Flow analysis device and flow analysis method

Abstract

The present invention addresses the problem of providing a flow analyzer capable of analyzing a mercury-containing sample with a precision equivalent to that of a conventional method while analyzing mercury without performing a complicated pretreatment. [Solution] This problem is solved by a flow analysis device provided with a sample introduction unit (1), a reagent introduction unit (3), and an analysis unit (4), and further provided with: a heating unit (5) for heating a sample to which a reagent has been added; a cooling unit (6) that cools the heat-treated sample conveyed through the conduit; and a gas-liquid separation unit (7) for removing gas present in the cooled conduit.

Description

Technical Field

[0001] The present invention relates to a flow analysis device and a flow analysis method, and in particular to a flow analysis device and a flow analysis method using mercury as an analysis object. Background Art

[0002] Mercury is highly toxic and has been the subject of emission restrictions in recent years. The Minamata Treaty, which came into effect in 2017, prohibits the production of mercury from mines and the import and export of mercury, etc., with the aim of protecting human health and the environment from the effects of anthropogenic release of mercury and mercury compounds. The use and import of mercury are also strictly restricted in the EU in accordance with the RoSH Directive.

[0003] Mercury is relatively easy to vaporize, so reduction vapor atomic absorption spectrometry, reduction vapor atomic fluorescence spectrometry, combustion vaporization-gold amalgam-atomic absorption spectrometry, etc. are used for its analysis. For example, in the Ministry of Health, Labor and Welfare Notice No. 261 of Heisei 15 (2003) on water quality inspection methods based on the Waterworks Law, it is stipulated in its Appendix 7 that mercury should be inspected by reduction vapor atomic absorption spectrometry (see Non-Patent Document 1). In addition, in the Environmental Agency Notice No. 59 of Showa 46 (1971) on environmental standards for water pollution, it is also stipulated in its Appendix 2 that mercury should be measured by reduction vapor atomic absorption spectrometry (see Non-Patent Document 2).

[0004] On the other hand, as a method for continuously analyzing metal elements in a sample, the following flow analysis method is known: a sample is continuously introduced into a pipeline, a reagent is introduced into the pipeline through which the sample flows to make it react, and analysis data is continuously measured in an analysis unit (for example, Patent Documents 1 and 2, etc.).

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent No. 6947463

[0008] Patent Document 2: Japanese Patent No. 6903366

[0009] Non-patent literature

[0010] Non-patent document 1: Attached Table 7 of the Ministry of Health, Labor and Welfare Notice No. 261 of Heisei 15

[0011] Non-patent document 2: Appendix 2 of Environmental Agency Notice No. 59, 1977 Summary of the invention

[0012] Problems to be solved by the invention

[0013] However, the above-mentioned conventional mercury analysis method requires very complicated steps in the pretreatment of the sample.

[0014] One aspect of the present invention has been developed in view of the above-mentioned problem, and aims to provide a flow analysis device and a flow analysis method, which can analyze mercury without complicated sample pretreatment and can analyze samples containing mercury with the same accuracy as conventional methods.

[0015] Technical solutions to solve problems

[0016] In order to solve the above-mentioned problems, the present inventors considered whether it is possible to analyze mercury without performing complicated pretreatment by continuously performing everything from sample pretreatment to analysis in a closed system according to a flow analysis method.

[0017] However, the inventors actually continuously introduced a sample containing mercury into a pipeline by a flow analysis method, introduced a reagent into the pipeline through which the introduced sample flowed and heated it to react, and continuously measured analysis data in an analysis unit. As a result, mercury could not be properly analyzed.

[0018] Therefore, as a result of in-depth research, it was discovered that a flow analysis method is used, in which a cooling unit is provided after heating the sample to which a reagent is added, to cool the sample transported in the pipeline after the heating treatment. Surprisingly, even without complicated pretreatment, the mercury in the sample can be continuously analyzed with the same accuracy as the conventional method.

[0019] That is, a flow analysis device according to one embodiment of the present invention comprises: a sample introduction section for introducing a sample into a pipeline; a reagent introduction section for adding a reagent to a sample transported in the pipeline; an analysis section for performing a quantitative analysis or a qualitative analysis on the sample after the reagent is added; and further comprises: a heating section for performing a heat treatment on the sample to which the reagent is added; a cooling section for cooling the sample transported in the pipeline after the heat treatment; and a gas-liquid separation section for removing the gas existing in the pipeline after cooling.

[0020] In addition, a flow analysis method involved in one embodiment of the present invention includes: a sample introduction process, which is used to introduce a sample into a pipeline; a reagent addition process, which adds a reagent to the sample transported in the pipeline; an analysis process, which performs a quantitative analysis or a qualitative analysis on the sample after the reagent is added; and also includes: a heating process, which heats the sample to which the reagent is added; a cooling process, which cools the sample transported in the pipeline after the heat treatment; and a gas-liquid separation process, which removes the gas present in the pipeline after cooling.

[0021] Effects of the Invention

[0022] According to one embodiment of the present invention, there is provided an effect of being able to provide a flow analysis device and a flow analysis method which can analyze mercury without complicated pretreatment and can analyze a sample containing mercury with the same accuracy as conventional methods. Brief introduction of the attached figure

[0023] Figure 1 This is a diagram showing a schematic configuration of a flow analysis device according to Embodiment 1 of the present invention.

[0024] Figure 2 This is a diagram showing a schematic configuration of a flow analysis device according to a second embodiment of the present invention.

[0025] Figure 3 It is a diagram showing a partial configuration of a flow analysis device according to another embodiment of the present invention.

[0026] Figure 4 It is a diagram showing the configuration of a marker detection unit in a flow analysis device according to another embodiment of the present invention.

[0027] Figure 5 This is a diagram schematically showing a state in which a plurality of segments partitioned by bubbles are created in a pipeline by a bubble blocking unit in a flow analysis device according to an embodiment of the present invention.

[0028] Figure 6 This is a diagram schematically showing bubbles in a pipe after heat treatment in a flow analysis device according to an embodiment of the present invention.

[0029] Figure 7 This is a diagram schematically showing how the gas existing in the pipeline is removed by the gas-liquid separation unit in the flow analysis device according to one embodiment of the present invention.

[0030] Figure 8 It is a diagram showing a partial configuration of a flow analysis device according to another embodiment of the present invention.

[0031] Fig. 9 This is a diagram showing a calibration curve prepared in Examples.

[0032] Fig.10 This is a diagram showing an example of a coil portion of a cooling unit in a flow analysis device according to an embodiment of the present invention. DETAILED DESCRIPTION

[0033] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to these contents, and various changes can be made within the scope of the description. Embodiments obtained by appropriately combining the technical solutions disclosed in different embodiments are also included in the technical scope of the present invention. In addition, all academic documents and patent documents described in this specification are incorporated into this specification as references. Also, in this specification, unless otherwise specified, "A to B" indicating a numerical range means "Above A (including A and greater than A) and below B (including B and less than B)".

