JP6501518B2 - Transfer method of internal standard solution and transfer device therefor - Google Patents

Description

  The present invention is suitable, for example, for quantitative analysis of volatile organic compounds contained in water, realizes automatic injection of the internal standard solution to the sample easily and inexpensively, uniformly distributes the internal standard solution to the sample, and is uniform The present invention relates to a method and apparatus for transferring an internal standard solution, which can obtain purge efficiency, suppress variation in recovery rates of components with low recovery rates and internal standard substances, and obtain analysis reliability.

When analyzing volatile organic compounds (VOCs) in samples such as water and sewage, environmental water, etc., a gas chromatograph mass spectrometer (GC / MS) is generally used after the purge / trap method, head space method, etc. are used as pretreatment. To detect.
When performing measurement using the GC / MS, there is a problem that the sensitivity of the detector changes with each measurement. In addition, 1,4-dioxane, which is a highly hydrophilic component among VOCs, is easily compatible with water, and the recovery rate from water is lower than other VOCs, and the recovery rate of pretreatment varies depending on the state of the sample. There is a problem that it is easy.
In order to solve these problems, an internal standard solution, which is usually a solution containing an internal standard substance, is injected into a fixed amount of sample for each measurement to correct the sensitivity of the detector and the recovery rate of the pretreatment device, and measure And I try to get the reliability of the analysis. The internal standard substance is a component which is not contained in the actual sample and which has similar physical properties, is detected at a position close to the target component for quantification, and is required to be a highly pure component.

  For example, in an analyzer applying the purge trap method, an internal standard gas automatic injection mechanism is inserted in the pipe between the purge gas supply port and the first six-way valve, and the automatic injection mechanism includes the internal standard gas cylinder, mass flow controller, And the three-way valve, the mass flow controller automatically controls the flow rate of the internal standard gas supplied from the gas cylinder, and controls the open / close time of the three-way valve, to control the open / close time of the three-way valve. The internal standard gas is concentrated and recovered together with the VOC in the sample and introduced into a gas chromatograph (GC) (for example, see Patent Document 1).

However, the analyzer introduces the purge gas into the purge vessel together with the internal standard gas, bubbles the liquid sample in the vessel with the purge gas, and sends out the purge component in the sample into the concentration pipe together with the internal standard gas. Therefore, when using internal standard solution in gasification, handling becomes more complicated than in liquid, and since internal standard solution is used in gasification, it can not be used for correction of recovery rate. there were.
In addition, the internal standard gas automatic injection mechanism requires a mass flow controller and a three-way valve, and has a problem that the structure is complicated and the cost and size increase are promoted.

On the other hand, when using the internal standard solution instead of the internal standard gas, place the sample behind the internal standard solution, and when pushing out the internal standard solution by the sample, the liquid phase is in front of the feeding direction of the internal standard solution. Since it does not exist, a phenomenon may occur in which the internal standard solution adheres to the wall surface or the like which is not the sample storage area of the purge pipe.
For example, in the case of an internal standard solution containing 1,4-dioxane-d8 as an internal standard substance, the adhesion of the internal standard solution to a wall surface or the like other than the sample storage area of the purge pipe results in It might not have the same purge efficiency as dioxane. In that case, a substance having high hydrophilicity and low recovery rate as an internal standard substance, for example, the above-mentioned 1,4-dioxane-d8 was concerned about having a large influence on measured values.
In addition, the internal standard solution and the sample may be sent to the purge / trap apparatus without being sufficiently stirred, and the distribution of the internal standard solution in the sample may become nonuniform to change the purge efficiency.

Unexamined-Japanese-Patent No. 2000-346759

  The present invention solves such problems and is suitable for quantitative analysis of volatile organic compounds contained in water, for example. Automatic injection of internal standard solution to sample is realized easily and inexpensively, internal standard solution to sample is uniform. Distribution method of internal standard solution and distribution uniformity, obtaining uniform purge efficiency, suppressing variation in recovery rate of low recovery components and internal standard substance, and obtaining analysis reliability The purpose is to provide a transfer device.

