WO2016085313A2 - Chemical element analysis device and method for contaminants in liquid - Google Patents

Abstract

The present invention relates to a chemical element analysis device and method for contaminants in a liquid. The chemical element analysis device for contaminants in a liquid according to the present invention comprises: a sample storage unit (10) for storing a sampled liquid sample (1); a laser unit (20) for emitting a laser beam (21: 21a, 21b, 21c) and irradiating the laser beam (21) to the sample (1: 1a, 1b, 1c) sprayed from the sample storage unit (10); and a spectrometer (30) for collecting plasma light (31: 31a, 31b, 31c) generated by irradiating the laser beam (21) to the sample (1), and measuring a spectrum of the plasma light (31).

Description

Chemical element analysis device and analysis method of pollutant in liquid

The present invention relates to an apparatus and method for analyzing chemical elements of contaminants in liquids. More specifically, the present invention relates to a chemical element analysis device and a method for analyzing a chemical element of a contaminant in a portable liquid that can be directly analyzed on-site the chemical element component of the contaminant in a liquid sample.

In general, the liquid analyzer is used to analyze the composition of the components of various industrial processes for the purpose of quality control, pollution treatment, and the like. In particular, since the need for environmental protection is becoming increasingly important, analyzing and treating the components of liquid waste is referred to as an important issue.

In general, a conventional liquid analyzer / analysis method collects a predetermined amount of a desired solution, transfers it to a desired place where an analyzer is installed, and then pre-processes the transferred sample solution under suitable conditions for analysis. The analyzer can be used for quantitative analysis. However, in the case of using the conventional liquid analysis device / analysis method as described above, there is a problem that it takes a long time to go through a complicated pretreatment process, an operation of measuring equipment, and the like. In addition, the disposal of a large amount of chemical reagents that are essentially used may be a problem.

On the other hand, due to the lack of traditional energy resources and rising oil prices, interest in shale gas, which is a non-traditional gas resource in recent years and is distributed evenly around the world, has been amplified. In the past, the problem of drilling technology made it difficult to produce shale gas mining, but the development of hydraulic fracturing technology accelerated the development of shale gas fields. Hydraulic fracturing technology is a technique in which a hydraulic fracturing fluid composed of water, sand, and chemical additives is injected into the shale layer at high pressure to cause cracking, and shale gas is collected through the crack.

When the hydraulic fracturing proceeds or is completed, the wastewater is treated. The chemicals and oils added to the hydraulic fracturing fluid are included in the recovered water, so the pollutants (pollutants) are analyzed. The procedure to deal with is necessarily involved. The chemical elemental analysis of such contaminants may be performed using an inductively coupled plasma (ICP) analysis method or an analysis method using atomic absorption spectroscopy (AAS). However, even when using a conventional analysis method such as ICP or AAS, the same problem occurs as the liquid analysis device / analysis method.

Therefore, there is an urgent need for a method for solving a problem occurring in the liquid analyzer / analysis method according to the prior art.

Accordingly, the present invention has been made to solve the above-mentioned problems of the prior art, has a light weight and portability, and can directly analyze the chemical element component of the collected liquid sample in the field without having to go through the pretreatment process. It is an object of the present invention to provide an apparatus and method for analyzing chemical elements of contaminants in liquids.

In addition, an object of the present invention is to provide a chemical element analysis device and an analysis method for contaminants in a liquid that can analyze the solid remaining after the liquid evaporation by heating and drying the liquid sample through a concentration process.

An object of the present invention is a chemical element analysis apparatus for contaminants in a liquid, comprising: a sample storage unit for storing a sample of a sampled liquid phase; A laser unit oscillating a laser beam to irradiate the laser beam to the sample injected from the sample storage unit; And a spectrometer for collecting the plasma light generated by irradiating the laser beam onto the sample and measuring a spectrum of the plasma light.

The sample storage unit may supply a sample to at least one of the first supply unit and the second supply unit.

The sample storage unit may include a droplet injection unit for atomizing and spraying the sample into the first supply unit.

The sample storage unit may further include a main gas injection unit for injecting an inert gas.

The apparatus may further include a first gas injection unit for injecting an inert gas into the sample before being sprayed at the end of the first supply unit.

The first supply unit may further include a pump for transporting the sample.

The membrane filter further comprises a membrane filter for filtering the sample before the sample is stored in the sample reservoir, wherein the membrane filter is formed in a membrane shape, the filter hole for filtering the sample through the surface, the particulate form in the sample The material and the ionic material can be separated.

The second supply unit may spray the sample to be positioned above the transport plate.

The transport plate may be formed in a rotatable plate shape, and the sample injected by the second supply unit may be adsorbed on the upper surface, and the position may be moved so that the sample is irradiated to the laser beam as the transport plate rotates. .