[0034] [1] Flow analysis device

[0035] A flow analysis device according to one embodiment of the present invention comprises: a sample introduction unit for introducing a sample into a pipeline; a reagent introduction unit for adding a reagent to a sample transported in the pipeline; an analysis unit for performing a quantitative analysis or a qualitative analysis on the sample after the reagent is added; a heating unit for performing a heat treatment on the sample to which the reagent is added; a cooling unit for cooling the sample transported in the pipeline after the heat treatment; and a gas-liquid separation unit for removing gas existing in the pipeline after cooling.

[0036] According to the flow analysis device, mercury can be analyzed without complicated pretreatment, and a sample containing mercury can be analyzed with the same accuracy as the conventional method. Furthermore, according to the flow analysis device, since the sample is transported in the pipeline without contacting the external air, the volatilization of mercury can be prevented, thereby enabling high-precision measurement.

[0037] [1.1] Implementation Method 1

[0038] An embodiment of the present invention will be described with reference to the drawings. Figure 1 The schematic configuration of a flow analysis device according to the first embodiment of the present invention is shown.

[0039] The flow analysis device involved in embodiment 1 of the present invention includes: a sample introduction part 1, which is used to introduce a sample into a pipeline 2; a marker introduction part 8, which is used to introduce a marker into the pipeline 2; a bubble isolation part 10, which performs bubble isolation on the sample and the marker introduced into the pipeline 2, and produces a plurality of segments divided by bubbles in the pipeline 2; a reagent introduction part 3, which adds a reagent to the flow of the sample transported in the pipeline 2; a heating part 5, which heats the sample transported in the pipeline 2 and to which the reagent is added; a cooling part 4, which cools the sample after the heating treatment; a gas-liquid separation part 7, which removes the gas present in the pipeline after cooling; an analysis part 4, which performs quantitative analysis or qualitative analysis on the sample from which the gas is removed in the gas-liquid separation part 7; a marker detection part 9, which detects the marker and outputs a detection signal to the analysis part 4, and the analysis part 4 is designed to obtain analysis data based on the detection signal.

[0040] (Sample introduction section)

[0041] The sample introduction unit 1 is a device for introducing a sample into the pipeline 2, for example, sampling a sample and introducing it into the pipeline 2. In one embodiment of the present invention, the sample introduction unit 1 comprises: a collection tube for introducing the sample into the pipeline 2; and a sampling pump for applying suction force to the collection tube. The sample is introduced into the pipeline 2 at a predetermined flow rate by the sampling pump.

[0042] (Marker introduction section)

[0043] The marker introduction unit 8 is a device for introducing a marker into the pipeline 2. In one embodiment of the present invention, the marker introduction unit 8 comprises: a collection tube for introducing the marker into the pipeline 2; and a pump for applying suction force to the collection tube. The marker may include a substance that can be detected by the marker detection unit 9, or may be the substance, a solution containing the substance, or a dispersion containing the substance.

[0044] Here, the marker introduction section 8 and the sample introduction section 1 can alternately introduce the marker and one or more predetermined number of samples into the pipeline 2. That is, it is designed so that the introduction of the marker from the marker introduction section 8 into the pipeline 2 and the introduction of one or more predetermined number of samples from the sample introduction section 1 into the pipeline 2 can be alternately switched. This switching can be performed manually or automatically.

[0045] When it is possible to alternately introduce the marker and a sample into the pipeline 2, the marker is introduced into the pipeline 2 before a sample each time. Then, for each sample, the marker detection unit 9 that detects the marker outputs a detection signal of the marker to the analysis unit 4, and the analysis unit 4 acquires analysis data based on the detection signal. Thus, even if the liquid cannot be stably fed at a uniform time from the introduction of the sample to the analysis unit 4, since the timing of acquiring the analysis data does not deviate, the sample can be stably and continuously measured.

[0046] In addition, when it is possible to introduce the marker and two or more specified numbers of samples alternately into the pipeline 2, the marker is introduced into the pipeline 2 once before the two or more specified numbers of samples. Then, the marker detection unit 9 that detects the marker outputs the detection signal of the marker to the analysis unit 4, and based on the detection signal, the analysis unit 4 sequentially obtains the analysis data of the specified number of samples. Thus, even when the liquid cannot be delivered stably at a uniform time from the introduction of the sample to the analysis unit, the deviation of the timing of obtaining the analysis data can be reduced to a certain range, so that the sample can be measured stably and continuously. The upper limit of the specified number can be appropriately selected according to the type of sample, the method of pretreatment, etc., for example, it can be 80, 70, 50, 20, 15, or 10.

[0047] There is no particular restriction on the marker that can be detected by the marker detection unit 9, but it is preferably a substance that is not contained in the sample and / or a substance other than the substance of the analysis object. In addition, the marker is preferably a reagent added between the introduction into the pipeline 2 and the marker detection unit 9 and a substance that does not decompose when heated. For example, the marker can be a substance that can be detected by a spectrophotometer. There is no particular restriction on the substance involved, and examples include rhodium, palladium, nickel, copper, chromium, manganese, iodine, cobalt, nitrate ions, phosphate ions, and silicate ions. Alternatively, the substance can be a substance that can be detected by a voltammeter. There is no particular restriction on the substance involved, and examples include copper, cadmium, nickel, mercury, arsenic, and selenium. Alternatively, the substance can be a substance that can be detected by an ion electrode instrument. There is no particular restriction on the substance involved, and examples include calcium, potassium, fluorine, and ammonia. Alternatively, the substance can be a substance that can be detected by an ion chromatograph. There are no special restrictions on the substances involved, and examples thereof include ions of inorganic acids and organic acids, phenol, hydrazine, amino acids, and polysaccharides. Alternatively, the substance may be a substance that can be detected by a turbidimeter. There are no special restrictions on the substances involved, and examples thereof include particulate matter that is insoluble in acids other than hydrofluoric acid, i.e., silicon dioxide. Alternatively, the substance may be a substance that can be detected by a fluorescence photometer. There are no special restrictions on the substances involved, and examples thereof include benzene, coumarin, and naphthalene. Among them, from the perspective of ease of detection, particularly preferred markers are rhodium, palladium, cobalt, nickel, and copper.

[0048] (Bubble barrier)

[0049] like Figure 5As shown, the bubble isolation unit 10 is a device for performing bubble isolation on the sample and marker introduced into the pipeline 2, and making a plurality of segments divided by bubbles 13 in the pipeline 2. In one embodiment of the present invention, the bubble isolation unit 10 comprises: a gas introduction pipe 10a, which introduces gas into the pipeline 2; and a gas introduction pump (not shown) which imparts suction force to the gas introduction pipe. By performing bubble isolation, reagents and the like can be properly mixed by the vortex in the isolation liquid divided by the bubbles 13. In addition, the isolation liquid, that is, the sample formed into each segment divided by the bubbles 13, is divided by the bubbles 13 and flows independently in the pipeline 2, so that mutual diffusion between the samples can be prevented. The gas for bubble isolation is preferably air, but it can also be an inert gas such as argon and helium, and various gases such as nitrogen and oxygen can also be used. These gases can also be used alone, or two or more gases can be mixed and used. In this way, after introducing a reagent into a continuous flow in a pipeline where a sample is separated by bubbles and performing a reaction operation, the bubbles are removed and the method of analyzing with a detector arranged downstream is called continuous flow analysis (CFA). In addition, in this specification, downstream refers to the downstream of the flow of the sample in the pipeline of the flow analysis.

