may irradiate visible light or ultraviolet rays using a visible light irradiation bulb and an ultraviolet irradiation bulb, and may be provided with both the visible light irradiation bulb and the infrared irradiation bulb, or may be detachable as needed.

The visible light using the visible light irradiation bulb can be irradiated using a visible light LED lamp or a visible fluorescent lamp capable of irradiating light with a wavelength of 380 nm to 1100 nm. One or more visible LED lamps or visible fluorescent lamps can be used, and the visible light wavelength can be adjusted according to the wavelength of light required during the experiment. .

The ultraviolet rays using the infrared irradiation bulb can be irradiated using an ultraviolet LED lamp capable of irradiating light with a wavelength of less than 200 nm to 380 nm. One or more ultraviolet LED lamps can be used, and the wavelength of ultraviolet light can be adjusted according to the wavelength of light required during the experiment. .

The luminol injection unit 120 includes a luminol container unit 122 containing a luminol solution, a luminol injection device 124 for delivering the luminol solution provided in the luminol container unit 122, and the luminol injection device 124 that delivers the luminol solution provided in the luminol container unit 122. It includes a luminol injection port 126 through which a luminol solution is injected into the analysis object of the chamber unit 110.

The luminol container unit 122 may be a container of various shapes, but specifically, it may be a container in the form of a cylinder or a polygonal column, and may be a group made of glass and pottery, which are materials that are resistant to alkalinity due to sodium hydroxide, the solvent of the luminol solution. It may be one of the materials.

Preferably, it may be a column-shaped container made of glass, and more preferably, a glass beaker may be used.

The luminol injection device 124 is an automatic injection device that delivers a constant concentration or a certain amount of the luminol solution in the aqueous state of the luminol container portion 122 to the luminol injection port 126. The automatic injection device is a pump device. there is.

The luminol injection device 124 can control the flow rate of the luminol solution flowing into the luminol injection port 126. The flow rate of the luminol solution can be adjusted through the injection speed of the luminol solution.

The luminol inlet 126 may have a sharp inlet end in the shape of a cone or polygonal horn, and the end may be directed toward the reactor of the chamber unit 110. Additionally, the luminol solution can be dropped into the reactor 112 of the chamber portion 110 in the form of droplets using the tip.

The optical fiber unit 130 detects a wavelength of light generated by chemiluminescence resulting from a chemical reaction between the reactive oxygen species in the analysis object contained in the reactor 112 of the chamber unit 110 and the luminol solution. It plays a role in conveying to.

The optical fiber unit 130 is made of optical fiber, which includes multi-mode optical fiber (MMF), single-mode step index fiber (SMF), and dispersion compensated fiber (DCF). , may be one selected from the group consisting of low water peak fiber (LWPF).

The detection unit 140 may be a spectrophotometer that detects and analyzes the wavelength of light and then converts it into an electrical signal. In particular, the detection unit 140 can convert the wavelength of light transmitted through the optical fiber unit 130 into an electrical signal and transmit it in real time to the calculation device 150 that converts the amount of reactive oxygen species generated.

The calculation device 150 may include a monitor that can calculate the electrical signal converted from the detection unit 140 and then convert it into numbers or images and transmit it.

The calculation device 150 may be a personal computer (PC) or a terminal device that converts the electrical signal for the wavelength of light detected by the detection unit 140 into the amount of reactive oxygen species generated.

The above calculation can calculate the amount of reactive oxygen species produced according to equation 1 below.

[Calculation Formula 1]

Amount of reactive oxygen species produced (μM) = α Х Amount of luminol reaction (μM) = α´(μM/μW) Х Intensity of actual light generated (μW).

In the above calculation equation 1, the actual intensity of light generated (μW) = the measured light intensity (μW) Х e ^(k*d) , where α is the reaction constant between the amount of reactive oxygen species produced during the luminol reaction and the reaction amount (1 ≤α) and is a dimensionless constant, where α´ is the reaction constant between the amount of reactive oxygen species generated during luminol reaction and the actual luminous intensity (α´≤1), and k is the reduction rate of the actual intensity of light generated according to distance. , and d(cm) is the distance from the actual light generation location to the optical fiber.