The transport plate is formed in a plate shape having a predetermined length, and the sample injected by the second supply unit is adsorbed and disposed on an upper surface, and the sample moves to the laser beam as the transport plate moves along the length direction. The location can be moved to be irradiated.

A plurality of placement holes recessed to adsorb the sample may be formed on the upper surface of the transport plate.

The heating plate may further include a heating unit disposed inside the transport plate or disposed under the transport plate to heat and dry the sample by applying heat to the transport plate.

The apparatus may further include a second gas injection unit for injecting an inert gas to the sample to which the laser beam is irradiated.

In addition, the above object of the present invention, a chemical element analysis method of contaminants in a liquid, comprising the steps of: (a) storing a sample of the sampled liquid phase; (b) spraying a stored sample and irradiating a laser beam with the sprayed sample; (c) measuring the spectrum of the plasma light by collecting the plasma light generated by the laser beam irradiated to the sample is achieved by a liquid analysis method.

The sample may be atomized by spraying droplets, and a laser beam may be irradiated onto the sprayed sample.

Inert gas may be injected into the stored sample.

Inert gas may be injected into the sample before the sample is sprayed.

Before storing the sample, the particulate matter and the ionic material in the sample may be separated by using a membrane filter formed in a membrane shape and penetrating a filter hole for filtering the sample on the surface.

The sample may be sprayed to be adsorbed on the upper surface of the transport plate, and the position may be shifted so that the sample is irradiated to the laser beam as the transport plate is moved.

A plurality of placement holes recessed to adsorb the sample may be formed on the upper surface of the transport plate.

The heating unit may be disposed inside the transport plate or under the transport plate to heat-dry the sample by applying heat to the transport plate.

Inert gas may be injected onto the sample to which the laser beam is irradiated.

According to the present invention configured as described above, it is lightweight and has portability, and there is an effect that the chemical element component of the collected liquid sample can be directly analyzed in the field without having to go through the pretreatment process.

In addition, according to the present invention, by heating and drying the liquid sample through a concentration process, there is an effect that can analyze the solid remaining after the liquid evaporation.

1 and 2 are schematic diagrams of an apparatus for analyzing chemical elements of contaminants in a liquid according to one embodiment of the present invention.

3 is a cross-sectional view of the membrane filter shown in FIG. 1.

4 is a partial schematic view of an apparatus for analyzing chemical elements of contaminants in a liquid according to another embodiment of the present invention.

5 is a front view of the transport plate shown in FIG. 4.

6 is a perspective view of the transport plate shown in FIG. 4.

7 and 8 are graphs showing measurement results according to an embodiment of the present invention.

9 to 12 are tables showing detection wavelengths of target elements for various liquid samples.

FIG. 13 is a table illustrating elemental analysis results of Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES) and Laser Induced Breakdown Spectroscopy (LIBS) through a first process according to an embodiment of the present invention.

14 is a table showing the results of elemental analysis of ICP-OES and LIBS through the second process according to an embodiment of the present invention.

<Description of the code>

1, 1a, 1b, 1c: sample

5: inlet

10: sample storage unit

11: first supply

15: second supply unit

20: laser unit

21, 21a, 21b, 21c: laser beam

30: Spectrometer

31, 31a, 31b, 31c: plasma light

40: controller

50: membrane filter

60: main gas injection unit

70: first gas injection unit

80: second gas injection unit

90, 100: transport board

95 and 105: heating section

102: placement hole

DETAILED DESCRIPTION The following detailed description of the invention refers to the accompanying drawings that show, by way of illustration, specific embodiments in which the invention may be practiced. These embodiments are described in sufficient detail to enable those skilled in the art to practice the invention. It should be understood that the various embodiments of the present invention are different but need not be mutually exclusive. For example, certain shapes, structures, and characteristics described herein may be embodied in other embodiments without departing from the spirit and scope of the invention with respect to one embodiment. In addition, it is to be understood that the location or arrangement of individual components within each disclosed embodiment may be changed without departing from the spirit and scope of the invention. The following detailed description, therefore, is not to be taken in a limiting sense, and the scope of the present invention, if properly described, is defined only by the appended claims, along with the full range of equivalents to which such claims are entitled. In the drawings, like reference numerals refer to the same or similar functions throughout the several aspects, and length, area, thickness, and the like may be exaggerated for convenience.

DETAILED DESCRIPTION Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily implement the present invention.

1 and 2 are schematic diagrams of an apparatus for analyzing chemical elements of contaminants in a liquid according to one embodiment of the present invention. Hereinafter, the liquid analyzer will be described.