[0050] (Reagent introduction section)

[0051] The reagent introduction part 3 is a device for adding a reagent to the flow of the sample transported in the pipeline 2. The reagent introduction part 3 is equipped with: a reagent introduction tube, which introduces the reagent into the pipeline 2; and a reagent introduction pump, which imparts suction force to the reagent introduction tube. The reagent may be a reagent added in the pretreatment of the sample. As the reagent, it is not limited to these contents, but for example, acids such as nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, phosphoric acid, hydrogen peroxide, and hydrofluoric acid; stabilizers for mercury such as L-cysteine ​​and gold; alkalis such as sodium hydroxide, potassium hydroxide, sodium peroxide, calcium carbonate, and sodium carbonate, etc. These reagents can also be used alone or in combination of two or more. In the case of using two or more reagents, multiple reagent introduction parts 3 can also be set, or if at least two of the reagents can be mixed and introduced, the reagents that can be mixed can also be mixed and introduced from one reagent introduction part 3. The reagent can be appropriately selected according to the analysis object and the analysis method, but from the perspective of high-precision analysis of mercury, it is more preferable to include nitric acid or a combination of nitric acid and hydrochloric acid. When inductively coupled plasma mass spectrometry (ICP-MS) is used as the analysis method, nitric acid or a combination of nitric acid and hydrochloric acid is preferably included.

[0052] (Heating unit)

[0053] The heating unit 5 is a device for heating the sample transported in the pipeline 2. The heating unit 5 can be a thermostatic bath equipped with a heater. However, the composition of the heating unit 5 is not limited to these contents, and it can also be an ultrasonic decomposition device, a microwave, and a high-pressure steam decomposition device. In addition, in the heating unit 5, the pipeline 2 can also form, for example, a coil. In one embodiment of the present invention, the heating unit 5 is arranged downstream of the reagent introduction unit 3. By heating the sample to which the reagent is added, the reaction between the sample and the reagent can be promoted and pretreatment can be performed. In the heating unit 5, for example, heating decomposition and high-temperature and high-pressure decomposition of the sample can be performed.

[0054] The heating temperature in the heating unit 5 can be set, for example, so that the sample becomes above 50°C, above 60°C, above 70°C, or above 80°C. The upper limit of the heating temperature is preferably below 140°C, below 130°C, or below 120°C. In addition, the heating time of the sample is, for example, more than 5 minutes, more than 10 minutes, or more than 20 minutes for each unit of the introduced sample (one sample). The upper limit of the heating time is, for example, less than 80 minutes, and more preferably less than 40 minutes. By setting the heating temperature and heating time in the heating unit 5 to the above range, the compound containing the mercury compound in the sample can be fully decomposed.

[0055] Figure 6 FIG. 2 is a diagram schematically showing bubbles in a pipeline after heat treatment in a flow analysis device according to an embodiment of the present invention. Figure 6 As shown, the bubbles 13 introduced into the bubble blocking portion 10 are expanded by the heat treatment. In addition, there are cases where the reaction between the sample and the reagent is accompanied by the generation of gas. In such cases, the generated gas is also expanded by the heat treatment. The gas generated and expanded by the reaction is dispersed in the blocking liquid as bubbles 14, or is integrated with the bubbles 13 introduced into the bubble blocking portion 10. At this time, at least a part of the mercury contained in the sample is vaporized by the heat treatment and converted into the gas phase of the bubbles 13 or the bubbles 14.

[0056] exist Figure 1 In the example of , the flow analysis device includes a pretreatment unit consisting of a reagent introduction section 3 and a heating section 5 arranged downstream thereof, but in order to add multiple reagents, a plurality of reagent introduction sections 3 can be arranged upstream of the heating section 5 instead of the single reagent introduction section 3.

[0057] Also, in Figure 1In the example of , the flow analysis device includes a pretreatment unit consisting of a reagent introduction section 3 and a heating section 5 provided downstream thereof, but may also include one or more reagent introduction sections 3, a heating section 5 provided downstream thereof, and another reagent introduction section 3 provided downstream of the heating section 5 and upstream of the analysis section 4. In the reagent introduction section 3 provided downstream of the heating section 5 and upstream of the analysis section 4, nitric acid, hydrochloric acid, or nitric acid and hydrochloric acid may be added as a reagent. In the case of using an inductively coupled plasma mass spectrometer (ICP-MS), by adding hydrochloric acid to the nitric acid solution upstream of the heating section 5 or downstream of the heating section 5 and upstream of the analysis section 4, mercury can be measured more stably.

[0058] Also, in Figure 1 In the example of , the flow analysis device has one pretreatment unit, but the flow analysis device may also have a plurality of pretreatment units, and in the case involved, the plurality of pretreatment units may also have different numbers of reagent introduction parts 3. By having a plurality of pretreatment units, for example, it is possible to perform a pretreatment in the form of adding acid again after acid decomposition under heating and performing acid decomposition under heating. In the case of having a reagent introduction part 3, the reagents added through each reagent introduction part 3 may be the same or different.

[0059] Also, in Figure 1 In the example, the reagent introduction part 3 is arranged downstream of the bubble barrier 10, but the configuration of the reagent introduction part 3 is not limited to these contents. The reagent introduction part 3 may also be arranged upstream of the bubble barrier 10. In the case where multiple reagent introduction parts 3 are provided, the reagent introduction part 3 may also be arranged upstream and downstream of the bubble barrier 10. Alternatively, there is also a case where the reagent introduced through the reagent introduction part 3 is a reagent for detecting a marker (for example, a color developing solution, etc.), and the case involved is that the reagent introduction part 3 is arranged downstream of the heating part 5. Alternatively, one or more reagent introduction parts 3 for introducing reagents for pretreatment may be arranged upstream of the heating part 5, and one or more reagent introduction parts 3 for introducing reagents for detecting markers may be arranged downstream of the heating part 5.

[0060] (Cooling section)

[0061] The cooling section 6 is a device for cooling the sample transported in the pipeline 2 after the heating treatment in the heating section 5. The cooling section 6 is designed to transport the sample therein, and preferably includes a tube of 0.5m to 3.0m. The pipeline 2 is connected to both ends of the tube of the cooling section 6, and the sample transported in the pipeline 2 after the heating treatment in the heating section 5 is directly and continuously transported in the tube of the cooling section 6, and the sample passing through the tube continues to be continuously transported in the pipeline 2. In other words, the tube of the cooling section 6 becomes the pipeline 2. The pipeline 2 is connected to the connecting parts at both ends of the tube of the cooling section 6, so that the sample transported in the tube and the gas are sealed in the pipeline. If the sample can be transported continuously, the inner diameter of the pipeline 2 and the inner diameter of the tube of the cooling section 6 can be the same or different.