The above calculation formula is a calculation formula that can confirm the amount of production and reaction of reactive oxygen species by utilizing the actual luminescence intensity during chemiluminescence of luminol and reactive oxygen species. Depending on the reactor using the reaction constant (a') between the amount produced and the actual luminous intensity and the amount of reactive oxygen species produced, it may be used in situations other than one embodiment of the present invention, depending on changes and modifications.

Figure 2 shows a step diagram of a chemiluminescence spectrometry method for evaluating the behavior of reactive oxygen species according to another embodiment of the present invention.

The chemiluminescence analysis method includes preparing an analyte containing reactive oxygen species in the chamber part of a chemiluminescence analysis device for evaluating the behavior of reactive oxygen species (S100), and injecting a luminol solution into the analyte (S200). , a step of emitting light through a chemical reaction between the reactive oxygen species of the analyte and the luminol of the luminol solution (S300), a step of transmitting the wavelength of light caused by the light emission to the detection unit by the optical fiber unit (S400), and the step of transmitting the light from the detection unit to the detection unit (S400). It includes detecting a wavelength and converting it into an electrical signal (S500), and storing and calculating the value converted into the electrical signal in a calculation device (S600).

The step of preparing the analyte (S100) is to prepare an analyte containing reactive oxygen species generated externally by advanced oxidation processes (AOPs), or through reaction with reactants, photocatalysts, and light. An analyte containing reactive oxygen species, which is a reaction product, can be prepared.

The photocatalyst includes titanium oxide (TiO ₂ ), zinc oxide (ZnO), cadmium sulfide (CdS), zirconium oxide (ZrO ₂ ), gC ₃ N ₄ -TiO ₂ (Graphitic carbon nitride -titanium dioxide), a metal oxide semiconductor, and composite. It may be one or more selected from the group consisting of Fe-TNT (iron doped titania nanotubes), which is a metal oxide. Additionally, the Fe-TNT may be one selected from the group consisting of thin film Fe-TNT and granular Fe-TNT photocatalyst.

The photocatalyst increases the amount of reactive oxygen species produced through a photocatalytic reaction with the reactant, and as the amount of reactive oxygen species produced increases, the efficiency of chemiluminescence with luminol increases, thereby improving analysis efficiency.

The light may be visible light or ultraviolet (UV) light.

In the step of injecting the luminol solution into the analysis object (S200), a certain amount of the luminol solution is moved to the reactor in the chamber portion through the luminol injection device.

In the step of injecting the luminol solution into the analysis object (S200), the luminol concentration of the luminol solution used in one embodiment of the present invention was set so that no oxygen species could not react when the maximum reactive oxygen species was generated.

The luminol concentration of the luminol solution reaches its maximum intensity at about 1.5 times the concentration of reactive oxygen species, so a concentration of 1 to 1.5 times is an appropriate concentration.

The concentration of the luminol solution according to an embodiment of the present invention is prepared to be about 1.5 times the maximum amount of reactive oxygen species generated and moved to the reactor 112 of the chamber unit 110 using a luminol injection device.

The maximum concentration of reactive oxygen species according to an embodiment of the present invention is 2.2 Χ 10 ^-1 μM, so the luminol concentration of the luminol solution can be prepared and used at a concentration of 33.4 Χ 10 ^-2 μM, which is about 1.5 times higher. Therefore, the luminol concentration of the luminol solution used in one embodiment of the present invention may be 2.2 Χ 10 ^-1 μM to 33.4 Χ 10 ^-2 μM, and preferably 33.4 Χ 10 ^-2 μM.

If the luminol concentration is 2.2 Χ 10 ^-1 μM or less, the emission retention time is reduced and identification is impossible, and if the luminol concentration is more than 33.4 Χ 10 ^-2 μM, the intensity of light during chemiluminescence exceeds the maximum, making it useless. It is unnecessary in

In the step of injecting the luminol solution into the analysis object (S200), the luminol solution injection speed can vary depending on the photocatalyst input amount and the capacity of the reactor in the chamber portion.

