JP3177134B2 - Time-division high-speed sampling device, automatic analyzer, automatic analysis method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a time-division high-speed sampling apparatus, an automatic analyzer, and an automatic analysis method for collecting a sample gas and performing various analyzes on the sample gas.

[0002]

2. Description of the Related Art A rapid change between a certain steady state in a gas and another steady state and a detailed state of a change in a dynamic state in a gas are required to elucidate the mechanism of the change. It is also important.

[0003] To grasp the above change, sample gas is sampled at many places in the gas, and the sample gas is sequentially analyzed, or a large number of sample gases are chronologically sampled at an arbitrary place in the gas. A method of sampling and sequentially analyzing the sample gas can be considered.

Conventionally, in contrast to such analysis, the method of performing one analysis on one sample gas as a first method has been extended, and the number of sample gases by a conventional sampling method such as using a sampling bag has been extended. Simply increase
The analysis was performed sequentially. As a second method, the number of analyzers is increased, and more sample gas is analyzed in the same time.

[0005]

However, in the case of the conventional gas sampling method, especially when sampling is performed by a sampling bag or the like, a large amount of sample is collected, that is, a relatively long sampling is performed. Could not be obtained. That is, no matter how many sampling points are increased, a faster change cannot be tracked unless one sampling time is made faster. As described above, according to the conventional method, the sampling interval of the sample gas cannot be reduced so much (that is, it is difficult to measure in a time-division manner), and a change in a situation caused by a short-time transient phenomenon is tracked. I couldn't do that.

For example, in an automobile exhaust gas automatic analyzer, which is one of the conventional methods, only the total amount of organic components in a sample gas can be measured. Could not do.

[0007] In a direct sampling gas chromatograph (Japanese Patent Laid-Open No. 7-55780), which is one of the conventional methods, the sampling interval of the sample gas is determined by the analysis time of the sample gas in the gas chromatograph (gas chromatograph).

[0008] Then, in order to shorten the analysis time of the sample gas in the gas chromatograph, only the sample gas having a poor distribution ratio is used.
It has been attempted to reduce the measurement time by introducing the gas chromatography column again. However, there is a limit to the shortening of the measurement time, which is about 8 minutes at the fastest. For this reason, in the analysis and measurement of fast-changing phenomena such as transient phenomena in gas, it is not sufficient to simply shorten the gas chromatography measurement time.

[0009] In addition, a bag-collecting gas chromatography which is one of the conventional methods ("Automotive Technology" Vol. 49, No. 4, 1).
995), the sample gas can be sampled at intervals of 5 to 10 seconds. However, the composition of the sample gas averaged during the sampling back,
There is a risk of deterioration.

[0010] In addition to the sampling device described above,
Various sampling devices and analysis devices have conventionally existed. However, all of these methods are not suitable for grasping the state of a gas that causes a sudden change due to a long sampling interval of the sample gas.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has as its object to provide a time-division high-speed sampling apparatus, an automatic analyzer, and an automatic analysis method capable of sampling a sample gas at minute time intervals.

[0012]

According to the present invention, there is provided a flow path switching valve for switching an inlet flow path to a sampler or an outlet flow path, an inlet pipe for introducing a sample gas from the flow path switching valve to a sampler, and the sampler. The sampler is provided on the gas inlet side and the gas outlet side, and has a pair of rotary valves which rotate synchronously and a pair of rotary valves. A plurality of sample gas sampling pipes disposed therebetween, and operating the flow path switching valve and the sampler to communicate the inlet flow path with the outlet flow path via the flow path switching valve; A time-division high-speed sampling device characterized by having a controller for switching between an inlet channel and an outlet channel via a channel switching valve.

The operation of the present invention will be described. In the present invention, the sample gas is introduced into the sampling device by switching the flow path switching valve. At this time, by appropriately operating the rotary valve in the sampling device, the sample gas can be successively introduced into the plurality of sample gas sampling pipes in time series. Further, by operating the rotary valve at a high speed, the sampling interval in the sample gas sampling tube can be reduced.

As the flow path switching valve and the rotary valve, an air drive valve, an electromagnetic valve, or the like can be used. In particular, in order to realize high-speed sampling, it is preferable to use an air-driven valve. As the number of switching stages of the flow path switching valve and the rotary valve, two-way switching, multi-way switching, and the like are selected as necessary.

