JPH1090134A - Method and analyzer for analyzing water for trace volatile organic compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method and instrument for analyzing water for trace volatile organic compound suitable for the pre-treating device of a qualitative and quantitative measuring instrument for organic matters. SOLUTION: After sample water 2 and an internal standard sample 47 are introduced to a concentrator 51, the flow passage of the sample water 2 is cleaned. Before the sample water 2 is introduced to the concentrator 51, the sample water 2 from a water collecting source 1 is made to flow through the flow passage of the sample water 2 on the upstream side of an analyzer enclosure 4 for a prescribed period of time. After the standard sample 47 is introduced to the concentrator 51, the sample water 2 is introduced to the concentrator 51 so that the standard sample 47 remaining in the flow passage of the internal standard sample can be removed with the sample water 2. When the concentrator 51 is drained, the concentrator 51 is cleaned by introducing a cleaning solution 29 to the concentrator 51.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention makes it possible to eliminate the trouble of preparing sample water, prevent the risk of contamination and human error, realize online measurement of water quality, and accurately and rationally input a drug. In addition to enabling the automatic cleaning of the filter that filters the sample water, promoting its function recovery and regeneration, the sample water flow path and related equipment are rationally cleaned, and the internal standard sample remaining in the flow path is removed. The present invention relates to a method and an apparatus for analyzing trace volatile organic compounds in water, which are removed to improve the reliability of analysis and are suitable for a pretreatment apparatus of a qualitative / quantitative measurement apparatus for organic substances such as GC / MS.

[0002]

2. Description of the Related Art Conventionally, determination of trace volatile organic compounds (VOC) contained in environmental water, lakes, marshes, seawater, tap water, and treated water has been carried out by the qualitative analysis of organic substances such as GC / MS (gas chromatography / mass spectrum). A purge and trap device, which is a pretreatment device of the quantitative measurement device, has been used.

[0003] In this pretreatment apparatus, a method has been adopted in which the sample liquid is introduced manually, or the sample liquid is sealed in a large number of vials or purge glass tubes and collectively measured by an autosampler. In this case, when the sample is dirty, a pretreatment device is required to guide the sample to a filter and remove the sample.

However, in the manual measurement and the autosampler, there is a problem that a sample has to be put into a vial bin or a sample tube at the time of sample preparation, which is troublesome, and the risk of contamination and human error are liable to occur. .

[0005] Incidentally, since it is known that some of VOCs give offfensive odors or harm human health, it is necessary to appropriately remove them. For example, activated carbon has conventionally been used as a means for removing trace VOCs in drinking water,
This was charged according to the above-mentioned trace VOC concentration. At that time, a purge and trap device equipped with an autosampler was used to control the amount of activated carbon charged, the VOC concentration was measured by the device, and a required amount of activated carbon was charged.

However, since the above-mentioned apparatus is not an online system, it is impossible to measure the change over time of a minute amount of VOC on holidays or at night, and usually, activated carbon is charged by estimation. Therefore, when the input amount of activated carbon is small, there is a problem that VOCs remain and give discomfort to the user or harm the health, and when it is too large, the activated carbon is wasted and the cost increases. .

By the way, the internal standard substance added for the purpose of correcting the error in the introduction amount of the sample liquid is not stable in water in many cases, and is used after being dissolved in a small amount of an organic solvent. Since the above-mentioned internal standard solution is generally relatively high in concentration compared to the sample solution, it is indispensable to accurately introduce a small amount of the solution. Results. Further, since the concentration of the sample and the internal standard solution is performed thereafter, there is a problem that the error is further increased and the analysis result is seriously affected.

[0008]

SUMMARY OF THE INVENTION The present invention solves such problems, eliminates the need for preparation of sample water, prevents the risk of contamination and human error, and enables the on-line production of trace volatile organic compounds in water. It realizes measurement and can supply the input chemicals accurately and rationally, enables automatic cleaning of the filter that filters the sample water, promotes its function recovery and regeneration, and establishes the flow path of the sample water and related equipment. Washing rationally and removing the internal standard sample remaining in the flow path to improve the reliability of analysis, suitable for pretreatment equipment for qualitative and quantitative measurement of organic substances such as GC / MS An object of the present invention is to provide a method and an apparatus for analyzing volatile organic compounds.

[0009]

For this reason, the invention of claim 1 provides a method of introducing a sample water and an internal standard sample into a concentrator, and then cleaning a trace amount of volatile organic compound in the water so as to wash the flow path of the sample water. In the compound analysis method, before introducing the sample water concentrating device, the sample water of the water intake source is circulated for a predetermined time upstream of the flow path of the sample water, and the inside of the flow path is replaced with the current sample water, and the analysis is performed. Ensure accuracy and reliability. In addition, compared to the case where the internal standard sample is introduced into the concentrating device before introducing the sample water, and this is introduced after introducing the sample water, the quantitative internal standard sample is introduced more stably, and the reliability of the analysis accuracy is improved. In addition, the internal standard sample remaining in the internal standard sample flow path can be removed via the sample water, thereby preventing the generation of an analysis error due to the remaining internal standard sample. Further, the cleaning liquid can be introduced into the concentrator when draining the concentrator, and the concentrator is rationally washed. The invention according to claim 2 controls the sequence of the circulation of the sample water, the introduction of the sample water and the internal standard sample into the concentrator, and the washing of the flow path of the sample water and the concentrator, thereby evaporating a trace amount of the sample water. Realization of online analysis of volatile organic compounds. According to a third aspect of the present invention, there is provided a water quality analyzer configured to wash a flow path of a sample water after introducing a sample water filtered by a filter and an internal standard sample into a concentrator, wherein The filter is selectively switchable, the filter can be switched when the filter is deteriorated, the filtration of the sample water is performed stably and reliably, and the analysis of trace volatile organic compounds in the sample water is promoted online, GC / M
It is suitable for a pretreatment device of a qualitative / quantitative measurement device for organic substances such as S.

According to a fourth aspect of the present invention, a plurality of filters having a coarse mesh are arranged on the upstream side of the flow path of the sample water, and a plurality of filters having a dense mesh are arranged on the downstream side thereof, so that the filtration of the sample water can be performed precisely. In addition to performing the operation reliably, the deterioration of the filter is suppressed. According to a fifth aspect of the present invention, a multi-port type filter switching valve is disposed in the flow path of the sample water, a plurality of filters are detachably connected to the switching valve, so that a large number of filters can be switched and replaced. Is facilitated. According to a sixth aspect of the present invention, a filter deterioration sensor capable of detecting the deterioration of the filter is provided in the flow path of the sample water, and the filter can be switched when the deterioration of the sensor is detected, so that the filter can be switched rationally and accurately.

