JP3216714B2 - Gas sampling device, gas analyzer and gas analysis method using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas sampling device for efficiently sampling a trace gas component or the like in order to continuously monitor a trace gas component or a trace volatile component in the atmosphere, and a gas using the gas sampling device. The present invention relates to an analyzer and a gas analysis method.

[0002]

2. Description of the Related Art Conventionally, for analysis of gas components in the atmosphere, a sample is taken on site and brought back to an analysis room for analysis by various analysis methods, or a specific component is sent to a site from a sensor and a recording device. A method of installing and monitoring an analyzer has been adopted. In most cases, on-site sampling is performed by absorbing the component to be analyzed with an absorbing solution or absorbent, and the analysis of the component is performed using the absorbing solution itself in the case of the absorbing solution and the absorbing solution itself in the case of the absorbing agent. Used an extract obtained by adding an extract to an absorbent to extract components.

[0003] Liquid chromatographs such as high-performance liquid chromatographs and ion chromatographs have the characteristic that multiple components in a liquid can be analyzed with high sensitivity by a single sample injection. In particular, ion chromatographs for the analysis of inorganic components have become widely used because other analysis methods can easily analyze anion components that require complicated analysis operations. In the method described above, a method of analyzing the absorption solution or the extract by ion chromatography after the sampling is performed as described above is also used.

[0004] In an analysis method for collecting gas by using an absorbing solution, ultrapure water or ultrapure water containing about 100 ppm of H ₂ O ₂ is put into a gas collecting device called a bubbler or an impinger as an absorbing solution, and is measured. A method of dissolving a component to be analyzed in an absorbing solution by suctioning a predetermined amount of air with a pump and bubbling the air is widely used. Atmospheric analysis by ion chromatography is performed by a manual batch process in which a measurer prepares a sample solution and supplies it to the ion chromatograph every time measurement is performed. Therefore, there is a problem that not only the preparation of the sample liquid is troublesome, but also an error occurs in the amount of dissolution into the absorption liquid during the preparation of the sample liquid, and it is difficult to perform accurate measurement.
In addition, contamination by the sample was a serious problem in the case of trace components due to manual sampling. Further, there is a disadvantage that the measurement cannot be performed continuously. In order to solve this problem, an automatic monitor using the analysis method has also been developed.
JP-A-9-257777, JP-A-10-2064
No. 09 discloses this.

[0005] In the analysis apparatus and analysis method of Japanese Patent Application Laid-Open No. 9-257777, an impinger (absorber) shown in FIG. 7 is used for gas sampling. In FIG. 7, the impinger 104 has a structure in which an outer tube 140 and an inner tube 145 are detachably combined.
The upper and lower ends of each of the 45 are open. Outer cylinder 14
The lower end 141 of the “0” is connected to a valve 153 so as to be openable and closable, and one upper end opening 142 is closed airtightly by a lid 146 provided in the inner cylinder 145. The opening 147 at the lower end of the inner cylinder 145 is
It is immersed in pure water 160 as an absorbing liquid stored in the chamber 0, and the upper end is an inlet 148 for introducing the sample air into the impinger 104.

The lid 146 is provided with an exhaust port 149 connected to an exhaust device (not shown) so as to be positioned above the liquid level of the pure water 160 stored in the outer cylinder 140. . Pure water 160 is provided beside the impinger 104.
The light emitting element 180 and the light receiving element 18
1 is provided, and the level sensor 108 is controlled so that the amount of pure water 160 stored in the impinger 104 becomes constant during analysis.

[0007] To the impinger 104, electromagnetic three-way valves 153, 154 and 155 are connected in series.
The valves 154 and 153 are opened, and pure water is supplied to the inside of the impinger 104 from the opening 141 at the lower end of the outer cylindrical portion 140 of the impinger 104 from the pure water circulation device. The sample air introduced from the inlet 148 is blown into the pure water 160 by sucking by an exhaust device (not shown) connected to the exhaust port 149, and the analyte in the sample air is absorbed by the pure water. The water 160 is sent to the analyzer main body (not shown) and analyzed by the analyzer main body.

As described above, the use of the automatic monitoring makes it possible to monitor on-site, and an analysis result can be obtained immediately on-site. For example, it is effective for managing a semiconductor manufacturing environment in which a change in the manufacturing environment greatly affects the yield and reliability of products. However, for automatic monitoring, it is necessary that there is no mutual interference between the measurements and that a stable and highly reliable analytical value can be obtained in the long term.

In the prior art disclosed in Japanese Patent Application Laid-Open No. 6-11496, the impinger 202 shown in FIG. 8 is used for gas collection, and the valves A to E and the pump P are set as shown in the flowchart of the analysis step of FIG. , "Open",
By performing the operation of "close", "movement", and "stop", the absorption liquid in the impinger is discharged and washed for each measurement, thereby preventing interference from the previous measurement.

In the prior art apparatus disclosed in Japanese Patent Application Laid-Open No. 10-206409, a nitrogen gas line 334 is connected to an intake pipe 332 on the sample air introduction side of an impinger, as shown in FIG. A switching valve 333 is connected, and a mechanism for purifying the inside of the absorbing liquid container 339 by purging with nitrogen gas is provided.

In the collection by the impinger, the collection rate of the analyte is dependent on the contact area and the contact time between the absorbing solution and the sample air, so that a high collection rate can be obtained stably.
In the apparatus disclosed in Japanese Patent Application Laid-Open No. H10-206409, as shown in FIG. 11, the absorption liquid container 339 has a long cylindrical shape, the intake pipe 332 is long enough to reach the bottom of the container, and the discharge port at one end of the intake pipe is provided. Reference numeral 359 is a plate having a large number of fine holes.

[0012]

However, in the analyzer described in JP-A-6-11496, pure water is supplied from the bottom of the analyzer and overflows from the upper part.
To clean the collection container, a large amount of pure water is required depending on the capacity of the collection container. In addition, simply supplying pure water into the container cannot sufficiently wash organic substances that are easily adsorbed on the surface of the container, and if used for a long period of time, the inner wall of the container will be stained. In the purging performed by the analyzer described in JP-A-10-206409, the cleaning ability is further inferior to the pure water cleaning.

When a monitoring device cannot be installed at the measurement point, a pipe is usually provided between the device and the measurement point with a sampling pipe such as a fluororesin pipe. Adsorption to the surface cannot be ignored. This problem is not considered at all in the prior art, and no countermeasure is taken.

Further, the structure having a fine hole at the outlet of the intake pipe, which is used in the prior art apparatus disclosed in Japanese Patent Application Laid-Open No. Hei 10-206409, is required to improve the collection rate of the analyte. Although it is effective as a method for increasing the particle size, fine particle components and the like in the sample atmosphere tend to accumulate, which may cause a problem when used continuously for a long period of time.