The luminol solution injection rate used in one embodiment of the present invention was set at 0.04 L/hr. In the case of one embodiment of the present invention, a batch experiment was conducted to inject a constant luminol solution into the reactor of the chamber portion, and the injection rate was adjusted according to Scheme 1 below to maintain the concentration inside the reactor of the chamber portion.

<Scheme 1>

(a) Batch reaction (L/hr): P = 1.5

In the case of a continuous reaction chamber, that is, a continuous reaction chamber manufactured to continuously supply the analysis object to the reactor in the chamber section through a small pump, the speed of the sample flowing into the reactor in the chamber section and the internal volume of the reactor in the chamber section are adjusted. It is calculated using the calculation formula in Scheme 2 below.

<Scheme 2>

(b) Continuous reaction (L/hr): P = C / (1-1.5

At this time, in Scheme 1 and Scheme 2, may be the luminol injection rate (L/hr), and T may be the residence (reaction) time of the reactor (hr).

The step of preparing the analyte (S100) and the step of injecting the luminol solution into the analyte (S200) may be performed in a reactor within the chamber portion, and the reaction within the reactor must occur uniformly, and the materials within the reactor must occur uniformly. Must be able to mix thoroughly.

In the step (S300) of emitting light through a chemical reaction between the reactive oxygen species of the analyte and the luminol of the luminol solution, the luminol of the luminol solution is a chemical substance that exhibits chemiluminescence, and the reactive oxygen species (OH·, O ₂ ^-) , which is an oxidizing agent, ·) reacts with it to generate chemiluminescence, which emits blue light.

The intensity of chemiluminescence is proportional to the amount of reactive oxygen species, which is the oxidizing agent, and the amount of luminol, and there is a limit to the intensity depending on the amount of reactive oxygen species.

In particular, there is a maximum intensity of light generated in chemiluminescence between reactive oxygen species and luminol. For example, when the reactive oxygen species generated on the photocatalyst surface is 1 mol, the maximum intensity of chemiluminescence is reached even if the luminol input amount is more than 1 mol, because only 1 mol of the reactive oxygen species is used, and vice versa.

The shape is not limited, but must be thoroughly mixed so that the reaction can occur uniformly.

The step of transmitting the wavelength of light by light emission (S400) is generated by chemiluminescence that appears when the optical fiber part of the chemiluminescence analysis device chemically reacts with the reactive oxygen species in the analysis object accommodated in the reactor of the chamber part and the luminol solution. This is the step of transmitting the wavelength of light to the detection unit.

In the step (S500) of detecting and converting the wavelength of the transmitted light into an electrical signal, the wavelength of the light of the transmission panel is analyzed by a spectrophotometer, which is a detection unit, and then converted into an electrical signal to calculate the amount of reactive oxygen species generated. This is the stage of real-time delivery.

The step of storing and calculating the converted electrical signal is a step of calculating the converted electrical signal using a calculation device and then displaying the converted electrical signal into a number or image and transmitting it to a monitor. The calculation device may be a personal computer (PC) or a terminal device that converts and calculates the electrical signal for the wavelength of light detected by the spectrophotometer, which is the detection unit, into the amount of reactive oxygen species generated.

The above calculation can calculate the amount of reactive oxygen species produced according to equation 1 below.

[Calculation Formula 1]

Amount of reactive oxygen species produced (μM) = α Х Amount of luminol reaction (μM) = α´(μM/μW) Х Intensity of actual light generated (μW).

In the above calculation equation 1, the actual intensity of light generated (μW) = the measured light intensity (μW) Х e ^(k*d) , where α is the reaction constant between the amount of reactive oxygen species produced during the luminol reaction and the reaction amount (1 ≤α), where α´ is the reaction constant (α´≤1) between the amount of reactive oxygen species generated during luminol reaction and the actual luminous intensity, k is the rate of decrease according to distance of the actual intensity of light generated, and d is the distance from the actual location of light generation to the optical fiber.

Figure 3 shows the configuration of a portable chemiluminescence analysis device 200 for evaluating the behavior of reactive oxygen species and the chemiluminescence analysis processing steps. The portable chemiluminescence analysis device 200 is of a portable-scale type.