According to a seventh aspect of the present invention, a filter having excellent durability, adsorbability and cleaning property with respect to a sample water is used for each mesh, and an optimum filter is selected from various angles with respect to the sample water. , Its reasonable use. According to the invention of claim 8, the filter and the flow path of the sample water around the filter can be externally observed, and the degree of deterioration of the filter and contamination of the sample water can be easily confirmed. The invention of claim 9 is
The filter can be washed for each filter having a coarse and dense mesh, thereby preventing reverse clogging of the filter when these are simultaneously washed.

According to a tenth aspect of the present invention, the washing liquid conduit is connected to the downstream side of the flow path of the sample water, and the washing liquid is moved from the downstream side to the upstream side of the flow path of the sample water so as to be drainable. The filter disposed in the road can be washed, and foreign matter discharged from the filter having a dense mesh is prevented from adhering to the filter having a coarse mesh. The invention according to claim 11 is characterized in that, on the upstream side of each filter switching valve disposed in the flow path of the sample water, a discharge pipe and a solenoid valve that can be drained to the outside are disposed,
Achieves cleaning of each filter with coarse and dense mesh. According to the twelfth aspect of the present invention, the filter switching valve is switched so that each filter can be washed, and it is possible to wash a contaminated filter which is being used and whose use has been stopped once.

[0013] According to the invention of claim 13, the washing liquid can be introduced into the filter having a dense mesh every time the filter is washed, the washing of the filter is carried out precisely, and the filtering function of the filter is surely restored. Perform water filtration with high accuracy. According to the fourteenth aspect of the present invention, the used filter can be regenerated, and the non-renewable filter can be replaced, so that the rational use of the filter and the reduction of the cost can be achieved. In the invention according to claim 15, a first switching valve is connected downstream of the flow path of the sample water, and the switching valve is connected to a transfer gas conduit and a sample distribution pipe inserted through a sample loop. A second switching valve communicable with the valve is provided, and an internal standard distribution pipe and an internal standard sample supply pipe interposed with an internal standard loop are connected to the switching valve, and an internal standard conduit communicating with the concentrator is connected. And the internal standard sample are reliably introduced into the concentrator. Claim 1
According to the invention of claim 6, the sample loop and the internal standard loop are filled with a predetermined amount of sample water and an internal standard sample, and the sample water is introduced into the concentrating device via the internal standard conduit when the first and second switching valves are communicated. Enable and ensure that sample water is introduced into the concentrator.

According to a seventeenth aspect of the present invention, after the sample water and the internal standard sample are introduced into the concentrating device, the washing solution is introduced into the sample distribution pipe and the sample loop to enable them to be washed, thereby improving the accuracy of the next analysis. According to the eighteenth aspect of the present invention, after the sample water and the internal standard sample are introduced into the concentrator, the drainage of the concentrator communicates the first and second switching valves, and the first switching valve communicates the transfer gas conduit. Then, the washing liquid in the sample distribution pipe and the sample loop is introduced into the concentrator and drained, and these flow paths and the concentrator can be washed, thereby improving the accuracy of the next analysis. The invention of claim 19 controls the operation of each filter switching valve, each solenoid valve, the first and second switching valves, the sample supply pump, and the cleaning liquid supply pump in sequence to analyze the trace volatile organic compound in the sample water. Realize online.

[0015]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A description will now be given of an embodiment in which the present invention is applied to the analysis of trace VOCs in drinking water. In FIGS. 1 to 8, reference numeral 1 denotes a drinking water 2 which is a sample water. An analysis housing 4 is installed at a position as close as possible to the water intake source 1 at a water intake source of a river or a lake stored through the wall 3.

A sample supply pump 5 is provided outside the casing 4, one end of a sample supply pipe 6 is connected to the pump 5, and the other end is immersed in the water supply source 1. One end of a sample supply pipe 7 is connected to the discharge side of the sample supply pump 5, and the other end is connected to an electric first switching valve 8. 10
Is connected.

Each of the filter switching valves 9 and 10 is composed of a 6-port switching valve, and has two diversion pipes 11 to 1 connected to its four ports.
4 are connected, and the tubes 11, 12 and 13, 14 are openable and closable with each other.
8 is detachably attached. That is, the branch pipe 1
Each of the filters 1, 12, 13, and 14 is configured such that when one of the filters is connected to the sample supply pipe 6, the other is shut off, and the filter inserted on the connection side performs a filtering action.

The filter switching valves 9 and 10 are automatically rotated when the filter deterioration sensor described later detects a signal of a predetermined value to switch the open / close mode of the flow dividing pipes 10 to 14 and communicate with the sample supply pipe 6. It allows for the use of filtered filters.

The filters 15, 16 and 17, 1
8 are of the same quality, and among them, filters 17 and 18 inserted in the filter switching valve 10 on the downstream side.
Is the filter 1 inserted in the filter switching valve 9 on the upstream side.
The mesh is made denser than 5 and 16, so that finer foreign substances in the drinking water 2 can be captured.

The filters 15 to 18 actually supply sample water to various filters made of, for example, hollow fibers, glass, Teflon, and metal, and perform experiments on filtration performance such as durability and adsorptivity in advance. The best one is used for each mesh.

The sample supply pipe 7 upstream of each of the filter switching valves 9 and 10 is provided with filter deterioration sensors 19 and 20 which can detect clogging of the filters 15 to 18, and in the embodiment, pressure sensors. In this case, a signal can be input to the controller 21. In this case, instead of the pressure sensor, an optical sensor may be used to optically detect the contamination of the drinking water 2, so that the contamination is prevented. Can be detected stably and accurately.

The filter deterioration sensor 19 is capable of detecting clogging of the filters 15 and 16, and the filter deterioration sensor 20 is capable of detecting clogging of the filters 17 and 18.

When the sensors 19 and 20 detect the unusable deterioration of the filters 15 to 18, in the embodiment, a predetermined pressure value, the controller 21 outputs a control signal to the filter switching valves 9 and 10, The valves 9 and 10 are switched to switch the open / close mode of the flow dividing pipes 11 to 14 so that the unused flow dividing pipe on the filter side is connected to the sample supply pipe 7 so that the filtering operation by the unused filter can be performed. .