Therefore, the present invention has been made in view of such problems, and prevents the adsorption of organic substances in the atmosphere on the inner wall surface of a gas collecting container, and collects them by washing with a small amount of pure water. An object of the present invention is to provide a gas sampling device having a self-cleaning function capable of maintaining the inside of a container clean and a function of increasing a trapping rate by enlarging the surface area of an absorbing solution, a gas analyzer using the same, and a gas analysis method. And

Still another object of the present invention is to provide a gas analyzer and a gas analysis method that do not delay sampling response until an accurate analysis value is obtained.

[0017]

According to the present invention, there is provided a gas sampling container main body for holding an absorbing solution for absorbing a component to be analyzed by passing the sample air to be measured, and the absorbing solution in the gas sampling container main body. A sample atmosphere supply pipe for supplying a sample atmosphere so as to contact the sample atmosphere, a sample atmosphere exhaust pipe for discharging the sample atmosphere from the inside of the gas sampling container main body after contacting the absorbing solution, and an ultraviolet light for the gas. An ultraviolet light source for irradiating at least the inner wall of the collection container main body, and when a cleaning liquid is supplied into the gas collection container main body for cleaning, the cleaning liquid flows down while wetting the inner wall of the gas collection container main body. And a cleaning liquid supply pipe disposed therein.

The present invention also relates to a gas analyzer having the gas sampling device, means for introducing a sample atmosphere into the gas sampling device, and component detecting means for detecting a component to be analyzed absorbed in the absorbing solution. .

Further, the present invention provides a sampling step of allowing a sample air to be measured to pass through an absorbing solution held in a gas sampling container main body to absorb a component to be analyzed; And a cleaning step of irradiating at least the inner wall of the gas collection container body with ultraviolet light and causing the cleaning liquid to flow down to wet the inner wall of the gas collection container body.

In the present invention, it is preferable to use the same liquid as the absorbing liquid as the cleaning liquid.

[0021]

DETAILED DESCRIPTION OF THE INVENTION According to the study of the present inventors, quartz and glass originally have a hydrophilic surface, but when exposed to the atmosphere, organic substances in the atmosphere, especially organic substances having a high affinity for silanol groups, are adsorbed. And the hydrophilicity decreases. However, the attached organic matter is decomposed when irradiated with ultraviolet light, and the hydrophilic surface is recovered by washing with pure water. Therefore, for example, the gas collection container body is formed of a hydrophilic material that transmits ultraviolet light, and during cleaning, the cleaning liquid is caused to flow along the inner wall surface while irradiating ultraviolet light.
The analysis accuracy can be improved by washing away the organic components and the like attached to the surface, and the hydrophilicity of the inner wall of the gas collection container body is improved and the inner wall is easily wetted with the absorbing liquid, so that the sample air is absorbed. The present inventors have found that the surface area of the absorbing solution is improved in the process, and the collection rate of the analyte in the air sample is increased, thereby completing the present invention. When the collection rate of the component to be analyzed is high as described above, it is possible to obtain a high-concentration analysis sample by reducing the amount of the absorbing solution. There is an advantage that the influence is extremely small.

<Gas sampling device> Example of gas sampling device of the present invention and gas analyzer using the same (first embodiment)
Will be described with reference to the drawings. FIG. 1 is an overall view of an example of a gas analyzer using the gas sampling device of the present invention, and FIG. 2 is a diagram showing the gas sampling device.

First, as shown in FIG.
Includes a gas collection container main body (hereinafter, also simply referred to as a collection container main body) 21, an ultraviolet light source 22, and a reflection plate 23.
In this example, the absorbent / cleaning liquid supply pipe 24 serves both as a cleaning liquid supply pipe and an absorbing liquid supply pipe, and the upper part of the collecting vessel main body 21 is supplied into the collecting vessel main body 21 so that the absorbing liquid and the cleaning liquid can be supplied from above. And the tip nozzle 24a
Is open inside. Further, a sample atmosphere supply pipe 26 for supplying the sample atmosphere into the gas sampling vessel 21 is provided at a lower portion of the sampling vessel main body 21 and in a state where the absorbing liquid is stored in the sampling vessel main body, the sample atmosphere is supplied from the lower portion. Bubbling can be done. Although the absorbing liquid supply pipe and the cleaning liquid supply pipe can be provided separately, it is usually preferable to use the same liquid as in this example.

The absorbent / washing liquid discharge pipe 25 is connected to a lower portion of the collection container main body 21 for discharging the absorption liquid and the cleaning liquid, and discharges the sample air from the inside of the collection container main body 21. Air exhaust pipe 27 for the sample is provided on the upper part of the sampling container main body 21.

At least the inner wall of the collection container main body 21 is hydrophilic. At the same time, at least the inner wall of the main body of the collection container is inert to the absorbing solution and the washing solution, and the elution of the analyte from the inner wall to the absorbing solution is extremely small (preferably, there is no elution at all), and the sample is analyzed. It is formed of a material that does not react with the components.

The example shown in FIG. 1 is an example in which ultraviolet light is irradiated from the outside of the collection container main body. In this case, the collection container main body 21 transmits the ultraviolet light at least in a portion irradiated with the ultraviolet light. It is formed of such a material. Therefore, the entire collection container body may be formed of a material that transmits ultraviolet light and is inactive with respect to the absorbing liquid and the cleaning liquid, or may be formed of a material that is not necessarily inert with respect to the absorbing liquid and the cleaning liquid. If it is a material that transmits light, the main body may be formed thereby and the inner wall may be coated with a material that is inert to the absorbing liquid and the cleaning liquid. Even when coating the inner wall, it is necessary to transmit ultraviolet rays as a whole.

As the material, it is preferable to use heat-resistant glass such as quartz or "Pyrex" (registered trademark), and quartz is most suitable.

According to the results of verification by the present inventor, when the ultraviolet light attenuation rate inside and outside the wall of the collection container main body is 90% or less, the cleaning described later is performed to perform the cleaning.
The inner wall surface is kept highly hydrophilic even after months of continuous use.
Further, it is preferable that the attenuation rate of ultraviolet light inside and outside the wall of the collection container main body is 50% or less.

Such a configuration in which ultraviolet light is irradiated from the outside of the collection container body is preferable because the structure inside the collection container body can be simplified and cleaning can be easily performed, but the present invention is not limited to such a case. Alternatively, the ultraviolet light source can be housed in, for example, quartz or "Pyrex" and placed inside the collection container body. In this configuration, the main body of the collection container is not necessarily required to be transparent, and may be formed of, for example, a metal and its inner wall may be coated with a material inert to an absorbing solution and a cleaning solution such as silica.