[0062] The sample transported in the pipeline 2 after the heat treatment in the heating section 5 is introduced into the tube and cooled during the transportation in the tube. The length of the tube is more preferably 0.7m to 2.5m, and more preferably 1.0m to 2.0m. If the length of the tube is 0.5m or more, the sample treated by the heat is fully cooled during the transportation in the tube, so it is preferred. In the conventional flow analysis device in which the gas-liquid separation section is arranged downstream of the heating section, the length of the pipeline from the heating section to the gas-liquid separation section is usually 0.5cm to 20cm. In the analysis that does not target mercury, it is not necessary to lengthen the pipeline from the heating section to the gas-liquid separation section. This is because even if the sample in the pipeline is removed from the gas under the high temperature state, there is no problem that the element of the measurement object and the gas are removed at the same time. In the case of mercury as the object of measurement, when the temperature in the pipeline is at a high temperature, since mercury is contained in the gas phase side, the mercury can be restored to the liquid phase by lowering the temperature in the pipeline, so that mercury and gas can be avoided from being removed at the same time. Furthermore, if the length of the tube is 3 m or less, it will not take much time to transport the sample, so that the time required for analysis can be shortened and the device can be miniaturized.

[0063] There is no particular limitation on the cooling method in the cooling section 6, but examples thereof include a method of air cooling the pipeline 2 for transporting the heated sample, or a method of cooling with a refrigerant such as water (for example, a water cooling method, a cooling method with ice water), etc.

[0064] The material of the tube is not particularly limited as long as it is a material inert to the sample transported in the tube, and examples thereof include fluororesins such as perfluoroalkoxy resin (PFA) and polytetrafluoroethylene (PTFE); olefin resins such as polypropylene and polyethylene; glass; PEEK resin (polyetheretherketone resin), etc. In addition, the material of the pipeline 2 in the flow analysis device involved in one embodiment of the present invention is not particularly limited as long as it is a material inert to the sample transported in the tube, and for example, the same material as the above-mentioned tube can be used.

[0065] The inner diameter of the tube is not limited to the above, but is preferably 0.5 mm to 3.0 mm, more preferably 1.2 mm to 2.5 mm, more preferably 1.5 mm to 2.3 mm, particularly preferably 1.8 mm to 2.2 mm, and most preferably 1.9 mm to 2.1 mm. If the inner diameter is 0.5 mm or more, the sample can be transported at an appropriate speed in the tube. In addition, if the inner diameter is 3.0 mm or less, the frequency of contact between the sample transported in the tube and the tube wall of the tube increases, so the sample can be cooled faster, which is preferred.

[0066] The shape of the tube is not particularly limited, and can be a straight line or a curved line. Preferably, the tube includes a coil portion. The shape of the coil portion is, for example, a spiral, an 8-shaped spiral, etc. Fig.10 An example of the coil portion is schematically shown. Fig.10 (a) is a spiral coil portion, and (b) is an 8-shaped spiral coil portion. The tube includes the coil portion, and the sample transported in the tube is transported while rotating in the tube. Since the sample is stirred and mixed, the mercury in the gas phase is more likely to be converted into the liquid phase while the sample is cooled. Therefore, the loss caused by mercury vaporization can be prevented, thereby performing high-precision analysis, which is preferred.

[0067] When the tube includes the coil portion, the tube may be a tube consisting of only the coil portion or a tube including the coil portion and a straight portion. However, from the viewpoint of performing a higher precision analysis, it is more preferable to include the straight portion while including the coil portion. The reason is not clear, but the coil portion has the function of converting mercury in the gas phase into a liquid phase while cooling the sample because the sample is stirred and mixed. Since the straight portion has the function of cooling the sample more effectively, it is presumed that by combining the two, the loss caused by mercury vaporization can be more effectively prevented. The configuration of the coil portion and the straight portion is not limited to these contents, but, for example, a configuration in which the coil portion is configured downstream of the straight portion can be cited. According to the configuration involved, it can be considered that the sample after the heat treatment is mainly cooled in the straight portion, and the mercury existing as gas in the sample becomes liquid, and then is stirred and mixed in the coil portion to be converted into a liquid phase. In the case involved, the ratio of the length of the straight portion of the tube to the length of the coil portion is, for example, 1:1 to 10:1, and more preferably 2:1 to 5:2. In addition, here, in the ratio of the length of the straight portion of the tube to the length of the coil portion, "the length of the coil portion" refers to the length of the tube forming the coil portion, that is, the length of the tube when the coil portion is stretched into a straight line. Also, in the configuration in which the coil portion is arranged downstream of the straight portion, a second straight portion may also exist downstream of the configuration in which the coil portion is arranged downstream of the straight portion. The case involved is that the ratio of the length of the straight portion of the tube to the length of the coil portion refers to the ratio of the length of the straight portion upstream of the coil portion to the length of the coil portion, and the purpose is to not consider the length of the second straight portion.

[0068] Alternatively, the configuration in which the coil portion is arranged downstream of the straight portion may be repeated multiple times, for example, 2 to 10 times. The situation involved is also the "length of the coil portion" as described above. Also, in the configuration in which the coil portion is arranged downstream of the straight portion, a straight portion of the final segment may also exist downstream of the multiple repeated configurations. The situation involved is that the ratio of the length of the straight portion of the tube to the length of the coil portion refers to the ratio of the total length of the straight portion upstream of the multiple coil portions to the total length of the multiple coil portions, with the purpose of not considering the length of the straight portion of the final segment.

[0069] The number of revolutions of the spiral shape, 8-shaped spiral shape, etc. of the coil portion is not particularly limited, but is, for example, 1 to 20 revolutions, more preferably 2 to 10 revolutions, and even more preferably 4 to 7 revolutions. If the number of revolutions is 1 or more, since the sample is more evenly stirred and mixed, mercury in the gas phase is more easily converted into the liquid phase while the sample is cooled, which is preferred. In addition, if the number of revolutions is 20 or less, it is preferred because the device can be miniaturized or the time required for analysis can be shortened.

[0070] When the shape of the coil portion is, for example, a spiral, the outer diameter of the spiral (referred to as a "coil diameter") is not particularly limited, but is, for example, 10 mm to 70 mm, more preferably 15 mm to 60 mm, more preferably 20 mm to 50 mm, and most preferably 25 mm to 40 mm. If the coil diameter is 10 mm or more, liquid can be stably transported, which is preferred. Also, if the coil diameter is 70 mm or less, liquid can be more appropriately mixed, which is preferred.