The controller 21 has a built-in microcomputer. The computer stores a sequence of a trace VOC analysis system. Based on the stored information, a series of switching valves, solenoid valves, pumps, meters, etc. Control signals can be output to related equipment sequentially.

In the drawing, reference numeral 22 denotes a discharge pipe having one end connected to the sample supply pipe 7 between the filter switching valves 9 and 10, the other end being connected to the water source 1, and 23 being the sample supply pump 5.
A bypass pipe, one end of which is connected to a sample supply pipe 7 between the filter switching valve 9 and the other end of the discharge pipe 2
2 connected. In the sample supply pipe 7 between the bypass pipe 23 and the discharge pipe 22 and the filter switching valves 9 and 10,
Further, the solenoid valves 24 to 24 are located upstream of the connection position of the discharge pipe 22.
The operation is controlled by the controller 21.

Reference numeral 27 denotes the first switching valve 8 and the filter switching valve 10
A washing tube having one end connected to the sample supply tube 7 between
The other end is connected to the cleaning liquid container 28, and the container 28
Contains a cleaning liquid 29 such as pure water. A cleaning liquid supply pump 30 is connected to the upstream side of the cleaning pipe 27, and electromagnetic valves 31 and 32 are inserted downstream of the pump 30, and their operations are controlled by the controller 21.

The first switching valve 8 is constituted by a 6-port switching valve, and its operation is controlled by the controller 21. The port P1 of the switching valve 8 is connected to the downstream end of the sample supply pipe 7, and the ports P2 and P5 are connected to both ends of the sample distribution pipe 33. Is connected.

One end of a transfer gas conduit 35 is connected to the port P3 of the first switching valve 8, and the other end is connected to a gas container 36 filled with helium gas, which is a transfer gas for pressurization. From the upstream side, a solenoid valve 37, a metering valve 38,
The pressure gauge 39 and the pressure regulator 40 are interposed, and the operation of the electromagnetic valve 37 is controlled by the controller 21.

A connecting pipe 42 communicating with the second switching valve 41 is connected to the port P4 of the first switching valve 8, one end of a drain pipe 43 is connected to the port P6, and the other end is connected to an analysis housing. 4 is piped outside. In the figure, reference numeral 44 denotes an electromagnetic valve inserted in the drain pipe 43, and its operation is controlled by the controller 21.

The second switching valve 41 is constituted by a motor-operated 6-port switching valve, the operation of which is controlled by the controller 21. One end of an internal standard sample supply pipe 45 is connected to the port P 1 of the switching valve 41, and the other end is connected to the internal standard sample container 4.
6 immersed in an internal standard sample 47 such as methanol.

The ports P2 and P5 of the second switching valve 41 have
Both ends of the internal standard flow pipe 48 are connected, and the internal standard loop 49 capable of filling a fixed amount of the internal standard sample 47 is connected to the pipe 48. One end of an internal standard conduit 50 is connected to the port P4 of the switching valve 41, the other end is connected to a sample tube of a purge and trap device 51 which is a concentrator, and one end of a drain tube 52 is connected to a port P6. The other end is connected to the outside of the analysis housing 4.

In the figure, reference numeral 53 denotes an electromagnetic valve inserted in the drain pipe 52, and its operation is controlled by the controller 21. Reference numeral 54 denotes a transfer gas distribution pipe branched from the upstream side of the transfer gas conduit 35, one end of which is connected to the transfer gas conduit 35 between the metering valve 38 and the pressure gauge 39, and the other end of which is an inner sample storage container 46. Connected to A pressure regulator 55, a pressure gauge 56, and an electromagnetic valve 57 are connected to the transfer gas distribution pipe 54, and the operation of the electromagnetic valve 57 is controlled by the controller 21.

The purging and trapping device 51 is capable of concentrating volatile organic compounds in the drinking water 2 as a sample liquid. The purging and trapping device 51 supplies a purging gas to the drinking water 2 sent from the internal standard conduit 50 to the sample tube 58. Rinse, drinking water 2
The volatile organic compound therein is temporarily held in an adsorbent filled in a trap tube (not shown), and then the trap tube is heated and desorbed, and can be introduced from the transfer tube 59 to a gas chromatograph 60 as a separation device. ing.

Reference numeral 61 denotes a detector, a mass spectrometer is used in the embodiment, and reference numeral 62 denotes a mode monitor.
The present analysis status can be displayed by a signal output from the
An error display, a warning display, or a warning sound can be generated by a signal output from 1.

In addition, reference numeral 64 in the figure denotes an electromagnetic valve inserted in the sample supply pipe 6 between the connection part of the bypass pipe 23 and the filter deterioration sensor 19, and its operation is controlled by the controller 21.
Is controlled by Numeral 65 denotes an electromagnetic valve inserted into the sample supply pipe 6 between the sample supply pump 5 and the electromagnetic valve 64, which is normally opened, and its operation is controlled by the controller 21.

The analyzer constructed as described above is connected to the water intake source 1
, One end of the sample supply pipe 6 is connected to the sample supply pump 5, the other end is immersed in the drinking water 2 as the sample water, and the drain-side end of the drain pipe 22 is connected to the water source 1. Place in place. In this case, the length of the sample supply pipe 6 is desirably as short as possible in order to reduce the residual contamination of the drinking water 2 and to reduce the power of the sample supply pump 5.

Before the above analysis, the drinking water 2 was actually passed through various filters such as hollow fibers, glass, Teflon, and metal, and its durability, adsorptivity, detergency, etc. were confirmed by experiments to determine the optimum. Filters are selected for each mesh, and these are used as filters 15-18,
Attach to ~ 14.

Thus, a series of preparation work is completed. This situation is as shown in FIG. 3, in which the sample supply pump 5 and the cleaning liquid supply pump 30 stop driving, and each of the electromagnetic valves 24 to 2 stops.
6, 31, 32, 37, 44, 53, 57, 64 and the gas container 36 are closed, and the solenoid valve 65 is opened. Therefore, before the analysis, the drinking water 2, the transfer gas and the cleaning liquid 2
9 is not introduced into the analyzer.

Under such an analysis standby condition, the detector 61
When the drive switch is turned on when the total number of times of measurement, in the embodiment, the infinite number of times and the appropriate measurement interval are input to the analyzer, the controller 21 operates, and the VOC analysis is performed based on the stored sequence. To start.

The controller 21 first executes the sample replacement, sends a control signal to the solenoid valve 24 and the sample supply pump 5, opens the solenoid valve 24, and drives the sample supply pump 5.