Referring to FIG. 1, a liquid analyzing apparatus according to an exemplary embodiment includes a sample storage unit 10 in which a sample 1 of a sampled liquid is stored; A laser unit 20 and a laser for oscillating the laser beams 21: 21a, 21b, 21c and irradiating the laser beam 21 to the samples 1: 1a, 1b, 1c ejected from the sample storage unit 10. The beam 21 includes a spectrometer 30 that collects the plasma light 31 (31a, 31b, 31c) generated by irradiating the sample 1 and measures the spectrum of the plasma light 31.

Referring to Figure 2, the basic principle of the liquid analyzer will be described below. The analysis of the sample 1 can utilize the spectroscopic analysis method which uses a plasma as an excitation source. The laser unit 20 is a device that oscillates the laser beam 21 and irradiates the sample 1. The laser unit 20 includes a laser generator 25 and a condenser lens 26. The laser beam 21 may be, for example, a high power laser beam 21 such as an Nd: YAG laser or the like. However, the laser beam 21 is not necessarily limited to the Nd: YAG laser. In this case, the output of the laser beam 21 may be controlled by the controller 40. The laser beam 21 may be focused through the condenser lens 26 and irradiated onto the sample 1.

When the laser beam 21 is irradiated to the sample 1, the sample 1 may be vaporized and separated into electrons and cations to generate a plasma. Plasma emits energy in the form of light as atoms and ions in the excitation state return to the ground state (ground state), which spectroscopically analyzes the plasma light, Can be analyzed quantitatively.

In this way, the laser beam 21 is irradiated onto the sample 1 through the liquid analyzer laser unit 20 according to the present invention, and the plasma light 31 generated at this time is spectroscopically analyzed. Spectroscopic analysis of the plasma light 31 may be performed through the spectrometer 30. The laser beam 21 may use a laser having a wavelength of 1064 nm. In addition, in order to reduce the spot size at which the laser beam 21 is focused, it may be set to reduce the focal length of the objective lens. The laser beam spot size may be configured as 4λf / πD (D: incident diameter, f: focal length), and the laser beam spot size can be reduced by reducing the focal length f of the objective lens. Thus, even if the laser portion 20 generates a low intensity laser, the laser beam 21 can be irradiated with a high intensity substantially through integration. Therefore, it is possible to minimize the heat generation according to the minimized laser intensity, thereby simplifying the configuration of the laser unit 20, there is an effect that can reduce the weight of the product. As a result, it can design as a portable analysis device which ensures mobility.

Spectrometer 30 is a spectrometer that measures the spectrum of plasma light 31. When an element returns from the excited state to the ground state, it emits its own wavelength according to its type and the excited state. Therefore, analyzing the spectrum of the wavelength allows qualitative and quantitative analysis of the components of the substance. According to this principle, by collecting the plasma light 31 using the spectrometer 30 and measuring the spectrum thereof, it is possible to qualitatively and quantitatively analyze the substance (pollutant) in the sample 1. On the other hand, the analysis result of the spectrum can be displayed by the computer 41.

Referring back to FIG. 1, the sample 1 is sampled from flowback water, general wastewater, mine wastewater (mine drainage), nuclear power wastewater, etc. generated during the drilling of a shale gas field. It may be a liquid sample (1), and any kind of liquid other than the above-mentioned wastewater may be employed as the sample (1). In particular, the recovery water generated during the drilling process of shale gas field will be described below.

Drilling of shale gas fields uses hydraulic fracturing. The hydraulic fracturing technology is a technique of causing cracking and collecting shale gas by spraying the hydraulic fracturing fluid at high pressure on the shale layer which is accumulated by sand and mud. On the other hand, the fluid, ie, recovered water, which is returned to the ground after the hydraulic fracturing is in progress or completed, includes clay, dissolved metal ions, dissolved solids, suspended solids, and chemical additives added to the hydraulic fracturing fluid. Therefore, it is essential to treat the recovered water containing contaminants such as heavy metals during the drilling of shale gas fields. Therefore, the liquid analyzing apparatus of the present invention was invented for the purpose of facilitating water treatment by analyzing contaminants such as recovered water, general wastewater, mine wastewater, and nuclear power wastewater in real time on site.

The sample 1 may be injected through the inlet 5 of the liquid analyzer and stored in the sample storage unit 10. The sample storage unit 10 may supply the sample 1 to at least one of the first supply unit 11 or the second supply unit 15 to a space in which the liquid sample 1 is stored.

The sample 1 may be filtered by the membrane filter 50 before being stored in the sample reservoir 10. Membrane filter 50 acts as a filter with a thin membrane that filters the material in sample 1. As shown in FIG. 3, the membrane filter 50 is formed in a membrane shape, and a filter hole 51 for filtering the sample 1 is formed therethrough to form a particulate material in the sample 1. 1 ') and the ionic material 1 "are separated.