The ultraviolet light used in the present invention may be any as long as it contains a wavelength of 280 nm or less.
It includes a wavelength of 30 to 280 nm. Note that the above-mentioned attenuation rate refers to an attenuation rate in a wavelength region of 230 to 280 nm. As a light source to be used, a low-pressure mercury lamp, a black light fluorescent tube, or the like can be used. Further, an ozone-less type that does not include a short wavelength is preferable.

When irradiating ultraviolet light from the outside of the collection container main body, as shown in FIG.
It is preferable that the ultraviolet light source 22 and the ultraviolet light source 22 are surrounded by a reflection plate 23. By installing in the space surrounded by the reflective material that reflects ultraviolet light in this way, it is possible to easily irradiate the entire periphery of the collection container body with ultraviolet light, and to make effective use of ultraviolet light. Can be.

The reflector may be installed alone, but the main body of the collection container may be housed in a jacket for protection in order to prevent cracking or the like. May be processed so as to reflect the light to form the reflection plate 23. Further, even in the case where an outer jacket is provided, a reflecting plate may be inserted between the outer jacket, the ultraviolet light source and the collection container main body.

In this gas sampling apparatus, a cleaning liquid is supplied from the nozzle 24a to the sampling vessel main body 21 when the absorbing liquid is stored in the sampling vessel main body and when the inside of the sampling vessel main body is cleaned. When storing the absorbent,
The cleaning liquid discharge pipe 25 is closed, and at the time of cleaning, the absorption liquid / cleaning liquid discharge pipe 25 is opened so that the cleaning liquid flows out.

At least at the time of cleaning, it is essential that the inner wall of the collection container is wet with the cleaning liquid. For example, as shown in FIG. 3, a hole is provided in the tube at the tip of the nozzle, and the cleaning liquid is directed toward the inner wall of the collection container. So that
The introduced cleaning liquid flows downward while wetting the inner wall of the collection container main body 2.

When the ultraviolet light source 22 is turned on at the time of this cleaning to irradiate the collection container main body 21 with ultraviolet light, organic substances attached to the inner wall surface are decomposed and washed away by the cleaning liquid. Either cleaning while irradiating ultraviolet light (referred to as UV cleaning) or cleaning including simply spraying and flowing a cleaning liquid without irradiating ultraviolet light (referred to as single cleaning) is performed for each measurement. The inner wall surface of the collection container main body 21 is maintained in a clean and highly hydrophilic state.
The cleaning liquid flowing down the inner wall surface wets the entire inner wall surface and forms a water film on the inner wall surface. This further increases the cleaning efficiency.

For example, after performing the UV cleaning for a predetermined time, the UV is turned off, and the simple cleaning is further performed. Even if reactive reactive radicals or the like are generated by irradiation of ultraviolet light, the radicals are washed away by the cleaning. The components to be analyzed in the sample air introduced into the sampling container main body 21 by the sampling of the sample are not chemically changed.

At the time of sampling the sample atmosphere, the sample atmosphere is blown into the sampling vessel main body 21 from below through the sample atmosphere supply pipe 26 with a predetermined amount of the absorbing liquid stored in the sampling vessel main body 21. Since the inner wall surface of the collection container main body 21 cleaned as described above is highly hydrophilic, as shown schematically in FIG. 4, the blown sample atmosphere comes into contact with the absorbing solution and then is wrapped in the absorbing solution. It rises while maintaining the state of the foam. The foam breaks when it comes into contact with the tip of the nozzle 24a. When the bubbles are repelled, the absorbing liquid, which has become a film of the bubbles, flows down on the inner wall surface of the collection container main body 21, and the sample air from which the analyte is absorbed and removed is discharged from the sample air discharge pipe 27. During the sampling in this way, the collection container body 2
By forming a water film on the entire inner wall surface of the sample 1, contact between the sample atmosphere and the absorbing solution is performed very efficiently.

The appearance of air bubbles in the sample atmosphere in the absorbing solution shown in FIG. 4 is a schematic one, and the smaller the bubbled bubbles are, the more efficient the contact with the absorbing solution is made. . For example, by narrowing the tip to allow fine bubbles to come out, or by attaching a porous member made of a material that does not elute a substance that adversely affects the analysis into the absorbing solution, such as a sintered body of glass or the like It can be carried out.

It is preferable that the tip of the nozzle is formed of a non-hydrophilic material so that bubbles of the absorbing liquid can be easily broken. The shape of the main body of the gas collection container is not limited as long as it has a shape that fulfills the functions described above, and may be cylindrical, square (square, hexagonal, etc.), flat cylindrical or square, or any of these. , And the cross-section becomes slightly narrower toward the upper part.
Generally, a cylindrical shape is preferable because it is easily available and easily processed. Further, the shape of the upper end and the lower end of the main body of the gas collection container is not limited as long as it has a shape that fulfills the functions described above.

The absorbing liquid used in the present invention is an aqueous liquid that can wet the wall surface of the hydrophilic gas sampling body without being repelled, and is, for example, pure water or a substance dissolved in accordance with a component to be analyzed. Aqueous solution. On the other hand, the cleaning liquid is a water-based liquid, and may be any liquid that can wet the wall surface of the hydrophilic gas sampling body without being repelled,
It may contain additives to enhance the cleaning effect, but in order to minimize the effect on the analysis,
It is preferable to use the same liquid as the absorbing liquid. Normally,
Even with the same liquid as the absorbing liquid, a sufficient cleaning effect can be obtained by the action of ultraviolet rays.

<First Gas Analysis Apparatus and Gas Analysis Method>
Embodiment> An example of a gas analyzer and a gas analysis method using the above gas sampling device will be described below. FIG.
3 is a flowchart showing one example of the gas analysis method of the present invention. In this example, ultrapure water was used for both the cleaning liquid and the absorbing liquid.

The first step is a drainage step (S101), and two concentration steps (S105) at startup and during continuous measurement.
Is a step of discharging the absorbent remaining in the collection container main body 21 from the collection container main body 21 after. In the example of the gas analyzer shown in FIG. 1, three-way valves 44 and 45 are provided as a switching mechanism for taking in or bypassing the sample air, and in the draining step S101, the three-way valves 44 and 45 are provided.
5 is set to the flow path indicated by the solid line, and the sample air sucked by the suction pump 41 is directly exhausted without being introduced into the gas sampling device.

Then, the three-way valve 16 is set to the flow path shown by the solid line, and the liquid supply pump 12 is operated to operate the collection container main body 2.
The absorbent remaining in 1 is drained to the waste liquid side of the liquid sending pump 12. At this time, the three-way valve 43 is set to the flow path shown by the broken line, and the extension of the sample atmosphere discharge pipe 27 is set to the open end, thereby preventing the inside of the collection container main body 21 from becoming a negative pressure when the liquid feed pump 12 operates. be able to. Second and third to be described later
In the step (3), the three-way valve 43 is set to the flow path indicated by the broken line for the same reason.