According to the invention of claim 1, the internal standard solution is injected into the aqueous solution, the internal standard solution contains the internal standard substance having hydrophilicity and volatility, and the aqueous solution is disposed before and after the internal standard solution. In the method of transferring the internal standard solution introduced into the extraction unit, the internal standard substance of the internal standard solution contains 1,4-dioxane-d8, which promotes the mixing or stirring of the internal standard solution with the aqueous solution, The internal standard solution is uniformly distributed in the solution so that it can be introduced into the gas phase extraction unit.
Therefore, uniform purge efficiency of each component can be obtained in the gas phase extraction unit, and for example, recovery of components with low recovery rate and internal standard substance such as 1,4-dioxane contained in volatile organic compounds in the sample It is possible to suppress the variation of the rate and obtain the reliability of the analysis accuracy.
According to the invention of claim 2 , the internal standard solution of a predetermined amount is introduced into the inside of the internal mark introduction valve in communication with the water supply tube of the aqueous solution and the internal standard conduit which transmits the internal standard solution. injected volume metering of standard solution, to adjust the optimum injection amount of the internal standard solution for an aqueous solution, and the optimal use and its effective internal standard solution in Figure so that.

The invention of claim 3 communicates the injection space inside the internal mark introduction valve with the internal mark conduit, introduces the internal standard solution into the injection space, and then pivots the internal mark introduction valve to send the injection space communicating with the tube, the internal standard solution which contains the injection space is introduced into the liquid feed pipe, and in so that to easily introduce internal standard solution from internal standard conduit by rotating the internal standard inlet valve into the liquid feed pipe ing.
According to the invention of claim 4, the amount of the internal standard solution introduced into the liquid feed pipe is metered through the resistance portion provided in the internal standard conduit downstream or upstream of the internal standard introduction valve, and it is optimum for the aqueous solution. to achieve introduction of the internal standard solution, and the proper use and effective use of the internal standard solution in Figure so that.
According to the invention of claim 5, after analyzing each component of the aqueous solution, the injection space of the internal mark introduction valve is communicated with the liquid feed pipe, an inert gas is introduced from the downstream side of the liquid feed pipe, and the injection space And the liquid feed tube is cleaned, and cleaning of the injection space and the liquid feed tube after component analysis is realized in a simple and quick manner.

In the invention of claim 6 , an internal standard solution containing an internal standard substance having hydrophilicity and volatility is provided in an aqueous solution so as to be pourable, the aqueous solution is disposed before and after the internal standard solution, and a gas phase extraction unit is provided. An internal standard of the internal standard solution containing 1,4-dioxane-d8 , and an internal standard for transporting the aqueous solution solution and the internal standard solution, in the transfer apparatus of the internal standard solution which can be transported. An internal mark introduction valve is rotatably provided at an intersection where communication with the conduit is possible, and an injection space which can selectively communicate with the liquid feed pipe and the internal mark conduit is provided inside the internal mark introduction valve, and the injection Connect the space to the internal mark conduit, and introduce a predetermined amount of internal standard solution into the injection space. After introducing the internal standard solution, rotate the internal mark introduction valve to communicate the injection space to the liquid delivery pipe. allows introduction of the internal standard solution was introduced into the infusion space in an aqueous solution of the liquid supply tube, the inner Encourage mixing or agitation of the standard solution and the aqueous solution is uniformly distributed internal standard solution in an aqueous solution so that can be introduced into the gas phase extractor.
Therefore, uniform purge efficiency of each component can be obtained in the gas phase extraction unit, and for example, recovery of components with low recovery rate and internal standard substance such as 1,4-dioxane contained in volatile organic compounds in the sample It is possible to suppress the variation of the rate and obtain the reliability of the analysis accuracy.

In the invention of claim 7 , the injection space is a slot formed in a direction perpendicular to the axial direction of the internal mark introduction valve, and the introduction of the internal standard solution from the internal mark conduit into the liquid delivery pipe is realized by a simple configuration. It has to be so that.
According to the invention of claim 8 , the resistance part is provided in the internal mark conduit on the downstream side or upstream side of the internal mark introduction valve to make it possible to measure the introduction amount of the internal standard solution to the liquid feed pipe, to achieve introduction of the standard solution, and the proper use and effective use of the internal standard solution in Figure so that.

In the invention of claim 9 , after analyzing each component of the aqueous solution, the injection space is communicated with the liquid feed pipe, an inert gas is introduced from the downstream side of the liquid feed pipe, and the injection space and the liquid feed pipe are It is made washable, and cleaning of the injection space and the liquid feed tube after component analysis is realized in a simple and quick manner.