The membrane filter 50 may be used to separately analyze the material in the sample 1. Specifically, by filtering the particulate matter 1 ′ in the sample 1 using the membrane filter 50, only the ionic material 1 ″ may be analyzed separately. In addition, the membrane filter 50 may be used. The sample 1 including the particulate matter 1 ′ and the ionic matter 1 ″ can be analyzed. As described above, by separating and analyzing the particulate matter 1 'and the ionic material 1 "separately, there is an advantage in that the difference between the particulate matter 1' and the ionic material 1" can be confirmed.

Depending on the diameter of the filter hole 51, the filtration is divided into microfiltration (MF, Microfiltration) and ultrafiltration (UF, Ultrafiltration). The membrane filter 50 may be a microfiltration membrane or an ultrafiltration membrane. In this case, the type of the membrane filter 50 is determined in consideration of the diameter of the material in the sample 1, the capacity of the sample 1, flow rate, cost and the like. In view of these factors, microfiltration membranes are preferred, but are not necessarily limited thereto. In addition, the membrane filter 50 is illustrated as being formed in the inlet 5, but is not necessarily limited thereto, and may be formed in the first and second supply parts 11 and 15.

Meanwhile, the main gas injection unit 60 may be further included to inject the inert gas into the sample storage unit 10. The main gas injection unit 60 may discharge the air contained in the sample 1 by injecting an inert gas such as argon gas or helium gas into the sample 1 of the sample storage unit 10. Air contains gases such as oxygen, nitrogen, hydrogen, etc., which can affect the spectrum when a plasma is generated. Accordingly, the main gas injection unit 60 may primarily inject an inert gas having little reactivity to the sample 1 of the sample storage unit 10 to remove air that may affect the spectrum. Thus, the liquid analyzing apparatus according to the present invention greatly improves the detection sensitivity, and can increase the repeatability of the analysis result.

The first supply part 11 is a pipe formed in a hollow tube shape. The sample 1a atomized into droplets in the first supply unit 11 may be moved (P1: first process) and sprayed through a nozzle at the end of the first supply unit 11. The sample 1a atomized into droplets may have a size of about 100 nm to several μm.

The sample storage unit 10 may include a droplet injection unit (not shown) for atomizing the sample 1 into droplets and spraying the first supply unit 11. Here, the droplet injection unit may include a nebulizer or an atomizer. The nebulizer has a relatively larger size of the droplet 1a than in the case of the atomizer, and is capable of simultaneous detection of ionic and particulate matter. On the other hand, the atomizer has a feature that the size of the droplet (1a) is small, can minimize the effect of water when drying. Since the sample 1a sprayed by the droplet injection unit does not undergo a separate drying process, it is preferable to use a nebulizer. However, the droplet injection unit is not necessarily limited to the nebulizer, and an atomizer may be used depending on the substance in the sample 1.

Before the sample 1a is sprayed through the nozzle at the end of the first supply unit 11, the first gas injection unit 70 may be further included such that an inert gas is injected into the sample 1a. The first gas injection part 70 sprays an inert gas such as argon gas, helium gas, or the like into the sample 1a before being sprayed through the nozzle at the end of the first supply part 11. It can release air secondary. Therefore, the liquid analysis device according to the present invention can further improve the detection sensitivity, and further increase the repeatability of the analysis results.

In order to transport the sample 1a more smoothly, a pump (not shown) may be further included in the first supply part 11. The pump may be disposed anywhere in the first supply portion 11 within a range that provides a suction force for transporting the sample 1a, but is preferably disposed at the end of the first supply portion 11.

The laser beam 21a is irradiated to the sample 1a injected from the end of the first supply part 11, and the plasma may be generated as the sample 1a is vaporized and separated into electrons and cations. The plasma emits plasma light 31a by returning from the excited state to the ground state, and collects the plasma light 31a from the spectrometer 30 to measure spectra to qualitatively and politically analyze the elements. Since the plasma light 31a may be generated at a wavelength of about 200 to 900 nm, the input lens (not shown) of the spectrometer 30 may have chromatic aberration in order to prevent a phenomenon in which the detection efficiency due to chromatic aberration is degraded. The lens may be prevented or the chromatic aberration may be corrected in the spectrometer 30. The controller 40 may control the output of the laser beam 21a, analyze the measurement result of the spectrometer 30, and display it on the computer 41 (see FIG. 2).