[0071] When the shape of the coil portion is, for example, a spiral shape, the coil pitch is not particularly limited, but is, for example, 0.7 mm to 40 mm, more preferably 0.8 mm to 30 mm, and even more preferably 0.9 mm to 25 mm. If the coil pitch is 0.7 mm or more, a coil portion wound around a tube of a preferred diameter can be formed, which is preferred. Also, if the coil pitch is 40 mm or less, the size of the coil portion is a size that does not occupy much space, which is preferred.

[0072] When the shape of the coil portion is, for example, an 8-shaped spiral, the maximum length of the 8 is the same as the coil diameter in the spiral shape, and the pitch is the same as the coil pitch in the spiral shape.

[0073] The cooling temperature in the cooling unit 6 is, for example, such that the sample can be cooled to below 30°C, preferably below 20°C, and more preferably below 10°C. In addition, there is no particular limitation on the cooling time of the sample as long as it is a time for the sample to be sufficiently cooled, but for each unit of the introduced sample, it is, for example, more than 2 minutes, more than 3 minutes, or more than 5 minutes. The upper limit of the cooling time is, for example, 15 minutes for each unit of the introduced sample. By setting the cooling temperature and cooling time in the cooling unit 6 to the above range, mercury existing as gas in the sample can be turned into liquid.

[0074] The cooling unit 6 is disposed between the heating unit 5 and the gas-liquid separation unit 7 . The sample and the bubbles 13 and 14 transported in the pipe 2 are cooled in the cooling unit 6 and transported to the gas-liquid separation unit 7 in the pipe 2 .

[0075] (Gas-Liquid Separation Section)

[0076] The gas-liquid separator 7 is a device for sequentially removing the gas present in the pipeline 2 . Figure 7 Schematically shows how the gas in the pipeline 2 is removed by the gas-liquid separation unit 7. Figure 7 As shown, the gas-liquid separation section 7 comprises: a three-way pipe 7b, which includes a pipeline (pipeline 2) that continuously transports the sample in the horizontal direction or downward in the downstream direction of the pipeline 2, and a degassing pipe 7a that branches upward; a pump (not shown) that applies suction to the pipeline 2 that continuously transports the sample in the horizontal direction or downward; and a degassing pump (not shown) that applies suction to the degassing pipe.

[0077] like Figure 7 As shown, since the gas (bubbles 13, 14) existing in the pipeline 2 floats upward, it is removed (degassed) through the degassing pipe branched upward toward the tee pipe.

[0078] (Analysis Department)

[0079] The analysis unit 4 is a device for analyzing the sample after the reagent is added, the sample is subjected to heat treatment by the heating unit 5, the sample is cooled by the cooling unit 6 after the heat treatment, and the sample is subjected to gas removal by the gas-liquid separation unit 7 after cooling. In one embodiment of the present invention, the analysis unit 4 can be an inductively coupled plasma mass spectrometer (ICP-MS) instrument. However, the analysis unit 4 is not limited to these contents, and can also be any type of analysis device, for example, it can also be an inductively coupled plasma emission spectrometer (ICP-OES) instrument, an atomic absorption spectrometer, a triple-rod quadruple inductively coupled plasma mass spectrometer, an ion electrode instrument, or a spectrophotometer. The analysis unit 4 is not limited to a device for determining only the presence or concentration of mercury, and a device capable of batch determination of other metal elements is also preferred. In addition, the analysis can be either quantitative analysis or qualitative analysis.

[0080] (Marker Detection Department)

[0081] The marker detection unit 9 is connected to a branch pipe between the gas-liquid separation unit 7 and the analysis unit 4, and the branch pipe extracts the sample and the marker that flow through the pipeline 2 in sequence from the pipeline 2. In other words, after the gas is removed by the gas-liquid separation unit 7, in the stage before being introduced into the analysis unit 4, the pipeline 2 is divided into two branches, one (also called pipeline 2 after the branch) is connected to the analysis unit 4, and the other (called the branch pipe) is connected to the marker detection unit 9. The marker detection unit 9 continuously measures the liquid extracted from the pipeline 2 through the branch pipe, and if the marker is detected, a detection signal is output to the analysis unit 4. And, in one embodiment of the present invention, if the analysis unit 4 receives the detection signal, it starts to acquire analysis data. In one embodiment of the present invention, the marker detection unit 9 is a spectrophotometer, and in the case where rhodium is contained in the marker, a detection signal is output to the analysis unit 4 when rhodium is detected. However, the marker detection unit 9 is not limited to a spectrophotometer, and can also be, for example, a voltammeter, an ion electrode meter, an ion chromatograph, a turbidimeter, and a fluorescence photometer. The marker and the sample flowing sequentially from the pipeline 2 and the branch pipe are introduced into the analysis unit 4 and the marker detection unit 9, respectively, at the same timing. Alternatively, the timing at which the marker and the sample flowing sequentially are introduced into the analysis unit 4 and the marker detection unit 9 may be deviated and different. In the case where the timing is deviated, the marker and the sample flowing sequentially need to be introduced into the marker detection unit 9 at an earlier timing than the analysis unit 4. In addition, in the one embodiment, the analysis unit 4 is designed to start acquiring analysis data if the detection signal is received, but it may also be set to start acquiring analysis data after a specified time after receiving the detection signal.

[0082] In one embodiment of the present invention, the analyzing unit 4 and the marker detecting unit 9 are arranged in parallel as described above. However, the analyzing unit 4 and the marker detecting unit 9 may also be arranged in parallel as described above. Figure 4 The embodiment shown is configured in series. Figure 4 In the illustrated embodiment, the marker detection unit 9 is disposed between the gas-liquid separation unit 7 and the analysis unit 4. After the gas is removed by the gas-liquid separation unit 7 and before the liquid is introduced into the analysis unit 4, the marker detection unit 9 continuously measures the liquid introduced from the pipeline 2, and if the marker is detected, a detection signal is output to the analysis unit 4. And, after receiving the detection signal, the analysis unit 4 starts acquiring analysis data. In this case, the timing for starting to acquire analysis data can be adjusted so that the analysis unit 4 can measure the arrived sample. For example, it can be set that the analysis unit 4 starts acquiring analysis data after a specified time after receiving the detection signal.

[0083] exist Figure 1In the example of FIG. 1 , the sample from which the gas is removed by the gas-liquid separation section 7 is transported to the marker detection section 9 or the analysis section 4 downstream thereof. However, a mixing coil for further mixing the sample may be provided between the gas-liquid separation section 7 and the marker detection section 9 or the analysis section 4. The mixing coil is a pipe 2 formed in a coil shape. When the sample passes through the mixing coil, the sample flowing through the pipe 2 is mixed. The shape of the mixing coil is not particularly limited, but may be similar to the following: Fig.10 The shape shown is the same shape.