In this manner, the drinking water 2 as a sample liquid is pumped up, guided to the sample supply pipe 6 and moved through the bypass pipe 23, from which the discharge pipe 22 is discharged.
And returned to the water intake source 1.

This situation is as shown in FIG. 3, in which the sample supply pipe 6 upstream of the analysis case 4 is replaced by the drinking water 2 of the water intake source 1, and this is circulated to the water intake source 1. Therefore, prior sample water, washing liquid, foreign matter, and the like remaining in the sample supply pipe 6 are removed and replaced with the current sample water, so that the reliability of the analysis is improved. This is effective when the introduction path of the sample supply pipe 6 is long.

After the replacement of the sample, the controller 21 simultaneously executes the preceding introduction of the sample and the internal standard sample. Among them, the controller 21 continues to drive the sample supply pump 5 when introducing the sample in advance,
A control signal is sent to the solenoid valves 24, 64, 26, 44 to close the solenoid valve 24 and open the solenoid valves 64, 26, 44.

In this way, the sample supply pump 5
The drinking water 2 pumped to the sample supply pipe 6 passes through the filter deterioration sensor 19, and is guided to the distribution pipe 11 of the filter switching valve 9 on the downstream side thereof, and moves the filter 15.

At this time, the sensor 19 detects the fluid pressure every moment and inputs the signal to the controller 21. When the detected pressure is equal to or lower than a predetermined value, the controller 21 allows the current filter 15 to perform filtration. On the other hand, when the pressure is equal to or higher than the predetermined value, the controller 21 sends a control signal to the filter switching valve 9 to switch the valve 9. .

As a result, the branch pipe 11 is connected to the sample supply pipe 6.
And the use of the filter 15 interposed in the pipe 11 is stopped, and the branch pipe 12 is connected to the supply pipe 6, and the drinking water 2 is guided to the pipe 12 to filter the filter 16.
Moved and filtered.

As described above, the present invention provides filters 15 and 16
The deterioration status of the filter 15 is monitored from time to time, the use of the deteriorated filter 15 is temporarily stopped, and another filter 16 is immediately
To ensure the filtration of the drinking water 2 at all times, to prevent contamination and failure of various devices, and to promote the analysis of the drinking water 2 online.

In this way, the drinking water 2 passes through the filter 15 or 16, is guided from the filter switching valve 9 to the sample supply pipe 6, passes through the filter deterioration sensor 20,
The filter 17 is guided by the branch pipe 13 of the filter switching valve 10 on the downstream side to move the filter 17.

At this time, the sensor 20 detects the fluid pressure every moment and inputs the signal to the controller 21. When the pressure is equal to or less than the predetermined value, the controller 21 allows the current filter 17 to perform filtering. On the other hand, when the pressure is equal to or more than the predetermined value, the controller 21 sends a control signal to the filter switching valve 10,
The valve 10 is switched.

As a result, the branch pipe 13 is connected to the sample supply pipe 6.
And the use of the filter 17 inserted in the pipe 13 is stopped, and the branch pipe 14 conducts the supply pipe 6, and the drinking water 2 is guided to the pipe 14 to filter the filter 18.
And the filter 17
More precisely filtered.

As described above, according to the present invention, two types of filters 1 are provided in the sample supply pipe 6 upstream of the first switching valve 8.
5, 16, 17, and 18 are arranged to accurately and reliably filter the drinking water 2 to prevent contamination and breakdown of various devices beforehand, and realize online analysis of the drinking water 2.

Thus, the drinking water 2 is supplied to the filter switching valve 1
After passing through the sample diverting pipe 3,
3, the sample loop 34 is filled with a fixed amount of drinking water 2, and discharged from the drain tube 43 to the outside of the analysis housing 4. This situation is as shown in FIG.

On the other hand, when the internal standard sample is introduced in advance, the gas container 36 is opened, and a control signal is sent from the controller 21 to the solenoid valves 53 and 57 to open them.

In this way, the transfer gas filled in the gas container 36 is guided to the transfer gas conduit 35 and flows into the internal standard sample storage container 46, and the internal pressure of the container 46 rises, The internal standard sample 47 stored in 46 is pushed out to the internal standard sample supply pipe 45.

The internal standard sample 47 is provided with an internal standard sample supply pipe 45.
Is guided to the second switching valve 41, and the inside of the
8, the internal standard loop 49 is filled with a fixed amount of the internal standard sample,
It is discharged from the analysis tube 4 through the drain tube 52.
This situation is as shown in FIG.

Under such circumstances, the controller 21
First, at the time of executing the internal standard sample introduction, the controller 21 sends a control signal to the electromagnetic valves 37, 53, 57 to open the electromagnetic valve 37 and close the electromagnetic valves 53, 57.

The controller 21 has a second switching valve 41
Output a control signal to switch the valve 41 to the port P2
, P3 and the ports P4 and P5 are communicated with each other, and the port P3 is communicated with the connecting pipe 42, and the ports P2 and P5 are connected.
5 to the internal standard distribution pipe 48, and port P4 to the internal standard conduit 5.
Communicate with 0.

In this way, the transfer gas filled in the gas container 36 is guided to the transfer gas conduit 35 and moves to the first switching valve 8, and the connection pipe 42 is connected to the ports P3 and P4.
To the second switching valve 41 through the ports P3, P2
The inner standard flow pipe 48 is moved further.

At this time, the transfer gas is supplied to the inner standard flow pipe 4.
8 and the internal standard sample filled in the internal standard loop 49 are pushed and moved, and the ports P5 and P4 and the internal standard conduit 5 are moved together with the sample.
0 is moved to the purge and trap device 51. During this time, the preceding introduction mode of the sample is continued, and the drinking water 2 moves from the first switching valve 8 through the sample dividing pipe 33 through the sample loop 34 and is discharged from the drain pipe 43 to the outside of the analysis casing 4. Is done. This situation is as shown in FIG.

Next, the controller 21 executes sample introduction. At this time, the supply of the transfer gas is continued, and the controller 21 sends the sample supply pump 5 and the solenoid valves 65 and 6.
4, 26, 44 to stop the operation of the pump 5 and to control the solenoid valves 65, 64, 26, 44.
Is closed.