The second supply part 15 is a pipe formed in a hollow tube shape similarly to the first supply part 11. However, in the second supply unit 15, the sample 1a atomized into the droplets does not move, but the sample 1b itself in the liquid state may move. The sample 1b moving to the second supply part 15 is not atomized by the nebulizer or atomizer, but a nebulizer or an atomizer may be used within the range where conversion to a droplet having a predetermined diameter or less is required. .

The movement (P2: second process) of the sample 1b to the second supply unit 15 may be performed when the limit of detection of the pollutant in the sample 1 is low or during real time monitoring in the first process P1. If the degree of detection greatly exceeds the reference value, it can be used by switching to the second process P2 for more accurate measurement. When the concentration of the sample 1 is equal to or less than a predetermined concentration value and the measurement by the spectrometer 30 is impossible by the movement P1 of the sample 1a to the first supply unit 11, the second supply unit 15 The sample 1b injected from the above can be dried by heating. The sample 1, which contains a lot of water relative to the contaminants, has a low detection sensitivity, and thus, even if the plasma light 31a of the sample 1a is analyzed through the first supply unit 11, a desired analysis value cannot be obtained. Therefore, the sample 1 is heated and dried to evaporate water, thereby increasing the concentration of the sample 1 above a predetermined concentration value and proceeding the analysis.

Meanwhile, the sample 1b moved through the second supply part 15 (P2) may be sprayed to be positioned above the transport plate 90. A nozzle or a syringe may be installed at the end of the second supply part 15 to inject the sample 1b into an appropriate droplet size. The transport plate 90 is formed in a rotatable plate shape, and the sample 1b may be adsorbed on one surface (upper surface).

One surface (upper surface) of the transport plate 90 may be added with a hydrophilic treatment. The hydrophilic treatment may be performed through a method of coupling a hydrophilic membrane coating or a hydrophilic filter to the transport plate 90. Liquid analysis using a conventional Al filter, such as due to the salt and contaminants in the sample, there was a problem that the crystallization proceeds. Thus, there was a problem in that the analysis accuracy of the sample was low and a uniform result was not obtained. However, in the present invention, as the hydrophilic treatment is added to the transport plate 90, the sample 1b may be easily adsorbed and disposed, and the sample 1b may be evenly spread on the transport plate 90. The time for drying (1b) can be shortened, and there is an advantage of preventing the crystallization from proceeding after the sample 1b is dried. Thus, the analysis accuracy is high and a uniform result can be obtained.

  In addition, a plurality of placement holes (not shown) may be formed in the upper surface of the transport plate 90 so that the sample 1b can be more stably adsorbed. The arrangement hole is a minute hole formed so that the sample 1b is stably adsorbed onto the transport plate 90. Therefore, even when the transport plate 90 is moved, the sample 1b disposed on the transport plate 90 is less susceptible to vibration or impact. The transport plate 90 may be rotated by a rotating member 91 such as a motor connected to the lower portion.

When the transport plate 90 rotates, the sample 1b adsorbed and disposed on the transport plate 90 may also move to move to the position where the laser beam 21b can be irradiated. The transport plate 90 may be formed of a material that does not affect the plasma light 31b depending on the material in the sample 1b. For example, when the material in the sample 1b is a heavy metal, it may be formed of nylon, and in the case of a carbon compound, it may be formed of a metal component. However, the transport plate 90 is not necessarily limited to these materials.

In order to heat-dry the sample 1, the heating unit 95 may be disposed inside the transport plate 90, but the heating unit may be disposed below the transport plate 90. The heating unit 95 is a heating device that heats the transport plate 90, and heats the sample 1b disposed on one surface of the transport plate 90 to evaporate water. In this case, the heating temperature of the heating unit 95 may be controlled by a controller (not shown).

The second gas injection unit 80 may be further included so that the inert gas is directly injected onto the sample 1b to which the laser beam 21b is irradiated. The second gas injection unit 80 corresponds to the first gas injection unit 70 described above. However, since the inert gas is directly injected to the sample 1b, the sample 1a before the laser beam 21a is irradiated is different from the first gas injection unit 70 for injecting the inert gas. This is because the sample 1b is in contact with the air in the process of moving through the transport plate 90, so that the inert gas is injected when the laser beam 21b is irradiated to more effectively remove the air in the sample 1b. to be. Since the air contained in the sample 1b can be discharged secondarily, the liquid analyzing apparatus according to the present invention can further improve the detection sensitivity and further increase the repeatability of the analysis results.

The laser beam 21b is irradiated to the sample 1b moved by the transport plate 90, and the plasma may be generated as the sample 1b is vaporized and separated into electrons and cations. The plasma emits plasma light 31b by returning from the excited state to the ground state, and collects the plasma light 31b from the spectrometer 30 to measure spectra to qualitatively and politically analyze the elements. The controller 40 may control the output of the laser beam 21b, analyze the measurement result of the spectrometer 30, and display it on the computer 41 (see FIG. 2).