The rotary valve preferably has, for example, the following structure. That is, the rotary valve includes a fixed plate and a rotary plate rotatably provided with respect to the fixed plate. The rotating plate has a gas hole communicating with the inlet pipe and a gas groove connected to the gas hole. On the other hand, when the fixed plate is overlapped with the rotating plate,
It has a plurality of gas holes that can communicate with the gas groove. The rotary valve on the gas introduction side and the rotary valve on the gas outlet side are arranged with their fixed plates facing each other. A sample gas sampling tube is provided so as to connect each gas hole in the fixing plate.

When the rotary valve is operated, the gas hole and the gas groove in the rotary plate communicate with one gas hole in the fixed plate, and the sample gas is connected to the sample gas sampling pipe connected to the gas hole. Gas can be introduced.

When the sample gas collection tube is filled with the sample gas, the rotary valve is operated again, and the sample gas collection tube connected to another gas hole different from the gas hole is rotated. Communicated with gas holes in the plate. By continuously performing the above operations, the sample gas can be sampled in a time-division manner.

The controller may be any controller that can send ON / OFF signals to the rotary valve and the flow path switching valve at any time and at any time interval. We do not choose kind. For example, a personal computer or the like can be used as the controller (see FIG. 7).

Next, it is preferable that the rotary valve in the sampler is operated at a time interval of 0.2 seconds or more. If the time interval is less than 0.2 seconds, the sample gas may not be able to completely fill the sample gas sampling tube. That is, there is a possibility that sampling by the sample gas sampling tube cannot be performed.

Next, the above-mentioned inlet channel is provided with a sample gas sampling port,
It is preferable to have an inlet switching valve capable of switching to at least one of a standard gas supply source and a cleaning gas supply source. When the analyzer for analyzing the sample gas is connected to the sampling device (refer to the automatic analyzer described later), the standard gas is connected to the inlet channel by connecting the standard gas supply to the analyzer. Can be supplied. Thereby, the standard condition in the analyzer can be tested.

On the other hand, by connecting the above-mentioned cleaning gas supply source to the inlet flow path, the remaining sample gas can be removed, and the flow path switching valve and other parts of the time-division high-speed sampling device can be cleaned.

It is to be noted that a plurality of the sample gas sampling ports may be provided for the inlet flow path. In this case, since the gas can be analyzed at multiple points, the spatial variation of the gas can be examined.

Next, it is preferable that the outlet channel has an outlet switching valve that can be switched to a vacuum system or an open system. By connecting the outlet channel to the vacuum system, the flow rate of the sample gas can be maintained at a high speed even when the sample gas is not a pressurized gas. When the flow rate of the sample gas is high, it is possible to fill the sample gas sampling tube in a shorter time, and therefore, it is possible to perform sampling at a higher speed.

On the other hand, by connecting the outlet channel to the open system, the pressure in each part of the time-division high-speed sampling device can be adjusted to exhaust the cleaning gas and the like.
Note that a decompression device such as a vacuum pump can be used as the vacuum system. Further, the open system can be configured by simply connecting an outlet pipe that can be led to the atmosphere to the outlet switching valve.

Next, as an automatic analyzer according to the present invention, a flow path switching valve for switching an inlet flow path to a sampler or an outlet flow path, and an inlet for introducing a sample gas from the flow path switching valve to the sampler. A pipe, and an outlet pipe for taking out the sample gas from the sampling device to the flow path switching valve. And a plurality of sample gas sampling tubes disposed between the rotary valves, and the above-mentioned flow path switching valve and the sampler are operated, and the inlet flow path is connected to the sampler via the flow path switching valve. A controller for switching between the case of communicating and the case of communicating the inlet flow path with the outlet flow path via a flow path switching valve, and an analyzer for analyzing the sample gas, , There is an automatic analyzer, characterized in that it comprises an analyzer switching unit for introducing the sample gas into the analyzer.

In the automatic analyzer, high-speed sampling of the sample gas is possible as in the time-division high-speed sampling apparatus. According to the automatic analyzer, the sampled sample gas is led out to the analyzer by switching the analyzer switching unit, and can be analyzed in the analyzer.

[0027] The gas can be led out to the analyzer by operating the rotary valve for each sample gas sampling pipe. Further, by combining with the above-mentioned flow path switching valve, it is possible to feed the analyzer to the analyzer without interfering with other parts of the time division high-speed sampling device. As a result, the sample gases sampled in a time-division manner can be separately analyzed, so that a time-series variation in the gas can be analyzed.