The invention of claim 1, internal standard internal standard solution, since that contains a 1,4-dioxane-d8, encourage mixing or agitation of the internal standard solution and an aqueous solution, internal standard solution in an aqueous solution Can be uniformly distributed and introduced into the vapor phase extraction unit.
Therefore, uniform purge efficiency of each component can be obtained in the gas phase extraction unit, and for example, recovery of components with low recovery rate and internal standard substance such as 1,4-dioxane contained in volatile organic compounds in the sample to suppress the variation rate can Rukoto obtain the reliability of analytical precision.
According to the invention of claim 2 , the internal standard solution of a predetermined amount is introduced into the inside of the internal mark introduction valve in communication with the water supply tube of the aqueous solution and the internal standard conduit which transmits the internal standard solution. since injected amount adjustment amount of standard solution, to adjust the optimum injection amount of the internal standard solution for aqueous solutions, optimal use of the internal standard solution and the effectiveness can FIG Rukoto.

The invention of claim 3 communicates the injection space inside the internal mark introduction valve with the internal mark conduit, introduces the internal standard solution into the injection space, and then pivots the internal mark introduction valve to send the injection space communicating with the tube, Rukoto be easily introduced from the introduction of an internal standard solution accommodated in the injection space feeding tube, the internal standard solution from internal standard conduit by rotating the internal standard inlet valve into the liquid feed pipe Can.
The invention of claim 4 is most suitable for a water-based solution because the amount of introduction of the internal standard solution to the liquid feed pipe is metered through the resistance portion provided in the internal mark conduit downstream or upstream of the internal mark introduction valve. achieves the introduction of an internal standard solution, it is FIG Rukoto proper use and effective use of the internal standard solution.
According to the invention of claim 5, after analyzing each component of the aqueous solution, the injection space of the internal mark introduction valve is communicated with the liquid feed pipe, an inert gas is introduced from the downstream side of the liquid feed pipe, and the injection space Since the liquid feed pipe is cleaned, it is possible to realize the washing of the injection space and the liquid feed pipe after the component analysis in a simple and quick manner .

According to the invention of claim 6 , the internal standard substance of the internal standard solution contains 1,4-dioxane-d8, and the water supply tube of the aqueous solution can communicate with the internal standard pipe for conveying the internal standard solution. An internal mark introduction valve is rotatably provided at the intersection, and an injection space capable of selectively communicating with the liquid feed pipe and the internal mark conduit is provided inside the internal mark introduction valve, and the injection space is used as the internal mark conduit. In communication, a predetermined amount of internal standard solution can be introduced into the injection space, and after the introduction of the internal standard solution, the internal mark introduction valve is rotated to connect the injection space to the liquid feed pipe, and the injection space Since the internal standard solution introduced in the column can be introduced into the aqueous solution of the liquid feed tube, mixing or stirring of the internal standard solution and the aqueous solution is promoted, and the internal standard solution is uniformly distributed in the aqueous solution to perform gas phase extraction. It can be introduced to the department.
Therefore, uniform purge efficiency of each component can be obtained in the gas phase extraction unit, and for example, recovery of components with low recovery rate and internal standard substance such as 1,4-dioxane contained in volatile organic compounds in the sample to suppress the variation rate can Rukoto obtain the reliability of analytical precision.

According to the invention of claim 7 , since the injection space is a slot formed in a direction perpendicular to the axial direction of the internal mark introduction valve, the introduction of the internal standard solution from the internal mark conduit into the liquid delivery pipe can be achieved by a simple configuration. You realize you can Rukoto.
The invention according to claim 8 is most suitable for a water-based solution because a resistance portion is provided in the inner-mark conduit downstream or upstream of the inner-mark introduction valve so that the introduction amount of the internal standard solution to the liquid feed pipe can be measured. achieves the introduction of an internal standard solution, it is FIG Rukoto proper use and effective use of the internal standard solution.

In the invention of claim 9 , after analyzing each component of the aqueous solution, the injection space is communicated with the liquid feed pipe, an inert gas is introduced from the downstream side of the liquid feed pipe, and the injection space and the liquid feed pipe are because was washable, can it to achieve a cleaning of the injection space and liquid supply tube after component analysis quickly easily.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an explanatory view showing an embodiment in which the present invention is applied to quantitative analysis of VOC in an aqueous solution, and shows a situation where the aqueous solution is introduced into first and second reservoirs upstream of the purge trap. The situation where the internal standard solution is introduced into the internal mark valve after introducing the aqueous solution into the first and second reservoirs is shown. The figure shows the situation where the internal standard solution and the aqueous solution are introduced into the purge / trap section after the internal standard solution is injected into the aqueous solution.