Referring to FIG. 3, the portable chemiluminescence analysis device 200 for evaluating the behavior of reactive oxygen species consists of a housing 201, a reactant injection device located inside the housing and injecting an analyte containing reactive oxygen species ( 205), a chamber part 210 for accommodating the analysis object, a luminol injection device 224 for injecting a luminol solution into the analysis object in the chamber part 210; An optical fiber unit 230 transmits a wavelength of light generated by chemiluminescence of the reactive oxygen species of the analyte and luminol of the luminol solution, and detects the wavelength of the light transmitted from the optical fiber unit 230 to generate an electrical signal. It includes a detection unit 240 that converts the electrical signal to , and a calculation device 250 that stores and calculates the electrical signal converted from the detection unit 240.

The analyte is prepared by preparing an analyte containing reactive oxygen species generated externally by advanced oxidation processes (AOPs), or reactive oxygen, which is a reaction product generated through reaction with a reactant, a photocatalyst, and light. Analytical objects containing species can be prepared.

The photocatalyst includes titanium oxide (TiO ₂ ), zinc oxide (ZnO), cadmium sulfide (CdS), zirconium oxide (ZrO ₂ ), gC ₃ N ₄ -TiO ₂ (Graphitic carbon nitride -titanium dioxide), a metal oxide semiconductor, and composite. It may be one or more selected from the group consisting of Fe-TNT (iron doped titania nanotubes), which is a metal oxide. Additionally, the Fe-TNT may be one selected from the group consisting of thin film Fe-TNT and granular Fe-TNT photocatalyst.

The photocatalyst increases the amount of reactive oxygen species produced through a photocatalytic reaction with the reactant, and as the amount of reactive oxygen species produced increases, the efficiency of chemiluminescence with luminol increases, thereby improving analysis efficiency.

The reactant injection device 201 is connected to a reactant preparation container 203 that stores the reactant.

The chamber unit 210 includes a small reactor 212 in which the analyte and the luminol solution react, and a light irradiation unit 214 that irradiates visible light or infrared rays to the small reactor 212.

The luminol injection device 224 is connected to the luminol container portion 222 that stores luminol.

The housing 201 may have a polygonal column shape, a hexahedral shape, etc., and the top or one side may be separated or opened and closed.

The size of the housing 201 may be 20 to 40 cm in width and 20 to 40 cm in height,

The height can be adjusted depending on the height of the chamber unit 210, and the preferred height may be within 10 cm.

The size of the housing 201 may be suitable for the size of a laptop tailored to its portable nature.

The specific size of the housing 201 may be 20 to 40 cm in width and 20 to 40 cm in length, and the height may be adjusted depending on the height of the chamber portion 210, and the preferred height may be within 10 cm.

The chamber unit 210 may further include a reactor 212 for accommodating the analysis object, and a light irradiation unit 214 for irradiating light to the analysis object accommodated in the reactor 212.

The reactor 212 that accommodates the analyte is injected into the chamber 210 using the reaction solution injection device 205 from the reactant preparation container 203 in which the analyte containing reactive oxygen species is prepared to prepare the analyte. Get ready.

The analyte containing reactive oxygen species in the reactant preparation container 203 may be an aqueous solution in which advanced oxidation processes (AOPs) are actively occurring externally.

The reactor 212 that accommodates the analysis object may be a reactor made of glass or ceramics, and the shape of the reactor is a flat reactor that can contain the analysis object, and its shape is not limited.

The reactor 212 may further include a magnetic bar, and the magnetic bar may rotate to assist chemical reaction by stirring the analyte.

The reaction liquid injection device 205 may be a first pump device that delivers the analysis reactant containing reactive oxygen species from the reactant preparation vessel 203 to the reactor 212 of the chamber unit 210.

The luminol injection device 224 may be a second pump device that delivers the luminol solution in the luminol container portion 222 to the reactor 212 in the chamber portion 210.

The luminol injection device 224 is an automatic injection device that delivers a constant concentration or a certain amount of the luminol solution flowing into the reactor 212 of the chamber portion 210. The flow rate of the luminol solution can be adjusted through the injection speed of the luminol solution.