The controller 21 has a first and a second
A control signal is output to the switching valves 8 and 41, and the switching valves 8 and 41 are switched. That is, the ports P2 and P3 and the ports P4 and P5 of the first switching valve 8 communicate with each other, the port P3 communicates with the transfer gas conduit 35, and the port P
2 and P5 are connected to the sample distribution pipe 33, and the port P4 is connected to the connection pipe 42. Further, the ports P3 and P4 of the second switching valve 41 are communicated, the port P3 is communicated with the connecting pipe 42, and the port P4 is communicated with the internal standard conduit 50.

In this way, the transfer gas filled in the gas container 36 is guided to the transfer gas conduit 35, moves to the first switching valve 8, and is guided to the sample distribution pipe 33 from the ports P3 and P2. Then, the sample loop 34 is moved to push the drinking water 2 as a sample filled therein, and the connecting pipe 42 is moved together with the sample through the ports P5 and P4.

Thereafter, the transfer gas and the sample are guided to the connecting pipe 42 and move to the second switching valve 41, and the internal standard conduit 50 is moved from the ports P3 and P4 to the purge and trap device 51. Will be introduced. This situation is as shown in FIG.

As described above, according to the present invention, since the internal standard sample is first introduced into the purge and trap device 51, a fixed amount of the internal standard sample can be introduced more stably and smoothly than when the internal standard sample is introduced after the sample introduction. While accurate and highly reliable analysis results can be obtained, even if the internal standard sample remains in the internal standard conduit 50, it is flushed with the sample water thereafter, so that there is no problem in the analysis.

That is, since the internal standard substance added for the purpose of correcting the error in the introduction amount of the sample liquid is often not stable in water, it is used after being dissolved in a small amount of an organic solvent. For this reason, since the internal standard solution has a relatively high concentration compared to the sample solution, it is indispensable to introduce a small amount of it accurately. The resulting error, and the subsequent concentration of the sample and internal standard solutions, alleviates the error that the error is magnified and has a significant impact on the analytical results.

When the internal standard sample is introduced into the purge and trap device 51, its detection signal is sent from an on-line sampler (not shown) to the controller 2.
1, a drive signal is input from the controller 21 to the purge and trap device 51, and the device 51 is driven. In this case, by driving the purge and trap device 51 when introducing the internal standard sample, the internal pressure of the device 51 is reduced, and the internal standard sample and the sample can be smoothly introduced.

The purge and trap device 51 is configured to be capable of concentrating volatile organic compounds in the drinking water 2 serving as a sample water. The purge and trap device 51 supplies a purge gas to the drinking water 2 sent into the sample tube 58, and removes the volatile gas therein. The organic compound is temporarily held in an adsorbent filled in a trap tube (not shown), and then the trap tube is heated and desorbed, and a concentrated gas is introduced from the transfer tube 59 to the gas chromatograph 60.

Thereafter, the controller 21 executes the sample loop cleaning. At this time, the controller 21 controls the electromagnetic valves 31, 32, 37, 44, the cleaning liquid supply pump 30 and the first
A control signal is sent to the switching valve 8 and the solenoid valves 31, 32, 44
Is opened, the electromagnetic valve 37 is closed, and the cleaning liquid supply pump 30 is driven.

Further, the first switching valve 8 is switched so that the port P1
, P2, ports P3, P4, ports P5, P6 communicate with each other, port P1 communicates with the washing liquid supply pipe 27, ports P2, P5 communicate with the sample distribution pipe 33, and port P6 communicates with the drain pipe 43. I do.

In this manner, the cleaning liquid 29 in the cleaning liquid container 28 is pumped out by the cleaning liquid supply pump 30, which is guided by the cleaning liquid supply pipe 27 and moves to the first switching valve 8, and from the ports P1 and P2. Guided by the sample distribution pipe 33, the sample loop 34 is moved, and at that time, the remaining sample water attached to the inner walls thereof is washed away, and these are guided to the drain pipe 43 through the ports P5 and P6, and the analysis casing 4 is provided.
To the outside of the

Next, the controller 21 cleans the filters 17 and 18 on the downstream side while driving the cleaning liquid supply pump 30. At this time, the controller 21
5 and 44 and the first switching valve 8 to send a control signal to the solenoid valve 2
5, the solenoid valve 44 is closed, and the first switching valve 8 is switched so that the ports P1, P6, ports P2, P3,.
The ports P4 and P5 communicate with each other, the port P1 communicates with the cleaning liquid supply pipe 27, and the port P6 communicates with the drain pipe 43.

In this manner, the cleaning liquid 29 in the cleaning liquid container 28 is pumped out by the cleaning liquid supply pump 30, which is guided from the cleaning liquid supply pipe 27 to the sample supply pipe 6 and moves to the filter switching valve 10. The filter 17 that is currently being used is guided to the filter diversion pipe 13
Is moved to wash out contaminants such as foreign substances adhering to the filter 17, guide them to the discharge pipe 22 and discharge them to the water intake source 1. This situation is as shown in FIG.

After cleaning the filter 17, the controller 2
1 sends a control signal to the filter switching valve 10, switches the valve 10, disconnects the filter distribution pipe 13 from the sample supply pipe 6, and connects the filter distribution pipe 14 to the sample supply pipe 6. In this way, the cleaning liquid 29 is guided to the filter distribution pipe 14, moves the filter 18 which is not currently used, and rinses out contaminants such as foreign substances attached to the filter 18, and guides them to the discharge pipe 22. Discharge to intake source 1. In this case, the washing may not be performed every time, but may be performed as appropriate.

Therefore, when the filter 17 is contaminated and deteriorated in function, the function is recovered and regenerated, so that the filter can be effectively used and the analysis cost can be reduced. The filter 17 regenerated in this manner is repeatedly used and regenerated in the future. If the number of repetitions finally measured by the controller 21 or the value detected by the filter deterioration sensor 20 at the time of cleaning or regeneration exceeds a specified value, an alarm is issued. A filter (not shown) is operated to prompt the replacement of the filter.

Further, the controller 21 continues to drive the cleaning liquid supply pump 30, and the filters 15 and 16 on the upstream side.
Perform cleaning. At this time, the controller 21 sends a control signal to the solenoid valves 24 to 26, 64, 65, and the solenoid valve 2
The valves 4, 26, 64 are opened, and the solenoid valves 25, 65 are closed.

In this way, the cleaning liquid supply pump 30
The washing liquid 29 pumped out to the sample supply pipe 6 moves to the filter switching valve 10 and is guided from the port to the filter branch pipe 13 or 14 to move the filter 17 or 18 after washing. It is led to the filter switching valve 9 via the sample supply pipe 6.