It is an expanded sectional view showing the situation at the time of whole quantity injection of internal standard solution by the internal mark valve to which the present invention is applied, (a) before internal mark injection, (b) at internal mark injection, (c) internal mark After injection, each situation is shown. It is sectional drawing which expands and shows the condition at the time of sending an aqueous solution and an internal standard solution to a purge * trap part. The situation where the adsorption component trapped by the trap device is introduced into the analyzer and analyzed is shown. It shows the situation where the reservoir is cleaned after analysis of the aqueous solution.

It is explanatory drawing which shows the principal part of the application form of the said embodiment of this invention, (a) injects an internal standard solution into a water-system solution, shows the condition which introduce | transduces into a purge trap part after introduce | transducing into a mixer and stirring. ing. (B) shows another form of the mixer, in which a large number of glass beads are accommodated in a straight tubular conduit. It is explanatory drawing which shows the internal mark introducing | transducing part of the principal part of 2nd Embodiment of this invention. The expanded sectional view which shows the condition at the time of injection of the desired quantity of the internal standard solution by the internal mark valve applied to the said 2nd embodiment in order, (a) before internal mark injection, (b) at internal mark injection, (c ) Shows each situation after injection of the internal mark.

  Hereinafter, the illustrated embodiment in which the purge and trap method is adopted as the component analysis of VOC of the aqueous solution which is the subject according to the present invention will be described. In FIGS. 1 to 7, 1 is a component analyzer. Water source solution containing water to the storage section, and an internal mark introducing section 2 for automatically injecting a liquid internal standard solution (hereinafter simply referred to as Component is extracted from the liquid phase into the gas phase, and the gas phase is concentrated and introduced into an analyzer equipped with a detector such as GC or GC / MS. An auto sampler unit equipped with a purge / trap unit 3 which is an extraction unit, a cleaning solution or a pressurized gas for transfer to the internal mark introducing unit 2 and with various mechanisms for collecting an aqueous solution and measuring, transporting and cleaning. It consists of 4 There.

The aqueous solution contains both the one containing the analysis target component and the one not containing it, and the internal label introducing unit 2 comprises a solenoid valve provided with an injection mechanism inserted in the middle stream part of the water supply tube 5 of the aqueous solution. The internal mark introduction valve 8 and the internal mark conduit 9 communicating with the internal mark introduction valve 8 have predetermined volumes of upstream and downstream positions of the liquid feed pipe 5 sandwiching the internal mark introduction valve 8. In the embodiment in which the first and second reservoirs 6 and 7 are provided, the liquid delivery pipe 5 is piped by bending a bendable transparent or semitransparent fluorine resin thin tube, and (2) Reservoir 6 and 7 are formed into a predetermined volume by winding a thin tube of the same quality as that described above in a loop shape of a predetermined diameter, and fitting the tube end portions on both sides thereof to liquid tube 5 The predetermined position of the liquid pipe 5 is wound and integrally configured.

The internal mark introduction valve 8 is rotatably disposed at the intersection of the liquid feed pipe 5 and the internal mark conduit 9, and its operation is controlled by a control device (not shown) utilizing a personal computer, and a groove described later The communication between the hole and the liquid feed pipe 5 or the internal mark conduit 9 can be switched.
The internal mark introduction valve 8 has a groove 8a formed in the cylindrical shaft and penetrating in the direction perpendicular to the axial direction, and the groove 8a functions as an injection space for the internal mark, depending on its rotational position. It is possible to communicate with the liquid delivery pipe 5 or the internal mark conduit 9.
One end of the internal mark conduit 9 is inserted into the internal mark storage container 11, the pressurized gas conduit 12 communicating with the inert gas source is inserted into the container 11, and the inert gas introduced from the conduit 12 The internal mark 13 in the container 11 is pushed to the internal mark conduit 9 so that it can be supplied to the internal mark introduction valve 8. Helium gas or nitrogen gas is used as the inert gas.

  The internal mark conduit 9 is disposed on the circumferential surface of the internal mark introduction valve 8 in a direction perpendicular to the liquid feed pipe 5, and the upstream portion thereof communicates with the pressurizing portion 45 such as the inert gas source, and the downstream end The part is inserted into the discharge container 10, and the surplus part of the internal mark 13 supplied to the discharge container 10 can be discharged.