In the luminol injection step, the luminol solution injection speed can vary depending on the photocatalyst input amount and the capacity of the reaction chamber. The injection rate of the luminol solution used in one embodiment of the present invention was set at 0.04 L/hr. Luminol was administered in proportion to the maximum amount of reactive oxygen species generated under the experimental conditions according to an embodiment of the present invention, and the injection rate at which circulation was possible within the reaction chamber was calculated.

The optical fiber unit 230 detects a wavelength of light generated by chemiluminescence resulting from a chemical reaction between the reactive oxygen species in the analysis object contained in the reactor 212 of the chamber unit 210 and the luminol solution. It plays a role in conveying to.

The optical fiber unit 230 is made of optical fiber, and the optical fiber includes a multi-mode optical fiber (MMF), a single-mode step index fiber (SMF), and a dispersion compensated fiber (DCF). , may be one selected from the group consisting of low water peak fiber (LWPF).

The detection unit 240 may be a spectrophotometer that detects and analyzes the wavelength of light and then converts it into an electrical signal.

The calculation device 250 may include a monitor that can calculate the electrical signal converted from the detection unit 240 and then convert it into numbers or images and transmit it.

The calculation device 250 may be a personal computer (PC) or a terminal device that converts the intensity of the wavelength of light detected by the detection unit 240 into the amount of oxygen species generated.

Therefore, it is possible to detect reactive oxygen species by converting the intensity of light from the reactor transmitted through the optical fiber unit 230 in the spectrophotometer, which is the detection unit 240, and connecting it to the computer, which is the calculation device 250.

Also, referring to FIG. 3, the steps of the chemiluminescence analysis processing method using the portable chemiluminescence analysis device 200 for evaluating the behavior of reactive oxygen species include a reactant injection step (S01), a reactant information transfer step (S02), and a reactant transfer step. Step (S03), luminol solution injection step (S04), luminol information transfer step (S05), luminol solution transfer step (S06), chemiluminescence reaction transfer step (S07), electrical signal conversion step (S08), small reactor occurrence situation It includes an information display step (S09) and a sample discharge step (S10).

The reactant injection step (S01) is a step in which water, sewage, and wastewater are moved to the portable chemiluminescence analysis device 200 using a pump. More specifically, this is the step of moving water, sewage, and wastewater existing outside the portable chemiluminescence analysis device 200 into the portable chemiluminescence analysis device 200 using a pump.

The reactant information transfer step (S02) is a step in which information about the concentration and injection speed of the reactant transferred to the portable chemiluminescence analysis device is transferred to the conversion calculator screen.

The reactant transfer step (S03) is a step in which water, sewage and wastewater injected into the chemiluminescence analysis device 200 through the reactant injection step (S01) are moved to the small reactor 232 through a pump.

The luminol solution injection step (S04) is a step of automatically injecting the luminol solution into the luminol cartridge 222 using the luminol injection device 224. More specifically, it is a step of moving from the luminol cartridge 222 to the luminol injection device 224.

The luminol information transfer step (S05) is a step in which the speed information of the luminol solution injected from the luminol cartridge 222 is converted and moved to the screen of the calculation device 250.

The luminol solution transfer step (S06) is a step in which the luminol solution is moved from the luminol cartridge 222 to the small reactor 232 using the second automatic pump, which is the luminol injection device 223. More specifically, this is the step in which the luminol solution moves from the luminol injection device 223 to the small reactor 232.

In the chemiluminescence reaction transfer step (S07), the optical fiber unit 230 transmits the chemiluminescence generated in the small reactor 232 to a spectrophotometer, which is the detection unit 240, by transmitting the wavelength of light.

The electrical signal conversion step (S08) converts the wavelength of light transmitted through the optical fiber unit 230 measured by the spectrophotometer, which is the detection unit 240, into an electrical signal and sends it to the screen of the calculation device 250. This is the transmission stage.

In the small reactor generation situation information display step (S09), information about the situation in which light is generated by the reaction of luminol and the analyte object in the small reactor and the progress status according to the temporal change in the intensity of light generation is moved to the screen. This is the step to display situation information.