The analyzer switching section may be another switching valve provided separately from the flow path switching valve. And
Similar to the above-described flow path switching valve and rotary valve, a structure including a rotating plate and a fixed plate may be employed. Also,
The analyzer switching section can be used also as the flow path switching valve. The analyzer switching section needs to heat the entire apparatus in order to prevent the adsorption of the sample gas and the dew condensation of moisture, and therefore, it is preferable to use a heat-resistant switching valve.

By installing a plurality of the above-mentioned automatic analyzers and operating them simultaneously and simultaneously, multipoint analysis of gas can be performed in a time-division manner. A personal computer or the like can be used as a controller for operating the plurality of automatic analyzers (see FIG. 7).

As the analyzer, a gas chromatograph can be used. In addition, a liquid chromatograph can be used as the analyzer. By using the above-mentioned gas chromatograph, it is possible to analyze C _{1 to} C ₄₀ organic substances and vaporizable inorganic substances. In addition, the use of a liquid chromatograph enables analysis of a liquid component. In particular, this method is more effective for the analysis of ammonia and organic compounds having a high boiling point.

The gas chromatograph detectors include a mass detector (MSD), a flame ionization detector (FID), a thermal conductivity detector (TCD), an electron capture detector (ECD), and a flame light detector. A photometric detector (FPD), an alkali thermal ionization detector (FTD), or the like can be used.

By using the MSD, the molecular weight of each component contained in the sample gas can be measured.
In addition, hydrocarbons are used by using the FID, inorganic gases such as H ₂ O are used by using the TCD,
A halogen compound such as chlorine can be mainly analyzed by using the ECD, a sulfur compound can be analyzed by using the FPD, and a nitrogen compound can be mainly analyzed by using the FTD.

Next, as an automatic analysis method according to the present invention, a flow path switching valve for switching an inlet flow path to a sampler or an outlet flow path, and an inlet for introducing a sample gas from the flow path switching valve to the sampler. A pipe, and an outlet pipe for taking out the sample gas from the sampling device to the flow path switching valve. And a plurality of sample gas sampling tubes disposed between the rotary valves, and the above-mentioned flow path switching valve and the sampler are operated, and the inlet flow path is connected to the sampler via the flow path switching valve. A controller for switching between the case of communicating and the case of communicating the inlet flow path with the outlet flow path via a flow path switching valve, and an analyzer for analyzing the sample gas, , An automatic analyzer using an automatic analyzer having an analyzer switching unit for introducing the sample gas into the analyzer, wherein the inlet passage is provided with a sampling gas sampling port, a standard gas supply source, An inlet operation for communicating with at least one of the cleaning gas supply sources, an outlet operation for communicating the outlet flow path with a vacuum system or an open system, and a sampling device or an outlet flow path connecting the inlet flow path. The sampling operation is switched to the sampling gas, and at the time of sampling the sample gas, the sampler and the analyzer are each closed circuit so that the sample gas is sampled in a time-division and high-speed manner into the sample gas sampling pipe, and then the sampling is performed. The analyzed sample gas is analyzed with an analyzer, and after the above analysis, the residual gas in the automatic analyzer is washed with a washing gas, and if necessary, the standard condition of the analyzer is adjusted with a standard gas. An automatic analytical method which is characterized in that strike.

According to the automatic analysis method, the flow path switching valve, the rotary valve, and the analyzer switching section are operated at a high speed, and the minute At time intervals, sampling of the sample gases is performed, and then these sample gases can be analyzed separately.

The details of the inlet operation, the outlet operation, and the sampling operation are the same as those described above. The same applies to the analysis of the sample gas, the cleaning with the cleaning gas, and the test in the standard state with the standard gas. The residual gas includes a sample gas, a standard gas, and the like that are not used for analysis (not sampled).

[0036]

BEST MODE FOR CARRYING OUT THE INVENTION

Embodiment 1 A time-division high-speed sampling device according to an embodiment of the present invention will be described with reference to FIGS. As shown in FIG. 1, the time-division high-speed sampling device 1
Switching valve 3 for switching the pressure to the sampling device 2 or the outlet flow channel 12, and the sampling device 2
An inlet pipe 13 for introducing the sample gas into the sampler 2 and an outlet pipe 14 for guiding the sample gas from the sampler 2 to the flow path switching valve 3 are provided.