The second step is a UV cleaning step (S1).
02). The UV light source 22 is turned on, and the three-way bulb 16 is turned on.
1 and the three-way valves 17, 18, and 19 and the flow path switching valve 32 shown in FIG. 1 are set to flow paths indicated by solid lines, and the three-way valve 43 is set to flow paths indicated by broken lines. By operating the liquid pump 11, the absorption liquid
Ultrapure water can be supplied from the cleaning liquid supply pipe 24 into the collection container main body 21 as a cleaning liquid.

This supply state is continued for a predetermined time, and the inside of the collection container main body is washed with ultrapure water while irradiating the collection container main body 21 with ultraviolet light. The ultrapure water that has flowed down to the bottom of the collection container body 21 is supplied to the absorbent / washing liquid discharge pipe 25 and the three-way valve 1.
6. Drained to the waste liquid side via the liquid feed pump 12 sequentially. As a result, the components to be analyzed in the pre-measurement remaining in the collection container are washed away.

The third step is a single cleaning step (S10).
3). Except that the UV light source 22 is turned off,
The valves and pumps are set in the same manner as in the second step, and the supply, flow, and discharge of the cleaning liquid are continued for a predetermined time.

In the second step and the third step, the ultraviolet light is continuously irradiated during the second step and the light is turned off in the third step. Only the steps may be performed, or the second and third steps may be repeated several times. In the second step, ultraviolet light may be irradiated in a pulsed manner.

It is preferable that the UV cleaning step of the second step is performed once for each measurement (one cycle of steps 1 to 8), but it is automatically and periodically performed several times (cycles). The UV cleaning may be performed once during) or may be arbitrarily performed according to an operator's instruction.

The fourth step is a water storage step (S104). The three-way valve 16 is set to the flow path indicated by the broken line, and the supply of the ultrapure water as the absorbing liquid from the absorbing liquid / washing liquid supply pipe 24 into the collection container main body 21 is continued by the liquid sending pump 11.
The supply of ultrapure water by the liquid sending pump 11 is continued for a predetermined time, and a predetermined volume of ultrapure water is stored in the collection container main body 21. Use the stored water for the absorbing solution.

The fifth step is a sampling step (S10
5). Stop the liquid supply pump 11 and set the three-way valve 4
4 and 45 are set to flow paths indicated by broken lines, and the sample air sucked by the suction pump 41 is passed through the sample air supply pipe 26 of the sampling container main body 21 into the absorbing solution, and further exhausted from the sample air discharge pipe 27. . The analyte in the sample atmosphere is absorbed by the absorbing liquid in the main body 21 of the collection container. This ventilation state is continued for a predetermined period of time to quantitatively collect the components to be analyzed. The sample air supply pipe between the three-way valve 45 and the collection container main body is preferably installed as close to the collection container main body as possible to reduce dead space. still,
In an actual device, the length of the sample air supply pipe between the three-way valve 45 and the collection container main body is about 10 cm,
On the other hand, the distance from the three-way valve 45 to a measurement point (intake of the sample atmosphere) (not shown) may be about 10 m.

The sixth step is a concentration step (S106). The three-way valves 44 and 45 are set to flow paths shown by solid lines,
The sample air sucked by the suction pump 41 is directly exhausted without being introduced into the gas sampling device, the liquid feed pump 11 is operated, and the three-way valves 16, 17, 18 and the flow path switching valve 32 shown in FIG. The three-way valve 19 is set to the flow path shown by the solid line in the flow path shown. Then, the absorbing solution having absorbed the analyte in the fifth step is a three-way valve 16,
17, 19, the liquid feed pump 11 and the flow path switching valve 32 are sequentially passed, and the liquid is sent to a concentration column 33 provided in an ion chromatograph constituting the gas analyzer. The analyte in the absorption liquid is captured by the concentration column 33 while passing through the concentration column 33, while the absorption liquid flowing out of the concentration column 33 is drained to the wastewater side of the three-way valve 18.

The duration of the sixth step is set to a time shorter than (total volume (ml) of the absorbing liquid in the collection container main body 21) / (liquid flow rate (ml / min) of the liquid feeding pump 11). However, it is preferable that the absorbing liquid remains in the collection container main body. In particular, after this step, it is preferable to set the time so that about 10% of the total volume of the absorbing solution remains in the collection container main body 21.

The seventh step is concentration 2 (S107).
The liquid feed pump 11 is continuously operated, and the three-way valve 18 shown in FIG. 1 is switched to the flow path shown by the solid line. The absorption liquid having absorbed the analyte in the fifth step is supplied to the three-way valves 16, 17, 19, the liquid sending pump 11, and the flow path switching valve 3.
2 and sequentially sent to the concentration column 33. The analyte in the absorbing solution is captured by the concentration column 33 while passing through the concentration column. The absorbent flowing out of the concentration column 33 is returned to the collection container main body 21 via the three-way valve 18. When returning to the collection container main body 21, the absorbing liquid was sprayed onto the inner wall of the collection container main body 21 from the nozzle 24a of the absorption liquid / washing liquid supply pipe 24, and thus scattered to the upper portion of the collection container main body 21 in the fifth step. The absorption liquid is washed down to the lower part of the collection container main body 21, and the analyte contained in the scattered absorption liquid is also collected. Thereby, the collection rate can be improved. This seventh continuation time is defined as (the volume (m) of the absorbent remaining in the collection container main body 21 after the sixth step.
l)) ÷ (liquid flow rate of liquid pump 11 (ml / mi)
When the time is set to 5 times or more of n)), the analyte contained in the absorbing solution remaining in the collection container main body 21 after the fifth step can be captured by the almost 100% concentration column 33.

The eighth step is a separation analysis step (S108). In the example of the gas analyzer shown here, the ion chromatograph 3 is provided, and as described above, the flow path switching valve 3 for switching the flow path of the absorbing liquid sent.
2 and a concentrating column 33 as a trapping / concentrating means for adsorbing and concentrating the analyte collected in the absorbing solution, and further sending an eluent for eluting the analyte adsorbed on the concentration column 33 And a separation column 34 for separating a plurality of analytes eluted from the concentration column 33 from each other. The eluent components in the eluate eluted from the separation column 34 are neutralized and backed up. It has a suppressor 36 for reducing the electrical conductivity of the ground, a liquid sending pump 37 for introducing a removing liquid into the suppressor, and a conductivity detector 35 for measuring the electrical conductivity of the eluent eluted from the suppressor.