The sample discharge step (S10) is a step in which the analyte (sample) and luminol solution in which the chemiluminescence reaction of reactive oxygen species and luminol has been completed are discharged from the small reactor 232.

Preparation example 1.

Bisphenol A (BPA) aqueous solution is prepared by adding 50 mg/L BPA to 1L distilled water, and the BPA aqueous solution, not the mixed sample, is first used as the target wastewater.

Preparation example 2.

The luminol solution is prepared by dissolving 0.46 g of luminol in 1 L of 0.1 M NaOH solution.

Preparation example 3.

Prepare distilled water.

Comparative Example 1.

<Adjusting the base line of the spectrophotometer>

Prepare the chemiluminescence analysis device of the present invention. By connecting the spectrophotometer of the chemiluminescence analysis device of the present invention and the computer program, the light intensity and wavelength range are confirmed before the start of the experiment, and the fixed light intensity and wavelength are set.

Using the sample (distilled water) of Preparation Example 3, set the range of wavelengths used in the experiment and set the light intensity of the main experimental range to 0. Afterwards, only the intensity of light generated by chemiluminescence analysis is measured and recorded.

Connect the computer program, Spectrophotometer, and Fiber to record the intensity of light observed through the sample (distilled water) of Preparation Example 3 above.

Based on the intensity of light measured in this way, the current intensity of light is designated as 0.

<Spectrophotometer basic performance evaluation of chemiluminescence analysis device>

Example 1.

The chemiluminescence intensity is measured using the chemiluminescence analysis device of the present invention, which includes a spectrophotometer with a base line set according to Comparative Example 1.

Without irradiating ultraviolet rays to the sample prepared according to Preparation Example 2 above, the chemiluminescence intensity is measured using a spectrophotometer with a base line set as above.

Example 2.

The same procedure as in Example 1 was performed, but the distilled water prepared according to Preparation Example 3 was irradiated with ultraviolet rays with an intensity of 5.6 W/m2sec for 1 hour, and then subjected to a spectrophotometer ( The chemiluminescence intensity is measured using the chemiluminescence analysis device of the present invention, which includes a spectrophotometer.

Example 3.

The same procedure as in Example 1 was performed, but the sample prepared according to Preparation Example 2 was irradiated with ultraviolet rays with an intensity of 5.6 W/m2sec for 1 hour, and then a spectrophotometer ( The chemiluminescence intensity is measured using the chemiluminescence analysis device of the present invention, which includes a spectrophotometer.

The measurement results of Examples 1 to 3 are shown in Figure 4.

Figure 4(a) is the result of Example 1 in which the chemiluminescence intensity of the sample prepared according to Preparation Example 2 was measured using a spectrophotometer without UV irradiation, and Figure 4(b) shows the results of distilled water prepared according to Preparation Example 3. This is the result of Example 2 in which the chemiluminescence intensity was measured using a spectrophotometer after irradiating ultraviolet rays with an intensity of 5.6 W/㎡sec for 1 hour, and (c) shows the intensity of the sample prepared according to Preparation Example 2 with an intensity of 5.6 W/㎡. This is the result of Example 3, in which the chemiluminescence intensity was measured using a spectrophotometer after irradiating sec ultraviolet rays for 1 hour.

Referring to FIG. 4, in FIG. 4(c), you can see the result of chemiluminescence due to the chemical reaction in which luminol reacts with reactive oxygen species.

<Confirmation of chemiluminescence intensity of reactive oxygen species and luminol>

Example 4.

The chemiluminescence intensity is measured using the chemiluminescence analysis device of the present invention, which includes a spectrophotometer with a base line set according to Comparative Example 1.

1500 ml of the sample prepared according to Preparation Example 1 was placed in the reactor of the chemiluminescence analysis device of the present invention, irradiated with ultraviolet light for 960 seconds, 1620 seconds, 2400 seconds, 3600 seconds, and 6000 seconds, and then applied to the base as above. The intensity of light was measured using a chemiluminescence analysis device including a spectrophotometer with a line set.

At this time, stirring using a magnetic bar is performed at 100 RPM inside the reactor inside the chemiluminescence analysis device. While stirring was maintained, the light intensity of chemiluminescence of reactive oxygen species was measured.