[0084] According to the flow analysis device involved in the above-mentioned embodiment 1, a sample is continuously introduced into the pipeline, bubbles are cut off, a reagent is introduced, a reaction is promoted by a heating unit, the sample and bubbles are cooled by a cooling unit so that the vaporized mercury is transformed into a liquid phase, and then the gas is removed by a gas-liquid separation unit, thereby preventing the loss of mercury caused by vaporization, and the analysis data can be continuously measured by the analysis unit. In addition, the flow analysis device includes: a marker introduction unit that introduces a marker into the pipeline; a marker detection unit that detects the marker and outputs a detection signal to the analysis unit, and the analysis unit can stably and continuously measure the sample by acquiring analysis data based on the detection signal.

[0085] Generally, when a flow analysis device is provided with a gas-liquid separation unit, a bubble blocking device for reintroducing gas into a pipeline is usually provided on the downstream side thereof, but in a flow analysis device according to an embodiment of the present invention, a bubble blocking device for reintroducing gas into a pipeline is provided between the gas-liquid separation unit and the analysis unit. Thus, mercury in the sample is introduced into the analysis unit 4 without volatilization, thereby preventing a decrease in analysis accuracy caused by the volatilization of mercury.

[0086] Furthermore, the flow analysis device according to one embodiment of the present invention may include a pressurizing unit that applies pressure against the flow of the sample to the heating unit 5 from the downstream side of the heating unit 5 . Figure 3 as well as Figure 8 1 is a partial schematic diagram showing an example of a flow analysis device including a pressurizing section 12 for applying pressure against the flow of a sample from the downstream side of a heating section 5 or from the downstream side of a cooling section 6. Figure 3 as well as Figure 8In the example, a pressure that resists the flow of the sample is applied from a pressurizing section 12 disposed on the downstream side of the gas-liquid separation section. The pressurizing section 12 includes, for example, a compressor and a valve. By having the pressurizing section involved, the sample can be decomposed at high temperature and high pressure in the heating section 5. Therefore, the decomposition of impurities including organic matter and the dissolution of mercury in the solution can be effectively performed, and thus it is preferred. The pressure applied by the pressurizing section 12 can be appropriately selected according to the heating temperature and heating time in the heating section 5, and there is no special limitation, but for example, it is less than 0.14 MPa, and includes a negative pressure of less than 0.1 MPa depending on the situation. The pressure is more preferably greater than 0.1 MPa and less than 0.13 MPa.

[0087] In the flow analysis device according to one embodiment of the present invention, an automatic sampler can be used as the sample introduction unit. In addition, an ultrasonic homogenizer or a stirrer can be provided to pulverize and / or stir the sample before sampling.

[0088] Alternatively, the flow analysis device according to one embodiment of the present invention may also include a dilution unit in the middle of the pipeline. Thus, when dilution is required according to the concentration of the sample, the desired dilution can be automatically performed in the flow analysis device. As the dilution unit involved, a commercially available automatic dilution device can be appropriately used.

[0089] Furthermore, the flow analysis device involved in one embodiment of the present invention may also be a device that incorporates a device for pretreating samples other than solid liquids and preparing liquid samples into the sample introduction section, or a device that is incorporated into the upstream of the sample introduction section. The flow analysis device is a device that uses a flow analysis method to analyze liquid samples, and samples other than solid liquids cannot be directly measured. Therefore, by incorporating a device that pretreats samples other than solid liquids to prepare liquid samples, it is possible to consistently perform the pretreatment of samples other than solid liquids until analysis. As the device involved, a device that performs fully automatic pretreatment of samples other than solid liquids is more preferred, for example, a fully automatic acid hydrolysis pretreatment device that can appropriately perform reagent addition, mixing, heating, and volume determination fully automatically.

[0090] [1.2] Implementation Method 2

[0091] Figure 2 The schematic configuration of a flow analysis device according to Embodiment 2 of the present invention is shown. For the sake of convenience, components having the same functions as those described in Embodiment 1 are denoted by the same reference numerals, and their description will not be repeated.

[0092] The flow analysis device according to the second embodiment of the present invention introduces a reagent into the flow of a sample in a pipeline that is not blocked by air bubbles, performs a reaction operation, and then performs analysis with a detector provided downstream, which is a method using flow injection analysis (FIA).

[0093] The flow analysis device involved in embodiment 1 of the present invention includes: a carrier introduction part 11, which introduces a carrier into the pipeline 2; a sample introduction part 1, which is used to introduce a sample into the flow of the carrier in the pipeline 2; a marker introduction part 8, which is used to introduce a marker into the flow of the carrier in the pipeline 2; a reagent introduction part 3, which adds a reagent to the flow of the sample transported in the pipeline 2; a heating part 5, which heats the sample transported in the pipeline 2 and to which the reagent is added; a cooling part 4, which cools the sample after the heating treatment; a gas-liquid separation part 7, which removes the gas present in the pipeline after cooling; an analysis part 4, which performs quantitative analysis or qualitative analysis on the sample from which the gas is removed in the gas-liquid separation part 7; a marker detection part 9, which detects the marker and outputs a detection signal to the analysis part 4, and the analysis part 4 is designed to obtain analysis data based on the detection signal.

[0094] The flow analysis device according to the second embodiment includes a carrier introduction section 11 upstream of a sample introduction section 1 for introducing a sample into a pipeline 2 and a marker introduction section 8 for introducing a marker into a pipeline 2, and is similar to the flow analysis device according to the second embodiment except that a bubble blocking section is not provided. Figure 1 The flow analysis devices shown have the same structure.

[0095] The flow analysis device involved in embodiment 2 is an analysis device using flow injection analysis (FIA), in which a carrier is introduced into pipeline 2 through a carrier introduction section 11, a sample is introduced into the flow in pipeline 2 through which the carrier flows through a sample introduction section 1, and a marker is introduced through a marker introduction section 8.

[0096] The carrier is not particularly limited as long as it is a liquid that does not adversely affect the pretreatment and analysis of the sample, and examples thereof include water, surfactants, acidic solutions, and alkaline solutions.

[0097] The other configurations of the flow analysis device according to the second embodiment have already been described in the first embodiment, and thus description thereof will be omitted.

[0098] [2] Flow analysis method

[0099] Hereinafter, a flow analysis method according to an embodiment of the present invention will be described. In addition, for the sake of convenience, the matters already described in the flow analysis device of [1] will not be repeated.

[0100] A flow analysis method according to one embodiment of the present invention comprises: a sample introduction step for introducing a sample into a pipeline; a reagent addition step for adding a reagent to the sample transported in the pipeline; an analysis step for performing a quantitative analysis or a qualitative analysis on the sample after the reagent is added; and further comprises: a heating step for performing a heat treatment on the sample to which the reagent is added; a cooling step for cooling the sample transported in the pipeline after the heat treatment; and a gas-liquid separation step for removing the gas existing in the pipeline after cooling.

[0101] The sample introduction step is a step of introducing a sample into the pipeline. For example, a plurality of samples are sampled by a sampling device and are sequentially and continuously introduced into the pipeline at a predetermined flow rate.

[0102] The reagent adding step is a step of adding a reagent to the flow of the sample transported in the pipeline, and the reagent is added through the reagent introducing section.