The sampler 2 includes a pair of rotary valves 20 and 21 which are arranged on the gas inlet side and the gas outlet side and rotate synchronously.
Five sample gas sampling tubes 29 arranged between 0 and 21
And one cleaning gas pipe 290.

Although not shown in FIG. 1, the flow path switching valve 3 and the sampler 2 are operated to allow the inlet flow path 11 to communicate with the sampler 2 via the flow path switching valve 3. And a controller for switching between a case where the inlet flow path 11 is communicated with the outlet flow path 12 via the flow path switching valve 3. The rotary valves 20, 21
Is an air-driven valve.

The automatic analyzer according to the present embodiment is such that an analyzer G for analyzing the sample gas is provided for the sampling device 1 having the above configuration. Further, it has an analyzer switching unit for introducing the sample gas into the analyzer G. The analyzer switching section is also used by the flow path switching valve 3. The analyzer G is a gas chromatograph.

Hereinafter, the time-division high-speed sampling device 1
Will be described in detail. First, as shown in FIG. 1, the inlet flow path 11 is provided with two inlet switching valves 4 and 5, both of which are connected by a pipe 119. The inlet switching valve 4 is provided with a gas introduction hole 411 connected to the sample gas sampling port A. Further, a gas inlet hole 410 for introducing a sample gas derived from another inlet switching valve 5 disposed upstream of the inlet switching valve 4, and a gas inlet hole 410 for guiding the introduced sample gas to the inlet channel 11. The gas outlet hole 412 is provided.

On the other hand, the inlet switching valve 5 is provided with a gas introduction hole 511 connected to the standard gas supply source B and a gas introduction hole 510 connected to the cleaning gas supply source C. Further, a gas outlet hole 512 for introducing the introduced gas to the inlet switching valve 4 via the pipe 119 is provided.

As shown in FIG. 1, the inlet switching valve 4 is provided with a gas groove 42. By switching the position of the gas groove 42, either the gas introduction hole 410 or 411 and the gas outlet hole 412 are connected. The connection between the two. The same applies to the gas groove 52 of the inlet switching valve 5.

Next, the outlet switching valve 6 has gas outlet holes 611 and 61 connected to the vacuum system D and the open system E.
0 is provided. Further, a gas introduction hole 612 connected to the outlet channel 12 is provided. The outlet switching valve 6 is also provided with a gas groove 62. By switching the position of the gas groove 62, a connection is established between the gas introduction hole 612 and one of the gas outlet holes 610, 611. is there. The vacuum system D is a vacuum pump. The open system E is a pipe having an outlet open to the atmosphere.

Next, the sampling device 2 will be described. As shown in FIG. 3, the sampler 2 includes a rotary valve 20 on the gas introduction side, a rotary valve 21 on the gas outlet side, five sample gas sampling pipes 29 disposed between the two, and one cleaning valve. It comprises a gas pipe 290.

As shown in FIG. 4, the rotary valve 20 on the gas introduction side comprises a fixed plate 23 and a rotary plate 22 rotatably provided with respect to the fixed plate 23.
2 has a gas groove 221 formed on its back surface in the radial direction from the center to the outer periphery. The gas groove 221
Communicates with the gas hole 220. The above gas hole 220
Is provided at the center of the rotating plate 23 and is configured to communicate with the inlet pipe 13.

On the other hand, the fixed plate 23 has six gas holes 230 provided at equal intervals on the outer peripheral edge thereof. The gas holes 230 allow the rotating plate 22 to contact the fixed plate 23. When rotated, one gas hole 230 is inserted into the gas groove 2.
21. Similarly, the rotary valve 21 on the gas outlet side also has a fixed plate 25 and a rotary plate 2.
4. The rotary plate 24 is provided with a gas groove 241 and gas holes 240 communicating therewith, and the fixed plate 25 is provided with six gas holes 250. The gas hole 240 is configured to communicate with the outlet pipe 14.

Next, the two rotary valves 20,
21 are arranged so that the respective fixing plates 23 and 25 face each other, and between the fixing plates 23 and 25, five five holes inserted into the six gas holes 230 and 250, respectively. Sample gas sampling pipe 29 and one cleaning gas pipe 290
And are arranged.