Before the injection of the internal mark, the internal mark introduction valve 8 is closed as shown by the solid line in FIG. 1, and the internal mark introduction valve 8 and the internal mark conduit 9 are shut off. Instead, the first and second reservoirs 6, 7 are closed. Are connected so that the aqueous solution 16 can be introduced into them.
That is, the groove 8a is disposed so as to be in communication with the liquid feed pipe 5 via the control device, so that the aqueous solution 16 introduced into the liquid feed pipe 5 can be introduced into the inside. This situation is as shown in FIG. 4 (a).

Next, when the internal mark 13 is injected, the internal mark introduction valve 8 is switched as shown by the broken line in FIG. 1 to open, and the internal mark introduction valve 8 is communicated with the internal mark conduit 9 to introduce the internal mark 13 , And the surplus can be discharged to the discharge container 10.
That is, the internal mark introduction valve 8 is turned clockwise by 90 ° from the situation before the internal mark injection via the control device, and the groove hole 8a is arranged to be able to communicate with the internal mark conduit 9, It is possible to introduce 13. This situation is as shown in FIG. 4 (b).

After the injection of the internal mark 13, the internal mark introduction valve 8 is switched as shown by the solid line in FIG. 1 to close and restore the internal mark introduction valve 8 to shut off the internal mark introduction valve 8 and the internal mark conduit 9; Instead, it is in communication with the first and second reservoirs 6 and 7.
That is, the internal mark introduction valve 8 is rotated by 90 ° counterclockwise from the time of internal mark injection via the control device, and the groove hole 8a is disposed so as to be able to communicate with the liquid feed pipe 5, The entire amount of the internal standard 13 introduced into the inside 8a can be poured into the aqueous solution 16 in the liquid feed pipe 5. This situation is as shown in FIG. 4 (c) and FIG. 5, and a predetermined amount of internal mark 13 is arranged in a sandwich form in the aqueous solution 16.

In the embodiment, the internal standard 13 is a component which is not contained in the target component in the aqueous solution, the physical properties are similar, it is necessary to elute at a position close to the quantitative target component and to be a high purity component in the embodiment fluorobenzene and 1,4-dioxane-d8, using four components of toluene-d8 p-Bed Romo fluorobenzene.
Among these, fluorobenzene, toluene-d8, p-Bed Romo fluorobenzene, aims to correct the sensitivity of the detector, 1,4-dioxane-d8 are to achieve correction of 1,4-dioxane.

The needle 14 of the inner and outer double pipe structure is disposed on the upstream side of the liquid feed pipe 5, and the pointed end of the needle 14 is always accommodated in the discharge container described later, and the outer passage (not shown). A gas conduit 15 capable of introducing an inert gas is connected.
Immediately below the needle 14, a container 17 for containing the aqueous solution 16 described above is disposed, and the tip of the needle 14 can be inserted into and removed from the lid.

Then, the tip of the needle 14 is inserted into the aqueous solution 16 in the container 17, the inert gas injected into the gas conduit 15 is introduced into the outer passage of the needle 14, and the aqueous solution 16 is not shown. Can be pushed out to the liquid feed pipe 5 communicating with the
In the figure, reference numeral 18 denotes a discharge container for containing the cleaning liquid discharged from the needle 14, and 19 denotes a discharge container for containing the surplus portion of the aqueous solution 16, which is disposed at the downstream end of the liquid feed pipe 5.

A first switching valve 20 is disposed upstream of the first storage portion 6 of the liquid delivery pipe 5, and a second switching valve 21 is disposed downstream of the second storage portion 7. The purge / trap introduction pipe 22 is connected, and the second switching valve 21 is connected to the pressurized gas conduit 23 communicating with the inert gas source.
The first and second switching valves 20 and 21 are constituted by solenoid valves, and their operation is controlled by the control device.

  That is, when the aqueous solution 16 is introduced into the first and second reservoirs 6 and 7, the first and second switching valves 20 and 21 are switched as shown by the solid line in FIG. When the aqueous solution 16 is introduced into the purge / trap introduction pipe 22, the first switching valve 20 and the second switching valve 21 are switched as shown by the broken line in FIG. 1, and the first and second reservoirs 6, 7 are cleaned and When drying, the first switching valve 20 is switchable as shown by a solid line in FIG. 1 and the second switching valve 21 is switched as shown by a broken line in FIG.