4 is a partial schematic view of a liquid analyzing apparatus according to another embodiment of the present invention, FIG. 5 is a front view of the transport plate shown in FIG. 4, and FIG. 6 is a perspective view of the transport plate shown in FIG. 4. 4 to 6 is different from the embodiment of FIG. 1 only in the configuration of the transport plate 100, and the rest of the components are the same, the description thereof will be omitted.

4 to 6, the sample 1c moved P2 through the second supply unit 15 may be sprayed to be positioned above the transport plate 100. The transport plate 100 is formed in a plate shape having a predetermined length, and the sample 1c may be adsorbed and disposed on one surface (upper surface).

One surface (upper surface) of the transport plate 100 may be added with a hydrophilic treatment to facilitate the adsorption arrangement.

One surface (upper surface) of the transport plate 100 may be added with a hydrophilic treatment. The hydrophilic treatment may be performed through a method such as bonding a hydrophilic membrane coating or a hydrophilic filter to the transport plate 100. As the hydrophilic treatment is added to the transport plate 100, the sample 1c can be easily adsorbed and disposed, the sample 1c can be spread evenly on the transport plate 100, and the sample 1c is dried. The time to be shortened, and there is an advantage of preventing the crystallization from proceeding after the sample 1c is dried. Thus, the analysis accuracy is high and a uniform result can be obtained.

In addition, a plurality of placement holes 102 may be formed in the upper surface of the transport plate 100 so that the sample 1c may be more stably adsorbed. The arrangement hole 102 is a fine hole formed so that the sample 1c can be stably adsorbed to the transport plate 100. Therefore, even when the transport plate 100 is moved, the sample 1c disposed on the transport plate 100 is less affected by vibration or impact.

Since the transport plate 100 moves 101 along the longitudinal direction, the sample 1c disposed on the transport plate 100 may be moved to be irradiated to the laser beam 21c after heat drying. The transport plate 100 may be formed of a material that does not affect the plasma light 31c depending on the material in the sample 1c. For example, when the material in the sample 1c is a heavy metal, it may be formed of nylon, and in the case of a carbon compound, it may be formed of a metal component. However, the transport plate 100 is not necessarily limited to these materials.

In order to heat-dry the sample 1, the heating unit 105 may be disposed below the transport plate 100, but the heating unit may be disposed inside the transport plate 100. The heating unit 105 is a heating device that heats the transport plate 100, and heats the sample 1c disposed on one surface of the transport plate 100 to evaporate water. In this case, the heating temperature of the heating unit 105 may be controlled by a controller (not shown).

The laser beam 21c is irradiated to the sample 1c moved by the transport plate 100, and the sample 1c may be vaporized to generate plasma as electrons and cations are separated. The plasma emits plasma light 31c while returning from the excited state to the ground state, and collects the plasma light 31c from the spectrometer 30 to measure spectra to qualitatively and politically analyze the elements. The controller 40 may control the output of the laser beam 21c, analyze the measurement result of the spectrometer 30, and display it on the computer 41 (see FIG. 2).

As described above, the liquid analyzing apparatus of the present invention has an effect of directly injecting the sampled liquid sample 1 and analyzing the sampled liquid. As a device that does not need to undergo a complicated pretreatment process and does not use chemical reagents or the like, it has portability, and thus, the component of the collected liquid sample 1 can be directly analyzed on site.

In addition, since the laser beam 21 is irradiated after atomizing and spraying the sample 1 or heating and drying, there is an effect of minimizing the laser intensity to be used. [60mJ / pulse, a laser beam 21 having an energy of 200 mJ / pulse is used. Since the laser intensity is minimized, heat generation can be minimized, thereby reducing the weight of the product. Therefore, it can design as a portable analysis device which ensures mobility.

Then, without considering the size and amount of the droplets of the sample 1 in the sample storage unit 10, the atomized sample 1a spread by the nebulizer or the atomizer is transferred to the first supply unit 11. Since it can be sprayed through the nozzle at the end, there is an effect that can accumulate droplets. In addition, by injecting an inert gas into the sample 1a to release the air contained in the sample 1a, it is possible to increase the integration efficiency and to block the influence from the ambient air, thereby further improving the detection sensitivity. It can be effective.

When the detection limit is low because the concentration of the pollutant is low, or when the degree of detection of the pollutant during the real-time monitoring greatly exceeds the reference value, the liquid sample 1 is heated and dried to be concentrated. The remaining solids can be analyzed. Thus, there is an effect of increasing the concentration of the sample 1 and increasing the detection sensitivity.