Next, the flow path switching valve 3 will be described.
As shown in FIG. 5 and FIG.
1 and a fixing plate 32. The fixing plate 32 has six gas holes 321 to 326 provided at equal intervals on the outer peripheral edge thereof.
Having. The rotating plate 31 is provided with three gas grooves 311 to 313 that can connect adjacent gas holes of the fixed plate 32 by contacting the fixed plate 32. For example, the gas groove 311 is
And 322, or gas holes 322 and 323 (see FIGS. 1 and 2).

As shown in FIG. 1, the gas holes 321 to 326 in the flow path switching valve 3 are connected to other flow paths as shown below. That is, the gas hole 321 is connected to the inlet pipe 13, and the gas hole 322 is connected to the inlet channel 11. The gas hole 323 is connected to the outlet channel 12, and the gas hole 324 is connected to the outlet pipe 14. In addition, gas hole 325
Is connected to an analyzer G (not shown), and the gas hole 326 is connected to a carrier gas supply source F.

Next, the time-division high-speed sampling device 1
A sampling method and an analyzing method of a sample gas using the method will be described. First, as shown in FIG. 1, an inlet operation for switching the inlet switching valve 4 so that the sample gas flows from the sample gas sampling port A into the inlet channel 11 is performed.

The outlet switching valve 6 performs an outlet operation so that the outlet channel 12 is connected to the vacuum system D. Note that the outlet switching valve 6 may be switched to switch the outlet channel 12 to the open system E depending on the situation.

Further, the flow path switching valve 3 is connected to the gas holes 321.
, 322, 323, 324, 325, and 326 are communicated with each other, and the sampler 2 performs a sampling operation for sampling the sample gas.

By the above sampling operation, the sample gas introduced from the inlet channel is transferred to the gas groove 31 of the channel switching valve 3.
1, through the inlet pipe 13, enters the sampling device 2.
Then, the sample gas is sampled in a time-division manner in each of the plurality of sample gas sampling pipes 29 by the operation of the pair of rotary valves 20 and 21 in the sampler 2.

That is, the rotary plates 22 and 2 in the pair of rotary valves 20 and 21 in the sampling device 2
4, the gas grooves 221 and 241 in the rotating plates 22 and 24 are rotated as shown in FIGS.
And one gas hole 230,
250 and one sample gas sampling pipe 29 connected to the gas holes 230 and 250 communicate with each other. Therefore, the sample gas introduced from the inlet pipe 13 into the one sample gas sampling pipe 29 is sampled.

Next, after the sampling in the one sample gas sampling pipe 29 is completed, the pair of rotating plates 2
By rotating the sample gas collection tubes 29 and 24, the next sample gas collection tube 29 different from the above-described sample gas collection tube 29 is communicated. Thus, the sample gas is sampled in different sample gas pipes 29.

During the sampling, the carrier gas introduced from the carrier gas supply source F into the flow path switching valve 3 via the pipe 190 is supplied to the gas groove 31 of the flow path switching valve 3.
3, through the pipe 19, is directly led to the analyzer G.

Next, a method of analyzing the sampled sample gas will be described. As shown in FIG. 2, only the flow path switching valve 3 is operated while the inlet switching valves 4, 5 and the outlet switching valve 6 are kept as they are, and the gas holes 321 and 326, 322, 323, 324 and 325 are communicated. At this time, the sampler 2 and the analyzer G constitute a closed circuit, and are separated from the flow path for another gas (excluding the carrier gas).

As described above, the sample gas introduced from the inlet channel 11 is led out to the outlet channel 12 through the gas groove 311 and discharged from the time-division high-speed sampling device 1.
On the other hand, the carrier gas is supplied to the gas groove 31 of the flow path switching valve 3.
3. The sample is introduced into the sampling device 2 via the inlet pipe 13.

The sample gas sampling tube 2 of the sampling device 2
The sample gas sampled at 9 is swept away by the carrier gas, and is led to an analyzer G (not shown) through an outlet pipe, a gas groove 312 and a pipe 19. The sample gas is led out to the analyzer G by operating the rotary valves 20 and 21 for each sample gas sampling pipe 29.

Next, after the above analysis is completed, the sample gas remaining in each part such as the flow path switching valve 3 is removed in order to sample the sample gas again. That is, the above-mentioned inlet switching valve 4,
5 is switched, the gas groove 52 makes the gas introduction hole 510 and the gas outlet hole 512 conductive, and the gas groove 42 makes the gas inlet hole 410 and the gas outlet hole 412 conductive. Further, the flow path switching valve is switched as shown in FIG.