After the first concentration step and the second concentration step,
The flow path switching valve 32 is set to the flow path indicated by the solid line, and the eluent is sent to the concentration column 33 by the liquid sending pump 31, the analyte is separated from the concentration column 33, and the separation column 3
In step 4, a plurality of analyte components are separated from each other by a difference in retention time.

The plurality of separated components to be analyzed are caused to flow sequentially into the conductivity detector 35 via the suppressor 36. Quantitative analysis of each of the analytes is performed from the measured value of the conductivity detector 35, and the concentration of the analyte in the sample air is calculated from the analyzed value. The suppressor 36 and the liquid feed pump 37 are not always required, but it is desirable to provide them when measuring the trace components. Also, the detector is not limited to the conductivity detector, but when the analyte is a component that dissolves in ions or water and ionizes, the conductivity detector is a highly sensitive and general-purpose detector, It is suitable for the purpose of the present invention.

Detection unit (not shown) by conductivity detector 35
The conductivity is measured at an intensity corresponding to the type and concentration of the analyte contained in the liquid passing through the sample, and the change over time in the conductivity is taken into a data processing / control unit (not shown). The data processing / control unit detects a change in the detected intensity caused by the component to be analyzed based on the captured data, and automatically calculates the concentration based on the calibration curve data input in advance.

The eluent is constantly supplied by the liquid supply pump 31 throughout the entire measurement process. In addition, the liquid sending pump 31
The flow rate of the liquid supplied from the liquid supply pump 37 is set to a predetermined value by a flow rate adjusting mechanism (not shown).

By repeating the above-described first to eighth steps as one measurement cycle (a specific step is deleted or repeated as necessary), continuous measurement of the sample atmosphere is possible.

Here, in the eighth step, if the flow path switching valve 32 shown in FIG. 1 is set to the flow path shown by the solid line,
Three-way valve 16, 17, 18, 19, 43, 44, 4
5. This is a step in which the analysis process in the ion chromatograph 3 can be independently performed regardless of the state of the liquid sending pumps 11, 12 and the suction pump 13. Therefore, the eighth step is performed in parallel with the first to fifth steps in the next measurement cycle, and the separation analysis is performed so that the eighth step is completed between the first to fifth steps. By adjusting various conditions, the measurement time can be reduced.

Further, in the present invention, a device (not shown) for controlling the temperature of the collection container main body 21 or the entire gas collection device 2.
Is added, and the temperature of a part or the whole of the collection container main body 21 is kept at 0 ° C. or more and room temperature or less, desirably 0 ° C. to 10 ° C.,
The analysis accuracy can be improved by suppressing the absorption liquid from evaporating and being discharged from the sample air discharge pipe 27 and disappearing from the sampling container main body 21.

As described above, by irradiating the ultraviolet light from the UV light source 22 to the collection container main body 21 having a hydrophilic surface, it is not possible to sufficiently wash it by merely passing water. During the process, the fouling components accumulated on the inner wall surface of the collection container main body 21 are efficiently oxidatively decomposed, so that the adsorption of the fouling components can be prevented. As a result, the inner wall surface of the collection container main body 21 is kept highly hydrophilic due to the prevention of adhesion of the fouling component, and when the sample atmosphere is blown into the absorbing liquid stored in the collection container main body 21, the absorption liquid is removed from the collection container main body 2.
The absorption liquid that has blown up to the upper portion of the sample 1 forms a water film on the entire inner wall of the collection container body and flows down. Therefore, the contact area between the sample atmosphere and the absorption liquid increases, and the sample to be analyzed is efficiently captured. Collection can be done. Further, the inner wall surface of the collection container main body is washed off evenly by the cleaning liquid jetted and supplied at the upper part of the collection container main body, and is efficiently cleaned. Since it is not necessary to periodically perform maintenance cleaning of the collection container main body 21, the gas analyzer of the present invention can reduce the burden on the user.

In the gas sampling apparatus of the present embodiment, as shown in FIG. 3, a nozzle 24a is provided at the tip of the absorption liquid / washing liquid supply pipe 24, and the collection vessel main body 21 is
Although the example of spraying the cleaning liquid on the inner wall of the nozzle is shown, the purpose of the nozzle is to supply the cleaning liquid from the upper part to the lower part of the inner wall of the collection container as much as possible regardless of the orientation, and if the purpose is satisfied, Absorbent / cleaning liquid supply pipe 24
May be other than that shown in FIG. For example, the structure may be such that the tip is branched, or the absorption liquid / cleaning liquid supply may be performed such that the cleaning liquid flowing out of the absorption liquid / cleaning liquid supply pipe 24 spirally flows from the upper part to the lower part of the collection container body 21. The tip of the tube may be installed on the collection container body 21. Even in these methods, since a water film due to the absorbing liquid is formed on the inner wall surface of the collection container main body 21 in the sampling step, the analyte can be collected with a high collection rate and with good reproducibility.

In this embodiment, the example in which the ion chromatograph 3 is used as the component detecting device for detecting the components of the gas collected by the gas collecting device 2 has been described. Is not limited to a liquid chromatograph such as an ion chromatograph 3, and it is desirable to use a component detection device corresponding to the component / component group to be analyzed.

The absorbing solution used in the present invention can be appropriately changed depending on the type of the analyte to be collected, but in any case, it is usually an aqueous solution.

<Second Gas Analyzer and Gas Analyzer Method>
Embodiment> FIG. 6 is a block diagram showing a second embodiment of the gas analyzer of the present invention. The configuration of the gas sampling device 2 is the same as that of the first embodiment.

In the gas analyzer 1 according to the first embodiment shown in FIG. 1, the suction pump 41 is always operated, and the three-way valves 44 and 45 are switched between the flow paths, whereby the suction pump 41 is operated.
In this case, the apparatus is configured to switch between a setting for introducing the sample air sucked by the above into the gas sampling device 2 and a setting for directly exhausting the gas. On the other hand, the gas analyzer 51 of the present embodiment shown in FIG. 6 includes the suction pump 41 for sampling and the pump 47 for directly evacuating, and the sample air is collected in the sampling process by the gas sampling device. In the case of introduction into 2, the suction pump 41 is operated, the three-way valve 46 is set to the side of the broken line in FIG. 6, and the suction pump 41 exhausts the gas through the valve 46, the collection container main body 21, and the valve 43, During the other steps, when the sample air is directly exhausted, the suction pump 47 is operated, and the three-way valve 46 can be set to a solid line flow path so that the sample air is sucked to the operating pump side. Have been. Other configurations are the same as those of the gas analyzer shown in FIG. 1 and the like.