[0103] The analysis process is a process for analyzing the sample transported along the pipeline. Here, the analysis includes the detection of the presence or absence of the analysis object or the determination of the concentration. In addition, the analysis can be either quantitative analysis or qualitative analysis. The analysis method is also not particularly limited, and can be any type of analysis, but for example, inductively coupled plasma mass spectrometry, inductively coupled plasma emission spectrometry, atomic absorption spectrometry, triple-rod quadruple inductively coupled plasma mass spectrometry, ion electrode analysis, or spectroscopic spectrum analysis can be listed.

[0104] The analysis object is not particularly limited, but examples thereof include tap water, groundwater, seawater, lake water, various wastewaters from factories, etc., ion exchange water, ultrapure water, reagents, pharmaceuticals, reagents for semiconductors and industrial use, and various aqueous samples. According to the flow analysis method involved in one embodiment of the present invention, when mercury is analyzed as the analysis object, the following effects are achieved: mercury can be analyzed without complicated pretreatment, and samples containing mercury can be analyzed with the same accuracy as traditional methods. In addition, the flow analysis method involved in one embodiment of the present invention can be applied to the simultaneous analysis of metal elements containing mercury. Therefore, the simultaneous analysis of mercury and other metal elements, which were previously difficult to analyze due to volatilization, becomes possible.

[0105] The heating process is a process of heating the sample to which the reagent is added in the reagent adding process, the cooling process is a process of cooling the sample transported in the pipeline after the heating process in the heating process, the gas-liquid separation process is a process of removing the gas existing in the pipeline after cooling in the cooling process, and the sample from which the gas is removed in the gas-liquid separation process is analyzed in the analysis process.

[0106] The flow analysis method according to one embodiment of the present invention comprises the sample introduction step, the reagent addition step, the heating step, the cooling step, the gas-liquid separation step, and the analysis step, and comprises a marker introduction step of introducing a marker into a pipeline between the sample introduction step and the subsequent sample introduction step. Here, the marker introduction step and the sample introduction step are preferably performed in a manner that the marker and one or more predetermined number of samples are alternately introduced into the pipeline.

[0107] Furthermore, a flow analysis method according to one embodiment of the present invention includes a marker detection step of detecting the marker and outputting a detection signal to an analysis device, and the analysis step acquires analysis data based on the detection signal.

[0108] The flow analysis method involved in one embodiment of the present invention may also be a method using a continuous flow analysis method (CFA) or a method using a flow injection analysis method (FIA). In the case where the flow analysis method involved in one embodiment of the present invention is a method using a continuous flow analysis method (CFA), the flow analysis method includes a bubble isolation step, which performs bubble isolation on the sample and marker introduced into the pipeline, and produces a plurality of segments divided according to bubbles in the pipeline. In the case where the flow analysis method involved in one embodiment of the present invention is a flow injection analysis method (FIA), the flow analysis method may include a carrier introduction step before the sample introduction step and the marker introduction step.

[0109] [3] Summary

[0110] One embodiment of the present invention includes the following configurations.

[0111] <1> The flow analysis device is characterized in that it includes: a sample introduction part, which is used to introduce a sample into a pipeline; a reagent introduction part, which adds a reagent to the sample transported in the pipeline; an analysis part, which performs quantitative analysis or qualitative analysis on the sample after the reagent is added; it also has: a heating part, which heats the sample to which the reagent is added; a cooling part, which cools the sample transported in the pipeline after the heat treatment; and a gas-liquid separation part, which removes the gas existing in the pipeline after cooling.

[0112] <2> according to <1> In the flow analysis device, the cooling part is designed to contain a tube of 0.5 m to 3 m, in which the sample is transported.

[0113] <3> according to <2> In the flow analysis device, the tube comprises a coil portion.

[0114] <4> According to the claim <1> to <3> The flow analysis device described in any one of the above further includes: a marker introduction unit, which is used to introduce a marker into the pipeline; a marker detection unit, which detects the marker and outputs a detection signal to the analysis unit, and the analysis unit is designed to obtain analysis data based on the detection signal.

[0115] <5> according to <4> In the flow analysis device, the marker introduction section and the sample introduction section enable alternate introduction of the marker and one or more predetermined numbers of samples into the pipeline.

[0116] <6> according to <1> to <5> In any one of the flow analysis devices described above, the analysis unit is an inductively coupled plasma mass spectrometer or an inductively coupled plasma emission spectrometer.

[0117] <7> according to <1> to <6> According to any one of the flow analysis devices described above, the reagent includes nitric acid.

[0118] <8> according to <1> to <7> According to any one of the flow analysis devices described above, the reagent includes hydrochloric acid.

[0119] <9> according to <1> to <8> The flow analysis device described in any one of the above is a device for measuring the concentration of metal elements including mercury.

[0120] <10> according to <1> to <9> The flow analysis device according to any one of claims 1 to 6 includes a bubble blocking unit that blocks bubbles from a sample introduced into a pipeline and creates a plurality of segments divided according to bubbles in the pipeline.

[0121] <11> The flow analysis method is characterized in that it includes: a sample introduction process, which is used to introduce the sample into the pipeline; a reagent addition process, which adds the reagent to the sample transported in the pipeline; an analysis process, which performs quantitative analysis or qualitative analysis on the sample after the reagent is added, and also includes: a heating process, which heats the sample to which the reagent is added; a cooling process, which cools the sample transported in the pipeline after the heat treatment; and a gas-liquid separation process, which removes the gas existing in the pipeline after cooling.

[0122] <12> according to <11> The flow analysis method does not perform bubble isolation after the gas-liquid separation process.

[0123] Example

[0124] The present invention is described in more detail through the following embodiments, but the present invention is not limited to these embodiments, and embodiments obtained by appropriately combining the technical solutions disclosed in the embodiments are also included in the scope of the present invention.

[0125] [Device]

[0126] As a flow analysis device, Figure 1 In the flow analysis device shown, Figure 1 The B part of the Figure 4 An analysis device of the structure. The flow analysis device comprises: a sample introduction part 1, which is used to introduce a sample into a pipeline 2; a marker introduction part 8, which is used to introduce a marker into the pipeline 2; a bubble isolation part 10, which isolates bubbles from the sample and the marker introduced into the pipeline 2; a reagent introduction part 3, which adds reagents to the flow of the sample transported along the pipeline 2 in the pipeline; a heating part 5, which heats the sample transported along the pipeline 2; a cooling part 6, which cools the sample after the heating treatment; a gas-liquid separation part 7, which removes the gas existing in the pipeline after cooling; an analysis part 4, which performs quantitative analysis or qualitative analysis on the sample from which the gas is removed in the gas-liquid separation part 7; a marker detection part 9, which detects the marker and outputs a detection signal to the analysis part 4, and the analysis part 4 is designed to obtain analysis data based on the detection signal. Between the gas-liquid separation part 7 and the analysis part 4, there is no bubble isolation part for reintroducing the gas into the pipeline.