As a result, the cleaning gas derived from the cleaning gas supply source C is introduced into the sampling device 2 via the inlet channel 11, the gas groove 311 in the channel switching valve 3, and the inlet pipe 13. . By the operation of the rotary valves 20 and 21 of the sampling device 2, the cleaning gas is led out to the outlet pipe 14 via the cleaning gas pipe 290. Thereafter, the cleaning gas passes through the gas groove 312 in the flow path switching valve 3, the outlet flow path 12, and the outlet switching valve 6, and
It is discharged from the time-division high-speed sampling device 1. As described above, the residual gas in the inlet channel 11 and the like can be removed.

If necessary, sample gas sampling, sample gas analysis, time-division high-speed sampling device 1
The standard condition of the analyzer G is tested with the standard gas between the cleanings of. In this case, the inlet switching valves 4 and 5 are switched to introduce the standard gas derived from the standard gas supply source B into the inlet channel 11. In addition, the above flow path switching valve is shown in FIG.
Switch as shown in.

As described above, the standard gas is supplied to the inlet channel 1
1, the sample gas sampling pipe 29 in the sampling device 2 is filled through the flow path switching valve 3 and the inlet pipe 13. Thereafter, the flow path switching valve 3 is switched as shown in FIG. 2, and the standard gas filled in the sample gas sampling pipe 29 is passed through the outlet pipe 14 and the flow path switching valve 3 by the carrier gas.
It is led to the analyzer G. As described above, the standard gas is analyzed in the automatic analyzer using the time-division sampling device 1.

It is to be noted that the operation timing and the like of each part of the device are controlled by a controller (not shown). A personal computer is used for the controller (see FIG. 7 in the second embodiment).

Next, the operation and effect of this embodiment will be described. In the time-division high-speed sampling device 1 of this example,
By switching the flow path switching valve 3, the sampling device 2
, A sample gas can be introduced. At this time, the rotary valves 20 and 21 in the sampler 2 are
As described in the above-described measurement method, the sample gas can be successively introduced into the five sample gas sampling pipes 29 in time series by appropriately operating.

The rotary valves 20, 21
Is an air-driven valve. For this reason, a minimum of 0.2
At second intervals, the rotary valves 20 and 21 can be driven, so that for different sampling tubes 29
A sample gas can be sampled every second. Therefore, the automatic analyzer having the time-division high-speed sampling device 1 of the present example can detect the fluctuation of the gas at intervals of about 0.2 seconds.

Embodiment 2 As shown in FIG. 7, this embodiment is an automatic analyzer 8 for measuring exhaust gas of an automobile engine using the time-division high-speed sampling device shown in Embodiment 1. Further, the result of analysis by the automatic analyzer 8 is compared with the result of analysis by a conventional general automobile exhaust gas analyzer.

As shown in FIG. 7, in the automatic analyzer 8, two time-division sampling devices 1 are installed before and after a catalytic converter 91 provided in an exhaust system 90 of an automobile engine 9.

That is, the sample gas sampling port 49 of one time-division high-speed sampling apparatus 1 is connected to the upstream side 901 of the catalytic converter 91 provided in the exhaust system 90, and the sampling of the other time-division high-speed sampling apparatus 1 is performed. Mouth 499
Is provided on the downstream side 902 of the catalytic converter 91.

The time-division high-speed sampling apparatus 1 is connected to a gas chromatograph 80 as an analyzer. An integrator 82 is connected to the gas chromatograph 80, and the total amount of organic substances (THC) in the sample gas sampled by the two time-division high-speed sampling devices 1 is compared and measured.

Further, the flow path switching valve and the sampler in the above two time-division high-speed sampling devices 1 are operated in conjunction with each other to connect the inlet flow path to the sampler via the flow path switching valve. Is provided with a personal computer 83 as a controller in order to make the communication with the outlet flow path via the flow path switching valve.

Next, the automatic analyzer 8 and a conventional general automobile exhaust gas analyzer, MEXA-8120D
Using HORIBA, Ltd., the changes with time of THC on the upstream side 901 and the downstream side 902 of the catalytic converter 91 were measured, and the results are shown in FIG. The vertical axis in FIG.
HC, the horizontal axis is time.

According to the automatic analyzer 8 according to the present invention shown in FIG. 7, the sharp peak (a) having a width of 2 seconds at the upstream side 901 of the catalytic converter 91 and the peak (a) slightly A slightly sharp peak (b) with a width of 3 seconds, which was suppressed, could be measured.