When such a gas analyzer is used, the first
Although there is a disadvantage that two suction pumps are required as compared with the embodiment of the present invention, a pump having a larger suction amount than the suction pump 41 is used as the suction pump 47 and the flow control
By setting 8 to a flow rate greater than the flow control 42, the time required for the adsorption between the surface of the pipe from the measurement point (not shown) to the three-way valve 46 and the sample air flowing through the pipe to reach equilibrium is reduced. Since it can be shorter than in the first embodiment, there is a feature that the difference between the actual concentration of the analyte in the sample atmosphere and the monitor value can be eliminated in a shorter time.

[0069]

Next, an embodiment of the gas analyzer of the present invention will be described with reference to the drawings.

(First Example) First, an example of the gas analyzer 1 according to the first embodiment shown in FIG. 1 and the like will be described.

The gas analyzer 1 according to the present embodiment includes a separation column 34 (“IonPac CS1” manufactured by Dionex).
"0": trade name, a concentration column 33 (manufactured by Dionex, "Ion Pac CG10": trade name), and a suppressor 36 (manufactured by Dionex, "CSRS-II"):
Product name) and conductivity detector 35 (Ion chromatograph main body (manufactured by Dionex, "DX320J": trade name))
This is a gas analyzer that analyzes sodium, ammonia, monoethanolamine, and potassium in the atmosphere using an ion chromatograph 3 (manufactured by Dionex, "DX320J": trade name) to which a built-in) is connected.

Ultrapure water was used as the absorbing solution and the washing solution, and a 20 mmol methanesulfonic acid solution was used as the eluent. The collection container body 21 has an inner diameter of 12 mm, an outer diameter of 16 mm, and a length of 3.
A 50 mm quartz cylinder and a PTFE upper end connection joint (not shown, absorbing liquid / cleaning liquid) connected to the upper end of the cylinder and connecting the cylinder, sample air exhaust pipe 27, and absorbing liquid / cleaning liquid supply pipe 24. The supply pipe 24 penetrates through the connection joint, and a lower end connection joint made of PTFE (not shown, connected to the lower end of the cylinder and connecting the cylinder, the sample air supply pipe 26, and the absorbent / washing liquid discharge pipe 25). The sample atmosphere supply pipe 26 is formed from the connection joint). The sample atmosphere supply pipe 26 is set so that the sample atmosphere blown from the sample atmosphere supply pipe 26 becomes small bubbles.
The tip portion of the side inserted into the cylinder is shaped into a tapered shape, and the inner diameter is reduced.

The collection container main body 21 is installed vertically with the upper part provided with the absorbing liquid / washing liquid supply pipe 24, the sample air supply pipe 26, and the sample air discharge pipe 27 facing upward.
A 10 W low-pressure mercury lamp was installed in parallel with the collection container main body 21. The flow rates of the liquid sending pumps 11, 12, 31, and 37 are 2 ml / min, 3 ml / min, and 1 ml, respectively.
/ Min, 2 ml / min, and the flow rate of the suction pump 41 was set to 0.5 l / min by adjusting the flow rate controller 42.

In the evaluation of the collection rate performed using a standard gas whose concentrations of ammonia and monoethanol were adjusted in advance,
When the flow rate of the suction pump 13 was 1 l / min or less, the concentrations of sodium, ammonia, monoethanolamine, and potassium contained in the standard gas could be determined at a collection rate of 100%.

The gas analysis is performed in accordance with the first to seventh steps described with reference to FIG. 5. The drainage time of the residual absorbent in the collection vessel main body 21 in the first step (drainage) is 1 minute, and The cleaning time in the second step (UV cleaning) is 2 minutes, the cleaning time in the third step (cleaning) is 6 minutes, and the supply and storage time of the absorbing liquid into the collection container body 21 in the fourth step (water storage). Is 2.5
Minute, the supply time of the sample atmosphere to the collection container main body 21 in the fifth step (sampling) is 10 minutes, the concentration time of the absorbing solution in the sixth step (concentration 1) is 1.75 minutes,
The concentration time of the absorbing solution in the seventh step (concentration 2) was set to 5 minutes, and the time of component analysis in the eighth step (separation analysis) was set to 20 minutes. The eighth step of the first measurement cycle was performed in parallel with the first to fifth steps of the second measurement cycle (the same applies to the following measurement cycles). The time required for one measurement cycle was 27.75 minutes.

When the sample atmosphere containing 20 μg / m ³ of monoethanolamine is continuously measured, in the measurement of the present embodiment, the first measurement is 12 μg / m ³ and the second measurement is 16 μg / m ³ .
/ M ^3, 3-th time and 18 [mu] g / m ^3, whereas the delay in response is three times, suction only during the sampling pump 41
Was operated and the detour and discharge of the sample air were not performed in the process other than the sampling process, the first time was 8 μg /
m ³ , second time 13 μg / m ³ , third time 16 μg / m ³
m ³ , the fourth response was 18 μg / m ^3, and there were four response delays. That is, according to the present invention, the response delay can be reduced, and
The monitor value at the first time improved 1.5 times.

The lower limit of detection of sodium, ammonia, monoethanolamine, and potassium using the gas analyzer 1 was 0.05 μg / m ³ . Note that the above device configuration, measurement conditions, measurement cycle, and detection lower limit have been optimized and obtained by study of the present inventors, but their device configuration, measurement conditions, and the like are not limited to the above. Not something.

(Second Example) Next, an example of the gas analyzer 51 according to the second embodiment shown in FIG. 6 and the like will be described.

The gas analyzer 51 of this embodiment is also a gas analyzer for analyzing sodium, ammonia, monoethanolamine, and potassium in the atmosphere, and the ion chromatograph 3 has the same separation column 34 as that of the first embodiment. , A concentration column 33, and a suppressor 36. In addition, the configurations of the collection container main body 21, the absorbing solution, the cleaning solution, and the eluent are the same as those in the first embodiment.

In this embodiment, the liquid feed pumps 11, 12, 3
The flow rates of 1 and 37 are 2 ml / min and 3 ml / m, respectively.
In, 1 ml / min, 2 ml / min, the flow rate of the suction pump 41 was adjusted to 0.5 l by adjusting the flow rate controller 42.
/ Min, and the flow rate of the suction pump 47 was set to 5 l / min by adjusting the flow controller 48. The gas analysis was performed according to the first to seventh steps described with reference to FIG. 5, and the time of each step was set to be the same as in the first embodiment.

When the continuous measurement of the sample atmosphere containing 20 μg / m ³ of monoethanolamine was performed according to the present example, the first measurement was 14 μg / m ³ , and the second measurement was 18 μg / m 3.
³ , the response delay could be reduced to two times, which is smaller than the measurement of the first embodiment.