Example 5.

The same procedure as in Example 4 was performed, but the sample prepared according to Preparation Example 1 was added to 1500 ml of the sample in the reactor of the chemiluminescence analysis device of the present invention at 10 ml/min of luminol solution, and 1000 mg/L of photocatalyst TiO ₂ was added. , After irradiating UV light for 960 seconds, 1620 seconds, 2400 seconds, 3600 seconds, and 6000 seconds, the light intensity is measured using a chemiluminescence analysis device including a spectrophotometer with the base line set as above. Measured.

At this time, 1000 mg/L of TiO2, a photocatalyst, was added to 1500 mL of the sample in the reactor inside the chemiluminescence analysis device, and then stirred at 100 RPM to spread the photocatalyst throughout the sample. While maintaining stirring, the prepared luminol solution is injected into the sample at a rate of 10 mL/min, and luminol and Measure the light intensity of chemiluminescence of reactive oxygen species.

Example 6.

The same procedure as Example 5 was performed, except that the sample prepared according to Preparation Example 2 was used instead of the sample prepared according to Preparation Example 1.

The experimental results of Examples 4 to 6 are shown in Figure 5.

Figure 5(a) is a graph comparing the chemiluminescence intensity of Example 4 and the chemiluminescence intensity of luminol and reactive oxygen species according to Examples 5 and 6.

Figure 5(b) is a table comparing the energy capacity of luminol and reactive oxygen species and the efficiency of ultraviolet irradiation amount during the ultraviolet irradiation time according to Example 5 and Example 6.

According to Figures 5(a) and 5(b), it can be seen that there is a difference in the chemiluminescence intensity of luminol and reactive oxygen species depending on the time during the ultraviolet irradiation time. Comparing the two experiments using the luminol solution of Example 6 and the experiment of Example 5 in which a luminol sample was mixed with bisphenol A, an organic material, the amount of light emitted when irradiated with light varies depending on the conditions of each sample. You can see that the intensity changes.

In particular, Figure 5(a) compares the energy capacity and efficiency according to ultraviolet irradiation time at the inflection point of the luminescence intensity, and the amount of reactive oxygen species generated and reaction amount can be confirmed due to the area of the graph.

As described above, although the present invention has been described using limited embodiments and drawings, the present invention is not limited to the above embodiments, and various modifications and variations can be made from these descriptions by those skilled in the art. This is possible. Therefore, the scope of the present invention should not be limited to the described embodiments, but should be determined by the claims and equivalents thereof as well as the claims described later.

100: Chemiluminescence analysis device
110, 210: chamber part 112: reactor
114, 214: Light irradiation department
120: Luminol injection part 122, 222: Luminol container part
124, 224: Luminol injection device 126: Luminol injection port
130, 230: Optical fiber unit
140, 240: detection unit
150, 250: Calculating device
200: Portable chemiluminescence analysis device
201: Housing of portable chemiluminescence analysis device
203: reactant preparation vessel 205: reaction liquid injection device
210: small reactor

Claims (12)