On the other hand, in the conventional apparatus, the width 2 in the upstream side 901 was delayed by about 3 seconds from the measurement by the apparatus of the present invention.
It was only possible to measure the second peak (c) and the 3-second width peak (d) on the downstream side 902. In addition, the rising state of these peaks (c) and (d) has a longer tail and is dull compared to the present invention.

That is, the conventional apparatus has a long pipe and a buffer for adjusting the pressure of the sample gas. For this reason, in the measurement of the conventional device, the position of the THC peak is shifted,
It has become slow.

As described above, in the present invention, the change of THC in the exhaust gas before and after the catalytic converter 91 could be clearly captured. On the other hand, in the conventional device, the change of THC in the exhaust gas before and after the catalytic converter 91 was hard to understand, and it was difficult to grasp the effect of the catalyst.

Embodiment 3 In this embodiment, the exhaust gas was analyzed using the automatic analyzer according to the present invention. The analysis result will be described with reference to FIG. 9 and Table 1. The automatic analyzer according to the present embodiment is the automatic analyzer (see FIG. 7) used in the second embodiment. A gas chromatograph manufactured by Hewlett-Packard Company was used. Using the above automatic analyzer under the conditions shown in Table 1,
Exhaust gas measurements were made. FIG. 9 shows the result.

As shown in FIG. 10, HC in the exhaust gas takes about 50 minutes.
(About 300 species) can be efficiently separated.
As an analyzer in the automatic analyzer, GC /
Using MS (Hewlett Packard),
By analyzing C, about 250 components of HC were identified (98% in the area of the gas chromatograph). Furthermore, the repetition reproducibility under the conditions in this example is 2 to 3 in CV value.
%, And the lower limit of quantification was 0.5 to 0.05 ppm.

The analysis of the exhaust gas is usually performed by a data processing device (integrator) for a gas chromatograph.
Is used to calculate the components and concentrations. In this example,
Since it is necessary to calculate the ozone generation capacity simultaneously with processing a large amount of data, a special program has been developed. The above program receives a retention time and an intensity from an integrator for a gas chromatograph, compares the retention time and intensity with a database created in advance, performs qualitative and quantitative determinations, and further calculates ozone generating ability. At this time, the deviation of the retention time can be automatically corrected by the reference peak method.

As described above, by selecting an analyzer to be mounted on the automatic analyzer of the present invention, optimizing analysis conditions, and creating a data processing program, separation of 300 kinds of organic components, 2
It was found that 50 kinds of organic components could be identified in a short time.

[0081]

[Table 1]

[0082]

As described above, according to the present invention, it is possible to provide a time-division high-speed sampling apparatus, an automatic analyzer, and an automatic analysis method capable of sampling a sample gas at minute time intervals.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of a time-division high-speed sampling device in a state where a sample gas is sampled in a first embodiment.

FIG. 2 is an explanatory diagram of a time-division high-speed sampling device in a state where a sample gas is analyzed by an analyzer in the first embodiment.

FIG. 3 is a development explanatory view showing a structure of a sampler in the first embodiment.

FIG. 4 is (a) a back view of a rotary plate and (b) a plan view of a fixed plate of the rotary valve in the first embodiment.

5A and 5B are a back view of a rotary plate and a plan view of a fixed plate of a flow path switching valve according to the first embodiment.

6A is a sectional view taken along the line AA in FIG. 5A,
(B) FIG. 5 (b) is a sectional view taken along the line BB.

FIG. 7 is an explanatory diagram of an automatic analyzer according to a second embodiment.

FIG. 8 is a diagram showing a time variation of THC in exhaust gas measured by the automatic analyzer according to the present invention and a conventional device in the second embodiment.

FIG. 9 is a diagram showing an analysis result of exhaust gas using the automatic analyzer according to the present invention in the third embodiment.