In addition, there is an effect capable of both quick and simple measurement through the first supply unit 11 (first process P1) and precise measurement through the second supply unit 15 (second process P2). In addition, there is an effect that it is possible to improve the analysis accuracy by presenting a result complementary to the analysis results through the first supply unit 11 and the analysis results through the second supply unit 15.

The sample 1b and 1c are sprayed and sprayed through the first and second supply units 11 and 15 in the sample storage unit 10, and the transport units 90 and 100 and the heating units 95 and 105. System automation is possible through analysis through the process of transferring).

Experimental Example

Hereinafter, look at the experimental results using the liquid analysis device of the present invention.

7 and 8 are graphs showing measurement results according to an embodiment of the present invention. As a result of analyzing the numerical value of Mg contained in the same liquid sample 1, FIG. 7 irradiates the laser beam 21a to the sample 1a atomized into droplets through the 1st supply part 11, and the plasma light 31a 8 is analyzed by the laser beams 21b and 21c after heating and drying the sample 1b injected through the second supply unit 15 on the transport plates 95 and 105. The plasma lights 31b and 31c are analyzed.

In the case of FIG. 7, 200 mJ / pulse laser energy was applied, and in FIG. 8, a hydrophilic filter [Filter paper 53 (HYUNDAI MICRO), diameter 110 mm, pore size 1-2 μm] was applied to the transport plates 95 and 105. Cover, heat-dry at 70 degreeC for 10 minutes, and added the laser energy of 60 mJ / pulse. In FIG. 7 and FIG. 8, graphs of increasing laser induced breakdown spectroscopy (LIBS) peak area were shown as the ppm of Mg was increased, and linearity (R ² ) was 0.9719 and 0.9948, which was close to 1. In particular, FIG. 8 was heated and dried to increase the concentration of contaminants. Therefore, the linearity was higher, and analysis was possible even using relatively low laser energy.

Therefore, it can be confirmed that a highly reliable analysis result is obtained through the liquid analyzing apparatus of the present invention, and it can be confirmed that real-time analysis can be performed in the field through the liquid analyzing apparatus having high portability.

9 to 12 are tables showing detection wavelengths of target elements for various liquid samples. The liquid analyzer of the present invention measures the spectrum of the target element included in the liquid sample 1 sampled from shale gas recovery water, general wastewater, mine wastewater (mine drainage), nuclear power wastewater, etc. with reference to FIGS. Thus, there is an advantage that quantitative / qualitative analysis of the element is possible.

FIG. 13 is a table illustrating elemental component analysis results of Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES) and Laser Induced Breakdown Spectroscopy (LIBS) through a first process P1 according to an embodiment of the present invention.

The X axis of FIG. 13 shows the concentration of the target component in the sample through ICP-OES, and the Y axis shows the sample sprayed from the first supply unit 11 as a measured value of the target component in the sample through the liquid analyzer (LIBS) of the present invention. The analysis result which irradiated the laser beam 21a immediately to (1a) is shown.

The sample 1 sampled from the shale gas recovered water was analyzed, and a laser beam 21a of 200 mJ / pulse was irradiated with a delay time of 1 ms, and the spectrometer 30 used LIBS2000 +.

The linearity (R ² ) of the data of ICP-OES and LIBS was 0.8261, 0.8068, 0.8338, and 0.8233, respectively, for Mg, Ca, Na, and K, respectively, in the sample. Through this, it was confirmed that the analysis results of the LIBS of the present invention is a reliable level when compared with the analysis results of the ICP-OES standard analysis method for the components in the sample.

14 is a table showing the results of elemental analysis of ICP-OES and LIBS through the second process (P2) according to an embodiment of the present invention.

The X axis of FIG. 14 represents the concentration of the target component in the sample through ICP-OES, and the Y axis of the sample is injected from the second supply unit 15 as a measurement value of the target component in the sample through the liquid analyzer (LIBS) of the present invention. An analysis result of irradiating the laser beams 21b and 21c after (1b and 1c) by heating and drying on the transport plates 90 and 100 is shown.

The sample 1 sampled from the shale gas recovered water was analyzed, and a 60 mJ / pulse laser beam 21b was irradiated with a delay time of 1 ms, and the spectrometer 30 used LIBS2000 +. In the second process P2, since the heat drying process of the sample is added, there is an advantage in that the laser beam 21b having a relatively low energy can be used. The hydrophilic filters were combined on the transport plates 90 and 100 to adsorb and place the samples 1b and 1c, and heat drying was performed at 70 ° C. for 10 minutes.

The linearity (R ² ) of the data of ICP-OES and LIBS was 0.8841, 0.9402, 0.8796, and 0.8810 for Mg, Ca, Na, and K, respectively. Since the analysis was concentrated, the numerical value was closer to 1 than the result of the first process (P1). Through this, it was confirmed that the analysis results of ICP-OES which is a standard analysis method for the components in the sample and the analysis results of LIBS of the present invention are substantially the same level.