The analysis results of the gas analyzer 51 such as the detection lower limit were the same as in the first embodiment.

[0083]

According to the present invention, since the inner wall surface of the collection container is kept highly hydrophilic, the inner wall of the collection container is always clean, and as a result, the absorption stored in the collection container is maintained. When the sample air is blown into the liquid, the absorbing liquid is blown up to the upper portion of the collection container, and the blown-up absorbing liquid forms a water film on the entire inner wall of the collecting container body and flows down. The contact area increases, and the analyte can be efficiently collected.

In addition, at the time of cleaning, the inner wall surface of the collection container main body is washed off evenly by the cleaning liquid jetted and supplied at the upper portion of the collection container main body, and is efficiently cleaned.
Since it is not necessary to periodically perform maintenance cleaning of the collection container, the gas analyzer of the present invention can reduce the burden on the user.

The accuracy of analysis can be improved by keeping the temperature of a part or the whole of the collection container at room temperature or lower, preferably at 0 ° C. to 10 ° C., and suppressing the absorption liquid from evaporating and disappearing.

In addition, by providing means for reducing air bubbles in the sample atmosphere to be ventilated into the absorbing solution at the inner end of the gas sampling container main body of the sample atmosphere supply pipe, the sample atmosphere passing through the absorbing solution can be miniaturized. And the absorption efficiency is improved.

Further, in the gas analyzer further provided with the capturing / concentrating means and the separating means, the analyte is detected in a concentrated state, so that the detection intensity of the analyte is increased,
Analysis accuracy can be improved.

Further, by adopting a configuration in which a part or all of the absorbing solution from which the analyte has been removed by passing through the capturing / concentrating means can be circulated and sent to a gas sampling device, All the components to be analyzed contained in the liquid can be supplied to the component detection device, and the analysis sensitivity can be improved.

[Brief description of the drawings]

FIG. 1 is a configuration diagram showing a first embodiment of a gas analyzer according to the present invention.

FIG. 2 is a schematic perspective view showing a detailed configuration of the gas sampling device shown in FIG.

FIG. 3 is a partially cutaway sectional view of a part of the gas sampling device shown in FIGS. 1 and 2;

FIG. 4 is a partially cutaway sectional view of a part of the gas sampling device shown in FIGS. 1 and 2;

FIG. 5 is a flowchart illustrating an analysis process of the gas analysis method according to the first embodiment.

FIG. 6 is a configuration diagram showing a second embodiment of the gas analyzer of the present invention.

FIG. 7 is a cross-sectional view of an impinger (absorber) in a conventional gas analyzer.

FIG. 8 is a cross-sectional view of an impinger (absorber) in a conventional gas analyzer.

FIG. 9 is a flowchart showing an analysis process of a conventional gas analysis method.

FIG. 10 is a diagram showing a conventional gas analyzer.

FIG. 11 is a sectional view of an impinger (absorber) in a conventional gas analyzer.

[Explanation of symbols]

1, 51 Gas analyzer 2 Gas sampling device 3 Ion chromatograph 11, 12, 31, 37 Liquid feed pump 41, 47 Suction pump 42, 48 Flow controller 16, 17, 18, 19, 43, 44, 45, 46 Three-way Valve 32 Flow path switching valve 21 Sampling container main body 22 Ultraviolet light source 23 Reflector 24 Absorbent / washing liquid supply pipe 24a Nozzle 25 Absorbent / washing liquid discharge pipe 26 Sample air supply pipe 27 Sample air discharge pipe 33 Concentration column 34 Separation column 35 Conduction Rate detector 36 Suppressor

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-11-83700 (JP, A) JP-A-9-257777 (JP, A) JP-A-6-11496 (JP, A) JP-A-10- 206409 (JP, A) JP-A-8-101102 (JP, A) JP-A-1-203968 (JP, A) JP-A-8-54380 (JP, A) JP-A-8-94502 (JP, A) JP-A-9-83005 (JP, A) JP-A-8-99041 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G01N 1/00-1/34 G01N 30/00 -30/96 JICST file (JOIS)

Claims (35)