After that, the washing liquid 29 is guided from the port of the filter switching valve 9 to the filter branch pipe 11, moves through the filter 15 currently in use, and removes contaminants such as foreign substances adhering to the filter 15. These are guided from the sample supply pipe 6 to the discharge pipe 22 via the bypass pipe 23,
Discharge to intake source 1. This situation is as shown in FIG.

After cleaning the filter 15, the controller 2
1 sends a control signal to the filter switching valve 9, switches the valve 9, disconnects the filter distribution pipe 11 from the sample supply pipe 6, and connects the filter distribution pipe 12 to the sample supply pipe 6. In this case, the washing may not be performed every time, but may be performed as appropriate.

In this manner, the washing liquid 29 is guided to the filter branch pipe 12, and the filter 16 which is not used at present is used.
To wash away contaminants such as foreign matter adhering to the filter 16, guide them from the sample supply pipe 6 to the discharge pipe 22 via the bypass pipe 23, and discharge them to the water intake source 1.
In this case, the washing may not be performed every time, but may be performed as appropriate.

Therefore, when the filter 15 is contaminated and its function is deteriorated, the function is recovered and regenerated, so that the filter can be effectively used and the analysis cost can be reduced. The filter 15 regenerated in this manner is repeatedly used and used thereafter, and finally, when the number of times of reproduction measured by the controller 21 or the value detected by the filter deterioration sensor 19 at the time of cleaning or reproduction exceeds a specified value, Activate an alarm (not shown) to prompt replacement of the filter.

As described above, according to the present invention, the filters 15 to 18 are washed while the supply of the sample water 2 is stopped after the sample water 2 is introduced into the concentrator 51. It can be cleaned rationally without any hindrance.

Further, the cleaning of the filters 15 to 18
The filter is divided into coarse and dense meshes. First, the filters 17 and 18 with the fine mesh are washed, and then the filters 15 and 16 with the coarse mesh are washed.
There is no concern about so-called reverse clogging, in which foreign matter remaining on the filters 7 and 18 adheres to the filters 15 and 16.

The filters 15 and 1 having a coarse mesh
When the filter 6 is washed, the filter 17 or 18 having a dense mesh is washed, so that the filter 17 or 18 can be washed precisely.

A bypass pipe communicating with the cleaning liquid supply pipe 27 is provided, and one end of the pipe is connected to the filter switching valve 9 and the electromagnetic valve 2.
If the filter is connected to the sample supply pipe 6 between the filter 6 and the filter 6, the filter can be washed separately for each of the coarse and dense filters 15, 16, 17, and 18, and the fear of the reverse clogging can be eliminated.

In this way, while the series of filters are being washed, the drinking water 2
The volatile organic compounds therein are concentrated, and after this concentration, a control signal is sent from the controller 21 to the gas chromatograph 60, and the gas chromatograph 60 is started.

The gas chromatograph 60 introduces the concentrated gas into the column, separates the concentrated gas, analyzes it with the detector 61, and records the volatile organic compound concentration in the sample water 2 online. Therefore, a chemical such as activated carbon is introduced into the water intake source 1 based on the above analysis result, and the amount of the introduced medicine is not too small or too small.

After a series of filter washing, a signal is input from the purge and trap device 56 to the controller 21. When the device 6 shifts to the desorption mode and discharges water,
The controller 21 executes the sample loop cleaning again while driving the cleaning liquid supply pump 30.

At this time, the controller 21 controls the solenoid valves 24 to
A control signal is sent to 26, 44, 64, 65 and the first switching valve 8, and the solenoid valves 24-26, 64 are closed, and the solenoid valves 44, 6
5, the first switching valve 8 is switched, the ports P1, P2, the ports P3, P4, the ports P5, P6 communicate with each other, the port P1 communicates with the cleaning liquid supply pipe 27, and the ports P2, P5. Is connected to the sample distribution pipe 33, and the port P6 is connected to the drain pipe 43.

In this way, the cleaning liquid supply pump 30
The washing liquid 29 pumped out of the pipe is guided to the washing liquid supply pipe 27 and moves to the first switching valve 8, and is guided to the sample branch pipe 33 through the ports P 1 and P 2, moves through the sample loop 34, and moves to the inner wall. Is washed again and precisely washed, and then moved to the drain tube 43 from the ports P5 and P6, and
Is discharged to the outside. This situation is the same as in FIG.

After that, the controller 21 executes the purge and trap device cleaning. At that time, the controller 2
Numeral 1 indicates that the cleaning liquid supply pump 30 continues to be driven, and that the electromagnetic valve 2
5 and 37 and the first switching valve 8 to send a control signal to the solenoid valve 2
5 and 37 are opened and the first switching valve 8 is switched,
Port P1, P6, Port P2, P3, Port P4, P
5 with each other, the port P1 with the washing liquid supply pipe 27, and the ports P2 and P5 with the sample distribution pipe 3
3, and the port P6 is connected to the drain tube 43.

In this manner, the cleaning liquid supply pump 30
The washing liquid 29 pumped to the sample supply pipe 27 is guided by the washing liquid supply pipe 27, reaches the sample supply pipe 6, and is divided from the pipe 6 in two directions. One of them moves to the first switching valve 8 and is discharged from the ports P1 and P6 to the outside of the analysis casing 4 through the drain pipe 43, and the other moves to the filter switching valve 10.
The filter 17 is guided from the port to the diversion pipe 13, moves through the filter 17, and is discharged from the sample supply pipe 6 to the water intake source 1 via the bypass pipe 22.

On the other hand, the transfer gas filled in the gas container 36 is guided to the transfer gas conduit 35 and moves to the first switching valve 8, and moves through the sample loop 34 from the ports P 3 and P 2 via the sample branch pipe 33. Then, the cleaning liquid remaining in the flow dividing pipe 33 and the sample loop 34 is blown off.

Thereafter, the transfer gas moves together with the blown-off cleaning liquid through the flow dividing pipe 33, from the pipe 33 through the connecting pipe 42 via the ports P5 and P4, and from the pipe 42 through the second switching valve 41. From the ports P3 and P4, to the internal standard conduit 50, to the purge and trap device 51, and discharged from the device 51 to the outside.

As described above, the present invention utilizes the drainage in the desorption mode of the purge and trap device 51 to transfer the cleaning liquid remaining in the sample distribution pipe 33 through the transfer gas to the connection pipe 42 and the second switching valve. 41 and the internal standard conduit 50 to clean the flow path and the discharge path of the trap device 51 rationally.