13 and 14, it can be seen that the analysis results with high reliability even through the liquid analysis device of the present invention, it was confirmed that the real-time analysis is possible in the field through the highly portable liquid analysis device.

Although the present invention has been shown and described with reference to preferred embodiments as described above, it is not limited to the above embodiments and various modifications made by those skilled in the art without departing from the spirit of the present invention. Modifications and variations are possible. Such modifications and variations are intended to fall within the scope of the invention and the appended claims.

Claims (24)

1. A device for analyzing chemical elements of contaminants in liquids,

   A sample storage unit for storing a sample of the sampled liquid phase;

   A laser unit oscillating a laser beam to irradiate the laser beam to the sample injected from the sample storage unit; And

   Spectrometer for collecting the plasma light generated by the laser beam irradiated to the sample to measure the spectrum of the plasma light

   Liquid analysis device comprising a.
2. The method of claim 1,

   And the sample storage unit supplies the sample to at least one of the first supply unit and the second supply unit.
3. The method of claim 2,

   And the sample storage part includes a droplet injection part for atomizing and spraying the sample into the first supply part.
4. The method of claim 1,

   And a main gas injection part for injecting an inert gas into the sample storage part.
5. The method of claim 4, wherein

   And a first gas injector for injecting an inert gas into the sample before being sprayed at the end of the first supply part.
6. The method of claim 4, wherein

   The first supply unit, the liquid analysis device further comprises a pump for transporting the sample.
7. The method of claim 1,

   Further comprising a membrane filter for filtering the sample before the sample is stored in the sample reservoir,

   The membrane filter is formed in a membrane shape, the filter hole for filtering the sample through the surface of the liquid analysis device, characterized in that to separate the particulate matter and the ionic material in the sample.
8. The method of claim 2,

   And the second supply unit sprays the sample so that the sample is positioned above the transport plate.
9. The method of claim 8,

   At least one surface of the transport plate is a liquid analysis device, characterized in that the hydrophilic treatment.
10. The method of claim 8,

    The transport plate is formed in a rotatable plate shape, and the sample injected by the second supply unit is adsorbed on the upper surface, and the position is moved so that the sample is irradiated to the laser beam as the transport plate rotates. Liquid analyzer characterized in that.
11. The method of claim 8,

    The transport plate is formed in a plate shape having a predetermined length, and the sample injected by the second supply unit is adsorbed and disposed on an upper surface, and the sample moves to the laser beam as the transport plate moves along the length direction. Liquid analysis device, characterized in that the position is moved to be irradiated.
12. The method according to claim 10 or 11, wherein

    And a plurality of arrangement holes recessed to adsorb the sample on the upper surface of the transport plate.
13. The method according to claim 10 or 11, wherein

    And a heating unit disposed inside the transport plate or under the transport plate to heat and dry the sample by applying heat to the transport plate.
14. The method according to claim 10 or 11, wherein

    And a second gas injection unit for injecting an inert gas to the sample to which the laser beam is irradiated.
15. Method for analyzing chemical elements of contaminants in liquids

    (a) storing a sample of the sampled liquid phase;

    (b) spraying a stored sample and irradiating a laser beam with the sprayed sample; And

    (c) measuring the spectrum of the plasma light by collecting plasma light generated by irradiation of the laser beam on the sample;

    Liquid analysis method comprising a.
16. The method of claim 15,

    And atomizing the sample into droplets, and irradiating the sprayed sample with a laser beam.
17. The method of claim 15,

    And injecting an inert gas into the stored sample.
18. The method of claim 15,

    And injecting an inert gas into the sample before the sample is sprayed.
19. The method of claim 15,

    Before storing the sample, the liquid analysis method characterized in that the particulate matter and the ionic material in the sample is separated by using a membrane filter formed in a membrane shape and the filter hole through which the filter hole for filtering the sample is penetrated.
20. The method of claim 15,

    And spraying the sample on the upper surface of the transport plate so as to be adsorbed, and moving the transport plate so that the sample is irradiated to the laser beam.
21. The method of claim 15,

    At least one side of the transport plate is a liquid analysis method characterized in that the hydrophilic treatment.
22. The method of claim 20,

    And a plurality of arrangement holes recessed to adsorb the sample on the upper surface of the transport plate.
23. The method of claim 20,

    And a heating unit disposed inside the transport plate or under the transport plate to heat-dry the sample by applying heat to the transport plate.
24. The method of claim 20,

    And injecting an inert gas to the sample to which the laser beam is irradiated.

Images