(57) [Claims] 1. A gas sampling container main body for holding an absorbing liquid that absorbs a component to be analyzed by passing the sample air to be measured, and a sample air inside the gas sampling container main body so as to contact the absorbing liquid. A sample atmosphere supply pipe to be supplied, a sample atmosphere exhaust pipe for discharging the sample atmosphere after coming into contact with the absorption liquid from the gas collection vessel main body, and irradiating at least an inner wall of the gas collection vessel main body with ultraviolet light. An ultraviolet light source for cleaning, and a cleaning liquid supply pipe arranged so that when the cleaning liquid is supplied into the gas collection container main body for cleaning, the cleaning liquid flows down while wetting the inner wall of the gas collection container main body. Equipped gas sampling device. 2. The cleaning liquid supply pipe is attached to an upper portion of the gas collection container main body and has a tip protruding into the gas collection container main body, and the tip injects the cleaning liquid toward a wall surface. 2. The gas sampling device according to claim 1, wherein the gas sampling device has a shape capable of being used. 3. The sample atmosphere supply pipe is attached to a lower portion of the gas collection vessel main body, and an opening of the sample atmosphere supply pipe in the gas collection vessel is at least below a liquid level of the absorbing liquid. The gas sampling apparatus according to claim 1, wherein the sample atmosphere can be bubbled in the absorbing solution. 4. The gas sampling apparatus according to claim 3, wherein a means for reducing air bubbles in the sample atmosphere to be passed through the absorbing solution is provided at an inner end of the gas sampling vessel main body of the sample atmosphere supply pipe. apparatus. 5. The sample atmosphere exhaust pipe is provided at an upper portion of the gas sampling container main body and at least above a position at which the bubbling and foamed absorbing liquid is broken. A gas sampling device as described. 6. The gas sampling device according to claim 1, wherein the cleaning liquid is the same liquid as the absorbing liquid. 7. The gas collection container body according to claim 1, wherein the gas collection container main body is formed of a material that transmits ultraviolet light, and the ultraviolet light source is disposed outside the gas collection container main body. Gas sampling device. 8. The gas collection device according to claim 7, wherein the ultraviolet light source and the gas collection container main body are installed in a space surrounded by a reflector that reflects ultraviolet light. 9. The gas collection device has a jacket for protecting the gas collection container main body, and an inner wall of the jacket is processed so as to reflect ultraviolet light, and the reflection material is configured. 9. The gas sampling device according to claim 8, wherein: 10. The gas collection device has a jacket for protecting the gas collection container main body, and a reflection plate is inserted between the jacket and the ultraviolet light source and the gas collection container main body. 9. The reflecting material is configured by the following.
A gas sampling device as described. 11. The collection container body has an attenuation rate of ultraviolet light of 90% or less inside and outside a wall thereof.
0. The gas sampling device according to any one of 0. 12. The gas collection device according to claim 11, wherein the collection container main body has an attenuation rate of ultraviolet light of 50% or less inside and outside the wall. 13. A temperature control device for controlling the temperature of the collection container body, a part of the gas collection device, or the entire temperature of the gas collection device.
The gas sampling device according to any one of the above items. 14. The gas sampling apparatus according to claim 13, wherein the temperature to be adjusted is set at 0 ° C. to room temperature. 15. The gas sampling device according to claim 1, a means for introducing a sample atmosphere into the gas sampling device, and detecting a component to be analyzed absorbed in the absorbing solution. A gas analyzer having component detection means. 16. A means for introducing the sample atmosphere, wherein, when sampling the sample atmosphere, a first flow path passing through the sample atmosphere supply pipe, the gas sampling container main body, and the sample atmosphere exhaust pipe; A flow path switching mechanism that bypasses the gas sampling container main body and can switch a second flow path through which the sample air flows directly from an inlet of the sample air supply pipe to an outlet of the exhaust pipe; 16. The gas analyzer according to claim 15, further comprising: a suction pump connected to an outlet of an atmospheric exhaust pipe and configured to exhaust the sample air in both the first flow path and the second flow path. 17. The apparatus according to claim 17, wherein the means for introducing the sample air comprises:
A first flow path that passes through the gas sampling container body and the sample air exhaust pipe, and a flow path switching unit that can switch between a second flow path that directly exhausts the sample air, A first suction pump connected to an outlet and exhausting the sample air when the first flow path is formed; and a second suction flow path connected to an inlet of the sample air supply pipe. The gas analyzer according to claim 15, further comprising: a second suction pump that directly exhausts the sample atmosphere when the sample is discharged. 18. A capturing and concentrating means for capturing and concentrating the analyte absorbed in the absorbing solution, and a releasing means for releasing the analyte to be captured by the capturing and concentrating means from the capturing and concentrating means. Claim 15
18. The gas analyzer according to any one of claims 17 to 17. 19. A method for concentrating a component to be analyzed absorbed in the absorbing solution, a flow path for sending the sampled absorbing solution to the capturing and concentrating means, and separating the analyte from the capturing and concentrating means. The gas analyzer according to claim 18, further comprising a switching mechanism for switching between a flow path formed for causing the gas analyzer and the flow path. 20. The gas analyzer according to claim 18, wherein the capture and concentration means is a concentration column filled with an adsorbent for adsorbing the analyte contained in the absorption liquid. 21. The gas analyzer according to claim 20, wherein the separation means has a mechanism for flowing an eluent through the concentration column to elute the analyte that has been adsorbed and concentrated. 22. The component detection unit according to claim 15, wherein the component detection unit is a liquid chromatograph or an ion chromatograph.
8. The gas analyzer according to any one of 7. 23. The gas analyzer according to claim 18, wherein the capturing / concentrating unit and the separating unit are provided in a liquid chromatograph or an ion chromatograph, which is a component detecting unit. 24. The apparatus according to claim 18, further comprising a mechanism for circulating the absorption liquid from which the analyte has been removed by passing through the capturing / concentrating means, to the gas sampling device.
The gas analyzer according to any one of claims 21 to 23 or Claim 23. 25. A sampling step of allowing a sample air to be measured to pass through an absorbing solution held in a gas sampling container main body to absorb a component to be analyzed, and analyzing the component to be analyzed absorbed by the absorbing solution. A gas analysis method comprising: a step of irradiating at least an inner wall of the gas collection container main body with ultraviolet light, and causing a cleaning liquid to flow down so as to wet the inner wall of the gas collection container main body. 26. In the cleaning step, the cleaning liquid is supplied to a cleaning liquid supply pipe (provided that the cleaning liquid supply pipe is
It has a tip attached to the upper part of the gas collection container main body and protruding into the gas collection container main body, and the tip is shaped so that the cleaning liquid can be sprayed toward a wall surface. 27. The gas analysis method according to claim 25, wherein the gas is injected from the gas. 27. In the sampling step, the sample atmosphere is supplied to a sample atmosphere supply pipe (provided that the sample atmosphere supply pipe is attached to a lower portion of the gas collection vessel main body, The opening in the inside is at least below the liquid level of the absorbing liquid so that the absorbing liquid can be bubbled.) 26. The gas analysis method according to item 25. 28. The sample atmosphere supply pipe according to claim 27, further comprising means for reducing air bubbles in the sample atmosphere to be ventilated into the absorbing solution at the inner end of the gas sampling container main body.
Gas analysis method as described. 29. In the sampling step, the sample atmosphere is raised in the form of a bubble wrapped in the absorbing liquid by raising the gas sampling container main body, and is broken when the tip of the cleaning liquid supply pipe is touched. 28. The gas analysis method according to claim 27, wherein the gas is exhausted from a sample atmospheric exhaust pipe attached above the bubble position. 30. The gas analysis method according to claim 25, wherein the same liquid as the absorbing liquid is used as the cleaning liquid. 31. The gas collection container main body is formed of a material that transmits ultraviolet light, and in the cleaning step, an ultraviolet light source disposed outside the gas collection container main body with respect to the gas collection container main body. The gas analysis method according to any one of claims 25 to 30, wherein the gas is irradiated with ultraviolet light. 32. The method according to claim 25, further comprising, before the analyzing step, a step of concentrating the analyte in the absorbing solution by passing the absorbing solution passed through the sample atmosphere through a capturing / concentrating means. The gas analysis method according to 1. 33. The concentrating step comprises the steps of: passing the absorbing solution passed through the sample atmosphere through a trapping / concentrating means; and discarding the passing liquid; and capturing and concentrating the absorbing solution passed through the sample atmosphere. 33. The gas analysis method according to claim 32, comprising two steps: passing the liquid through the gas collecting container main body and circulating the passed liquid again. 34. During the period of the sampling step, the flow path of the sample air is introduced into the main body of the gas sampling container by switching the flow path of the sample air, and the flow path of the sample air is excluded during the period other than the period during which sampling is performed. 32. The gas analysis method according to claim 25, wherein the air is exhausted from an air exhaust pipe outlet by bypassing the main body of the gas collection container by switching the gas sampling container main body. 35. During the period of the sampling step, a flow path of the sample air is introduced into the main body of the gas sampling container by switching a flow path of the sample air, and the flow path of the sample air is excluded except a period during which sampling is performed. 32. The gas analysis method according to claim 25, wherein the gas is directly exhausted from a suction pump connected to an inlet of the sample atmosphere supply pipe by switching the sample air supply pipe.