As described above, the present invention provides each of the filters 15 to 18.
By washing the pipes and each line and pre-processing the analysis rationally, smooth and stable measurement and analysis are promoted, and their online system is realized. Therefore, accurate measurement and analysis results can be obtained, and appropriate measures can be taken in response to this. Can be prevented.

[0096]

As described above, according to the first aspect of the present invention, the sample water of the intake source is circulated for a predetermined time in the upstream flow path of the sample water before introducing the sample water concentration device. The cleaning liquid and foreign matters remaining in the sample can be removed and replaced with the current sample water to ensure the accuracy and reliability of the analysis. Also, since the internal standard sample was introduced into the concentrator before introducing the sample water,
Compared to the case where the sample is introduced after the introduction of the sample water, the quantitative internal standard sample can be introduced more stably, and the reliability of the analysis accuracy can be improved. Further, after the introduction of the internal standard sample, the sample water was introduced into the concentrator, and the internal standard sample remaining in the internal standard sample flow path was removed via the sample water, thereby causing an analysis error due to the remaining internal standard sample. Can be prevented. Further, since the washing liquid is introduced into the concentrating device when the concentrating device is drained to clean the device, the concentrating device can be rationally cleaned. Claim 2
In the invention, the sequence control of the circulation of the sample water, the introduction of the sample water and the internal standard sample into the concentrator, and the cleaning of the flow path of the sample water and the concentrator was performed. Can be promoted, and the introduction of a drug for improving water quality can be rationally performed.

According to the third aspect of the present invention, a plurality of filters of the same quality are selectively switchably disposed in the flow path of the sample water, and the filters can be switched when the filters are deteriorated. The water quality analysis of the sample water can be performed smoothly and stably. Therefore, G
It is suitable for a pretreatment device of a qualitative / quantitative measurement device for organic substances such as C / MS, and can promote the online analysis of water quality of sample water. According to the fourth aspect of the present invention, a plurality of coarse-mesh filters are arranged on the upstream side of the sample water flow path, and a plurality of dense-mesh filters are arranged on the downstream side thereof. And each filter can be used efficiently. According to the invention of claim 5, a multi-port type filter switching valve is arranged in the flow path of the sample water, and a plurality of filters are detachably connected to the switching valve. Exchange can be facilitated.

According to a sixth aspect of the present invention, a filter deterioration sensor capable of detecting deterioration of the filter is provided in the flow path of the sample water,
Since the filter can be switched when the deterioration of the sensor is detected, the filter can be switched rationally and accurately. According to the seventh aspect of the present invention, since a filter having excellent durability, adsorptivity, and cleaning property with respect to the sample water is used for each mesh, an optimal filter for the sample water is selected, and Can be used. According to the invention of claim 8, since the filter and the flow path of the sample water around the filter can be observed from the outside, the deterioration of the filter and the degree of contamination of the sample water can be easily confirmed.

According to the ninth aspect of the present invention, since the filter can be washed for each of the coarse and dense filters, it is possible to prevent the filter from being clogged when the filters are simultaneously washed. The conduit was connected to the downstream side of the flow path of the sample water, and the washing liquid was moved from the downstream side to the upstream side of the flow path of the sample water to enable drainage, and the filter disposed in the flow path was made washable. In addition, it is possible to prevent foreign matter discharged from the filter having a dense mesh from adhering to the filter having a coarse mesh. According to the eleventh aspect of the present invention, since the discharge pipe and the solenoid valve which can be drained to the outside are arranged on the upstream side of each filter switching valve arranged in the flow path of the sample water, washing of each filter with a coarse mesh is realized. can do.

According to the twelfth aspect of the present invention, since the filter switching valve is switched to enable each filter to be cleaned, it is possible to clean a contaminated filter which is being used or whose use has been stopped once. According to the invention of claim 13, since the washing liquid can be introduced into the filter having a dense mesh every time the filter is washed, the washing of the filter can be performed precisely, and the filtering function can be recovered with high accuracy, and the sample water can be recovered. Filtration can be performed with high accuracy. According to the fourteenth aspect of the present invention, the used filter can be regenerated and the non-renewable filter is replaced, so that the rational use of the filter and the cost reduction can be achieved. In the invention according to claim 15, a first switching valve is connected downstream of the flow path of the sample water, and the switching valve is connected to a transfer gas conduit and a sample distribution pipe inserted through a sample loop. A second switching valve communicable with the valve was provided, and the internal standard branch flow pipe and the internal standard sample supply pipe with the internal standard loop interposed in the switching valve were connected to the internal standard conduit communicating with the concentrator. Water and the internal standard sample can be reliably introduced into the concentrator.

According to a sixteenth aspect of the present invention, a sample loop and an internal standard loop are filled with a predetermined amount of sample water and an internal standard sample,
Since the sample water can be introduced into the concentrator through the internal standard conduit when the first and second switching valves communicate, the sample water can be surely introduced into the concentrator. According to the invention of claim 17, after introducing the sample water and the internal standard sample into the concentration device, the washing liquid is introduced into the sample distribution pipe and the sample loop,
By making them washable, the accuracy of the next analysis can be improved. According to the eighteenth aspect of the present invention, after the sample water and the internal standard sample are introduced into the concentrator, the drainage of the concentrator communicates the first and second switching valves, and the first switching valve communicates the transfer gas conduit. Then, the washing liquid in the sample flow pipe and the sample loop is introduced into the concentrator and drained, and since these flow paths and the concentrator can be washed, the washing can be performed rationally without hindering the analysis, The accuracy of the next analysis can be improved. According to the nineteenth aspect of the invention, since the operation of each filter switching valve, each solenoid valve, the first and second switching valves, the sample supply pump, and the cleaning liquid supply pump is sequence-controlled, the water quality analysis of the sample water is realized online. can do.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing an embodiment of the present invention, together with a control system thereof.

FIG. 2 is an explanatory diagram showing an enlarged main part of the present invention.

FIG. 3 is an explanatory view showing an operation state of the present invention, and shows a state at the time of replacement of sample water.

FIG. 4 is an explanatory view showing an operation state of the present invention, showing a state at the time of prior introduction of sample water.

FIG. 5 is an explanatory view showing an operation state of the present invention, showing a state at the time of prior introduction of an internal standard sample.

FIG. 6 is an explanatory view showing an operation state of the present invention, showing a state when an internal standard sample concentrator is introduced.