[0127] Air is used as the gas for the bubble barrier, and is introduced into the pipeline 2 at a rate of once every 4 seconds. A mixture of 1 mol / L nitric acid and 1 mol / L hydrochloric acid in a volume ratio of 1:1 is used as the reagent. Palladium is used as a marker, and palladium is introduced into the pipeline 2 in the form of a palladium nitric acid acid solution (the concentration of palladium is 100 mg / L). The above-mentioned palladium nitric acid acid solution and the sample are alternately introduced into the pipeline 2. In addition, a spectrophotometer (manufactured by BL Technology Co., Ltd., SCIC4000) is used as a detection device of the marker detection unit 9, and an inductively coupled plasma mass spectrometer (manufactured by Agilent Technologies, Inc., Agilent 7800ICP-MS) is used as an analysis device of the analysis unit 4.

[0128] A pressure of 0.13 MPa was applied to the heating section 5 from the downstream side thereof by a compressor. This pressure was a pressure that resisted the flow of the sample. The heating temperature in the heating section 5 was set so that the sample reached 100°C.

[0129] The cooling part 6 uses a PFA tube with a length of 1.5m and an inner diameter of 2.0mm. The tube is composed of a 1.2m straight section, a 0.6m coil section, and a 0.3m straight section from the outlet of the heating part 5. The number of turns of the coil section is 5, the coil diameter is 40mm, and the coil pitch is 3.0mm. In addition, cooling is performed by air cooling, and the ambient temperature of the cooling part 6 is 15°C.

[0130] The marker detection unit 9 and the analysis unit 4 are as follows Figure 4In the series configuration shown, the sample removed by the gas-liquid separation unit 7 is continuously measured by the marker detection unit 9 before being introduced into the analysis unit 4 and then transported to the analysis unit 4. If the marker detection unit 9 detects the marker, it outputs a detection signal to the analysis unit 4, and the analysis unit 4 starts acquiring analysis data after receiving the detection signal.

[0131] [Example 1: Preparation of calibration curve]

[0132] A diluent prepared by mixing a mixture of 1 mol / L nitric acid and 1 mol / L hydrochloric acid in a volume ratio of 1:1 and ultrapure water in a volume ratio of 1:100 was used to prepare a standard solution containing mercury in a concentration range of 0.01 μg / L to 1 μ / L, and a calibration curve was prepared using the flow analysis device.

[0133] The obtained calibration curve is Fig. 9 As shown, it has been confirmed that a good straight line relationship is shown.

[0134] [Example 2: Analysis of dam lake bottom water]

[0135] The concentration of metal elements in the sample was measured using the flow analyzer. Dam lake bottom water was used as the sample. Mercury was added to the sample to 0.05 μg / L and 0.5 μg / L, and an addition recovery test was performed.

[0136] Table 1 shows the measurement results of the samples and the results of the addition recovery test.

[0137] [Table 1]

[0138]

[0139]

[0140] [Example 3: Analysis of groundwater]

[0141] The sample measurement and the addition recovery test were carried out in the same manner as in Example 2 except that groundwater was measured as the sample.

[0142] [Example 4: Analysis of tap water]

[0143] The sample measurement and the addition recovery test were carried out in the same manner as in Example 2 except that tap water was used as the sample.

[0144] According to the results shown in Table 1, a high recovery rate was obtained in any of the samples with a large amount of organic matter at the bottom of the dam lake, groundwater, and tap water. The same recovery rate was also obtained in the analysis according to the conventional official method, which confirmed that it is possible to analyze samples containing mercury with the same accuracy as the conventional method according to the flow analysis device and flow analysis method.

[0145] Possibility of Industrial Application

[0146] According to the present invention, it is possible to provide a flow analysis apparatus and a flow analysis method which can analyze mercury without complicated pretreatment and can continuously analyze a sample containing mercury with the same accuracy as that of a conventional method.

[0147] According to such a configuration, it is possible to contribute to the reduction of pollution of environmental water, tap water, etc. Thus, it is possible to contribute to the achievement of Goals 14 and 15 of the Sustainable Development Goals (SDGs).

[0148] Explanation of symbols

[0149] 1 Sample introduction section

[0150] 2 Pipeline

[0151] 3 Reagent introduction section

[0152] 4 Analysis Department

[0153] 5 Heating unit

[0154] 6 Cooling section

[0155] 7 Gas-liquid separation section

[0156] 8 Marker introduction unit

[0157] 9 Marker Detection Department

[0158] 10 Bubble barrier

[0159] 11. Vector introduction unit

[0160] 12 Pressurizing section

[0161] 13 Bubbles

[0162] 14 Bubbles

Claims

1. A flow analysis device, characterized in that include: A sample introduction part, used for introducing the sample into the pipeline; a reagent introduction section for adding a reagent to the sample transported in the pipeline; An analysis unit that performs quantitative or qualitative analysis on the sample after the reagent is added; Also available: A heating unit that heats the sample to which the reagent is added; a cooling unit for cooling the sample transported in the pipeline after the heating treatment; A gas-liquid separation unit removes the gas existing in the pipeline after cooling. 2 . The flow analysis device according to claim 1 , wherein the cooling unit is designed to include a tube of 0.5 m to 3 m in length, in which the sample is transported.

3. The flow analysis device of claim 2, wherein the tube comprises a coil portion.

4. The flow analysis device according to any one of claims 1 to 3, further comprising: A marker introduction part, used for introducing a marker into the pipeline; a marker detection unit that detects the marker and outputs a detection signal to the analysis unit; The analysis unit is designed to acquire analysis data based on the detection signal. 5 . The flow analysis device according to claim 4 , wherein the marker introduction unit and the sample introduction unit enable alternate introduction of the marker and one or more predetermined numbers of samples into the pipeline. 6 . The flow analysis device according to claim 1 , wherein the analysis unit is an inductively coupled plasma mass spectrometer or an inductively coupled plasma optical emission spectrometer.

7. The flow analysis device according to any one of claims 1 to 6, wherein the reagent comprises nitric acid.

8. The flow analysis device according to any one of claims 1 to 7, wherein the reagent comprises hydrochloric acid. 9 . The flow analysis device according to claim 1 , which is a device for measuring the concentration of metal elements including mercury. 10 . The flow analysis device according to claim 1 , further comprising a bubble blocking unit for blocking bubbles of a sample introduced into a pipeline and forming a plurality of segments divided by bubbles in the pipeline.

11. A flow analysis method, characterized in that include: A sample introduction process, which is used to introduce the sample into the pipeline; a reagent adding step of adding a reagent to the sample transported in the pipeline; An analysis step, which performs quantitative or qualitative analysis on the sample after the reagent is added; Also includes: A heating step, in which the sample to which the reagent is added is subjected to a heating treatment; a cooling step, which cools the sample transported in the pipeline after the heating treatment; The gas-liquid separation process removes the gas existing in the pipeline after cooling. 12 . The flow analysis method according to claim 11 , wherein bubble isolation is not performed after the gas-liquid separation step.

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