A chamber part that accommodates analytes or reactants containing reactive oxygen species generated externally by advanced oxidation processes (AOPs), analytes containing reactive oxygen species generated through the reaction step of photocatalysts, and light. ;
A luminol injection unit for injecting a luminol solution into the analysis object of the chamber unit;
an optical fiber unit transmitting a wavelength of light generated by chemiluminescence of reactive oxygen species of the analyte and luminol contained in the luminol solution;
a detection unit that detects the wavelength of light transmitted from the optical fiber unit and converts it into an electrical signal; and
It includes a calculation device that stores and calculates the electrical signal converted from the detection unit,
The luminol concentration of the luminol solution is 1 to 1.5 times the reactive oxygen species concentration,
The luminol concentration of the luminol solution is 2.2 Х 10 ^-1 μM to 33.4 Х 10 ^-2 μM. A chemiluminescence analysis device for evaluating the behavior of reactive oxygen species.
According to paragraph 1,
The chamber unit is a chemiluminescence analysis device for evaluating the behavior of reactive oxygen species, characterized in that it further comprises a reactor for accommodating the analysis object and a light irradiation unit for irradiating light to the analysis object accommodated in the reactor.
According to paragraph 2,
A chemiluminescence analysis device for evaluating the behavior of reactive oxygen species, wherein the light irradiation unit irradiates visible light or ultraviolet (UV) light.
According to paragraph 3,
The visible light has a wavelength of 380 nm to 1100 nm,
A chemiluminescence analysis device for evaluating the behavior of reactive oxygen species, characterized in that the ultraviolet ray uses a wavelength of less than 200 nm to 380 nm.
According to paragraph 1,
The luminol injection unit includes a luminol container unit containing the luminol solution;
A luminol injection device for delivering the luminol solution; and
A chemiluminescence analysis device for evaluating the behavior of reactive oxygen species, comprising a luminol injection port for injecting the luminol solution delivered from the luminol injection device into the analysis object in the chamber.
According to paragraph 1,
The optical fiber unit consists of multi-mode optical fiber (MMF), single-mode step index fiber (SMF), dispersion compensated fiber (DCF), and low water peak fiber (LWPF). A chemiluminescence analysis device for evaluating the behavior of reactive oxygen species, characterized in that it is any one selected from the group consisting of.
According to paragraph 1,
A chemiluminescence analysis device for evaluating the behavior of reactive oxygen species, characterized in that the detection unit is a spectrophotometer that detects and analyzes the wavelength of light and converts it into an electrical signal.
According to paragraph 1,
The calculation device is a chemiluminescence analysis device characterized in that it includes a monitor that can calculate the electrical signal converted from the detection unit and then digitize or image it and transmit it.
Preparing an analysis object containing reactive oxygen species in the chamber portion of the chemiluminescence analysis device of claim 1;
Injecting a luminol solution into the analysis object;
emitting light through a chemical reaction between reactive oxygen species of the analyte and luminol contained in the luminol solution;
transmitting the wavelength of light produced by the light emission to a detection unit by an optical fiber unit;
detecting the wavelength of light transmitted from the detection unit and converting it into an electrical signal;
Storing the converted electrical signal value in a calculation device and calculating the amount of reactive oxygen species,
The step of preparing an analyte containing the reactive oxygen species is,
Externally prepare an analyte containing reactive oxygen species generated by advanced oxidation processes (AOPs), or prepare an analyte containing reactive oxygen species generated through the reaction steps of reactants, photocatalysts, and light. Preparing,
The luminol concentration of the luminol solution is 1 to 1.5 times the reactive oxygen species concentration,
The luminol concentration of the luminol solution is 2.2 Х 10 ^-1 μM to 33.4 Х 10 ^-2 μM. Chemiluminescence spectrometry for evaluating the behavior of reactive oxygen species.
delete According to clause 9,
The photocatalyst includes titanium oxide (TiO ₂ ), zinc oxide (ZnO), cadmium sulfide (CdS), zirconium oxide (ZrO ₂ ), gC ₃ N ₄ -TiO ₂ (Graphitic carbon nitride titanium dioxide), a metal oxide semiconductor, and composite metal. A chemiluminescence analysis method for evaluating the behavior of reactive oxygen species, characterized in that one or more selected from the group consisting of oxide Fe-TNT (iron doped titania nanotubes).
According to clause 9,
Chemiluminescence spectrometry for evaluating the behavior of reactive oxygen species, characterized in that the calculation is calculated according to the following equation 1.

[Calculation Formula 1]
Amount of reactive oxygen species produced (μM) = α Х Amount of luminol reaction (μM) = α´(μM/μW) Х Intensity of actual light generated (μW).
In the calculation formula 1 above, the intensity of the actually generated light (μW) = the intensity of the measured light (μW) Х e ^(k*d) ,
The α is the reaction constant (1≤α) between the amount of reactive oxygen species produced and the reaction amount during the luminol reaction,
The α´(μM/μW) is the reaction constant (α´≤1) between the amount of reactive oxygen species produced during luminol reaction and the actual luminescence intensity,
The k is the rate of decrease according to distance of the intensity of the actually generated light,
The d(cm) is the distance from the actual light generation location to the optical fiber.