FIG. 7 is an explanatory diagram showing an operation state of the present invention, and shows a state at the time of introducing a sample water concentrating device.

FIG. 8 is an explanatory diagram showing an operation state of the present invention, and shows a state at the time of cleaning the sample loop.

FIG. 9 is an explanatory diagram showing an operation state of the present invention, and shows a state at the time of cleaning one filter (closer mesh side).

FIG. 10 is an explanatory view showing an operation state of the present invention, showing a state at the time of cleaning both filters.

FIG. 11 is an explanatory diagram showing an operation state of the present invention, and shows a state at the time of washing of the concentration device.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Intake source 2 Sample water 8 First switching valve 9,10 Filter switching valve 15,16 Filter (coarse mesh) 17,18 Filter (dense mesh) 19,20 Filter deterioration sensor 22 Discharge pipe 23 Discharge pipe (bypass pipe) 26 , 64 Solenoid valve 29 Cleaning liquid 33 Sample distribution pipe 34 Sample loop 41 Second switching valve 45 Internal standard supply pipe 47 Internal standard sample 48 Internal standard distribution pipe 49 Internal standard loop 50 Internal standard conduit 51 Concentrator (purge and trap device)

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI G01N 30/20 G01N 30/20 Z 33/18 33/18 B (72) Inventor Yasuhiko Kamiyama Sayamagahara, Iruma-shi, Saitama 237-2 Inside the Musashi Factory of GL Science Corporation

Claims (19)

[Claims] In a method for analyzing a trace amount of volatile organic compounds in water in which a sample water and an internal standard sample are introduced into a concentrating device and a flow path of the sample water is washed, before introducing the sample water into the concentrating device. The sample water of the water intake source is circulated for a predetermined time upstream of the flow path of the sample water, and after introducing the internal standard sample into the concentrator, the sample water is introduced into the concentrator, and the internal standard sample is passed through the sample water. A method for analyzing trace volatile organic compounds in water, wherein an internal standard sample remaining in a flow path can be removed, and a washing solution is introduced into the concentrator when draining the concentrator, and the concentrator can be washed. 2. A trace volatile organic compound in water obtained by controlling the circulation of the sample water, the introduction of the sample water and the internal standard sample into the concentrator, and the washing of the flow path of the sample water and the concentrator. Analysis method. 3. An apparatus for analyzing trace amounts of volatile organic compounds in water, wherein the sample water filtered by a filter and an internal standard sample are introduced into a concentrator, and the sample water flow path is washed. An analyzer for trace volatile organic compounds in water, wherein a plurality of filters of the same quality are selectively switchably disposed on a road, and the filters can be switched when the filters are deteriorated. 4. A trace volatile organic compound in water according to claim 3, wherein a plurality of coarse-mesh filters are arranged upstream of the flow path of the sample water, and a plurality of dense-mesh filters are arranged downstream thereof. Analyzer. 5. A trace volatile organic substance in water according to claim 3, wherein a multi-port filter switching valve is disposed in the flow path of the sample water, and a plurality of filters are detachably connected to the switching valve. Compound analyzer. 6. The analysis of trace volatile organic compounds in water according to claim 3, wherein a filter deterioration sensor capable of detecting the deterioration of the filter is provided in the flow path of the sample water, and the filter can be switched when the deterioration of the sensor is detected. apparatus. 7. The analysis device for trace volatile organic compounds in water according to claim 3, wherein the filter is excellent in durability, adsorptivity, and detergency for sample water for each mesh. 8. The apparatus for analyzing a trace amount of volatile organic compounds in water according to claim 3, wherein the filter and the flow path of the sample water around the filter are observable from the outside. 9. The apparatus for analyzing a trace amount of volatile organic compounds in water according to claim 3, wherein the filter can be washed for each of the coarse and dense filters of the mesh. 10. A washing liquid conduit is connected to a downstream side of a flow path of a sample water to move a washing liquid from a downstream side of the flow path of the sample water to an upstream side to enable drainage, and a filter arranged in the flow path. The apparatus for analyzing trace volatile organic compounds in water according to claim 3 or 4, wherein the apparatus can be washed. 11. The analysis of trace volatile organic compounds in water according to claim 9, wherein a discharge pipe and a solenoid valve capable of draining to the outside are disposed upstream of each filter switching valve disposed in the flow path of the sample water. apparatus. 12. The apparatus for analyzing a trace amount of volatile organic compounds in water according to claim 6, wherein the filter switching valve is switched so that each filter can be washed. 13. The apparatus for analyzing a trace amount of volatile organic compounds in water according to claim 9, wherein the washing liquid can be introduced into the filter having a dense mesh every time the filter is washed. 14. The filter after use can be regenerated,
The analyzer for trace volatile organic compounds in water according to claim 11, wherein a non-renewable filter is replaceable. 15. A first switching valve is connected downstream of the flow path of the sample water, a transfer gas conduit and a sample distribution pipe inserted through a sample loop are connected to the switching valve, and the first switching valve is connected to the first switching valve. 4. The communication device according to claim 3, further comprising a second switching valve that can communicate with the switching valve, wherein the switching valve is connected to an internal standard distribution pipe, an internal standard sample supply pipe, and an internal standard conduit that communicates with the concentrator. Analyzer for trace volatile organic compounds in water. 16. A sample loop and an internal standard loop are filled with a predetermined amount of sample water and an internal standard sample, and the sample water is filled in a first loop.
4. The apparatus for analyzing trace volatile organic compounds in water according to claim 3, wherein the apparatus can be introduced into the concentrating apparatus via an internal standard conduit when the second switching valve is in communication with the second switching valve. 17. The method according to claim 3, wherein after introducing the sample water and the internal standard sample into the concentrating device, a washing solution is introduced into the sample distribution pipe and the sample loop to enable them to be washed. Analysis equipment. 18. After the sample water and the internal standard sample are introduced into the concentrator, when the concentrator drains, the first and second switching valves are connected, and the transfer gas conduit is connected to the first switching valve. ,
18. The apparatus for analyzing trace volatile organic compounds in water according to claim 17, wherein the washing liquid in the sample distribution pipe and the sample loop is introduced into the concentrator and drained, and the flow path and the concentrator can be washed. 19. The analysis of trace volatile organic compounds in water according to claim 17, wherein the operation of each filter switching valve, each solenoid valve, the first and second switching valves, the sample supply pump and the cleaning liquid supply pump is sequence-controlled. apparatus.