[Explanation of symbols]

 1. . . 10. Time-division high-speed sampling device, . . 11. inlet channel, . . 12. outlet channel; . . 13. inlet pipe, . . Outlet pipe, 2. . . Sampler, 20, 21. . . Rotary valve, 3. . . Flow path switching valve, 4,5. . . 5. Inlet switching valve, . . Outlet switching valve, 8. . . Automatic analyzer,

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Fumiko Oshima 41-Yokomichi, Nagakute-cho, Aichi-gun, Aichi Prefecture Inside Toyota Central Research Institute, Inc. 41 at Yokomichi 1 Toyota Central Research Institute, Inc. (72) Inventor Kenichi Uchida 1 Toyota Town, Toyota City, Aichi Prefecture Toyota Motor Corporation (72) Inventor Go Watanabe 1 Toyota Town, Toyota City, Aichi Prefecture Toyota Motor (72) Inventor Kazuhisa Kunitake 1 Toyota Town, Toyota City, Aichi Prefecture Toyota Motor Corporation (56) References JP-A-7-55780 (JP, A) JP-A-58-206947 (JP) , A) JP-A-6-201538 (JP, A) JP-A-53-1388 (JP, U) (58) Fields investigated (Int. Cl. ⁷ , DB name) G01N 30/20 G01N 1/00 G01N 1/22

Claims (7)

(57) [Claims] 1. A flow path switching valve for switching an inlet flow path to a sampler or an outlet flow path, an inlet pipe for introducing a sample gas from the flow path switching valve to the sampler, and a flow path switching valve from the sampler. An outlet pipe for taking out the sample gas to the sampler. The sampler is arranged between a pair of rotary valves which are arranged on the gas inlet side and the gas outlet side and rotate synchronously, and are arranged between the rotary valves. A case having a plurality of sample gas sampling pipes and operating the flow path switching valve and the sampler to communicate the inlet flow path with the sampler via the flow path switching valve;
A time-division high-speed sampling apparatus, comprising: a controller for switching between an inlet channel and an outlet channel via a channel switching valve. 2. The time-division high-speed sampling apparatus according to claim 1, wherein the rotary valve in the sampling device operates at a time interval of 0.2 seconds or more. 3. The method according to claim 1, wherein the inlet passage has an inlet switching valve capable of switching to at least one of a sample gas sampling port, a standard gas supply source, and a cleaning gas supply source. Characteristic time-division high-speed sampling device. 4. The method according to claim 1, wherein:
The time-division high-speed sampling device, wherein the outlet flow path has an outlet switching valve that can switch between a vacuum system and an open system. 5. A flow path switching valve for switching an inlet flow path to a sampler or an outlet flow path, an inlet pipe for introducing a sample gas from the flow path switching valve to the sampler, and a flow path switching valve from the sampler. An outlet pipe for taking out the sample gas to the sampler. The sampler is arranged between a pair of rotary valves which are arranged on the gas inlet side and the gas outlet side and rotate synchronously, and are arranged between the rotary valves. A case having a plurality of sample gas sampling pipes and operating the flow path switching valve and the sampler to communicate the inlet flow path with the sampler via the flow path switching valve;
A controller for switching between an inlet flow path and an outlet flow path via a flow path switching valve; and an analyzer for analyzing the sample gas, and introducing the sample gas into the analyzer. Automatic analyzer having an analyzer switching unit for the automatic analyzer. 6. The automatic analyzer according to claim 5, wherein the analyzer is a gas chromatograph. 7. A flow path switching valve for switching an inlet flow path to a sampler or an outlet flow path, an inlet pipe for introducing a sample gas from the flow path switching valve to the sampler, and a flow path switching valve from the sampler. An outlet pipe for taking out the sample gas to the sampler. The sampler is arranged between a pair of rotary valves which are arranged on the gas inlet side and the gas outlet side and rotate synchronously, and are arranged between the rotary valves. A case having a plurality of sample gas sampling pipes and operating the flow path switching valve and the sampler to communicate the inlet flow path with the sampler via the flow path switching valve;
A controller for switching between an inlet flow path and an outlet flow path via a flow path switching valve; and an analyzer for analyzing the sample gas, and introducing the sample gas into the analyzer. For performing automatic analysis using an automatic analyzer having an analyzer switching section for connecting the inlet channel to at least one of a sample gas sampling port, a standard gas supply source, and a cleaning gas supply source. The entrance operation to
An outlet operation for connecting the outlet channel to a vacuum system or an open system, and a sampling operation for switching the inlet channel to a sampler or an outlet channel are performed. The sample gas is sampled in a time-division and high-speed manner into the sample gas sampling pipe by closing each circuit with the sampler, and the sample gas sampled is analyzed by an analyzer. An automatic analysis method characterized by cleaning residual gas in a device with a cleaning gas and, if necessary, testing a standard condition of the analyzer with a standard gas.