The purge / trap unit 3 traps the purge pipe 24 which purges a predetermined component of the aqueous solution 16 introduced from the purge / trap introduction pipe 22, and the trap pipe 25 which traps the purged gaseous VOC. And an analyzer 26 for analyzing the components of the VOC.
Among them, the purge pipe 24 is formed substantially in a U-shape, and the closed closed ends on both sides thereof are disposed on the upper side, and the end of the purge / trap introduction pipe 22 is inserted into one closed end thereof. An aqueous solution 16 into which a mark 13 is injected is introduced, and one end of a purge conduit 27 is inserted into the upper portion of the purge pipe 24.

  Further, a pressurized gas conduit 28 communicating with an inert gas source is connected to the other closed end of the purge pipe 24 and this inert gas is introduced into the purge pipe 24 as a purge gas, and the aqueous solution 16 and internal mark 13 are introduced. The VOC contained therein is separated from the water, and the separation gas staying above can be pushed out to the purge conduit 27. In the figure, 29 is a solution in which the aqueous solution 16 and the internal standard 13 are mixed.

The trap tube 25 accommodates therein the adsorbent 30 capable of trapping the separation gas and is inserted into the trap conduit 31. A heater (not shown) is attached to the outer peripheral surface of the trap tube 25 to heat and adsorb the heater. The separated gas trapped in the agent 30 is desorbed and can be introduced into the analyzer 26 through the analysis conduit 32.
The analyzer 26 is a GC or GC / MS equipped with a detector, and the analysis conduit 32 is heated to a predetermined temperature via the transfer line 33 to ensure analysis accuracy without forming a cold spot.

  A third switching valve 34 is interposed downstream of the purge conduit 27, and the switching valve 34 is constituted by a solenoid valve to enable communication with and shut off from the purge conduit 27 during purge and trap of the aqueous solution, The operation is controlled by the controller. Further, a pressurized gas conduit 35 communicating with an inert gas source is connected to the third switching valve 34 so that the inert gas can be introduced into the third switching valve 34.

That is, at the time of purge and trap of the aqueous solution, the third switching valve 34 is switched as shown by a solid line in FIG. 1 and communicated with the purge conduit 27 to make the separated gas movable to the trap pipe 25.
Further, the third switching valve 34 is switched as shown by the broken line in FIG. 1 at the time of dehumidification and drying of the trap pipe 25 to shut off the communication between the pressurized gas conduit 35 and the purge conduit 27 to the upstream side. A conduit 35 is in communication with the purge conduit 27 downstream so that inert gas can be introduced into the trap tube 25.

A fourth switching valve 36 is connected to one end of the trap conduit 31, and the switching valve 36 is constituted by an electromagnetic valve, and is switched as shown by the solid line in FIG. The separated gas moving through the conduit 27 is adsorbed to the adsorbent 30, and the separated gas after adsorption can be discharged to the outside.
A pressurized gas conduit 37 communicating with an inert gas source is connected to the fourth switching valve 36, and the switching valve 36 is switched as shown by a broken line at the time of analysis to separate the separated gas desorbed from the adsorbent 30 by the inert gas. It is transportable to the analyzer 26.

The downstream end of the purge conduit 27, one end of the trap conduit 31, and one end of the analysis conduit 32 are connected to each port of the fifth switching valve 38, and the switching valve 38 is composed of a solenoid valve, and its operation is Is controlled by the controller.
The fifth switching valve 38 is switched as shown by the solid line in FIG. 1 at the time of purge and trap to connect the purge conduit 27 to the trap conduit 31 so that the separated gas moving through the purge conduit 27 can be transferred to the trap tube 25. There is.
Further, the pressurized gas conduit 39 communicating with the inert gas source is connected to the fifth switching valve 38, and the conduit 39 is switched as shown by the solid line in FIG. Gas can be introduced into the analyzer 26.

On the other hand, a sixth switching valve 40 and a seventh switching valve 41 are disposed on the upstream side of the pressurized gas conduit 23 separately from each other, these are constituted by solenoid valves, and the operation thereof is controlled by the control device .
Among them, the sixth and seventh switching valves 40 and 41 are switched and communicated as shown by the solid line in FIG. 1 when introducing the aqueous solution 16 into the first and second reservoirs 6 and 7, and the seventh switching valve It is possible to supply an inert gas to the gas passage 15 connected to 41.
When the aqueous solution 16 is introduced into the purge / trap portion, the sixth and seventh switching valves 40 and 41 are switched as shown by the solid line in FIG. It is made transferable to the trap introduction pipe 22.

  Also, when cleaning the first and second reservoirs 6, 7, the sixth and seventh switching valves 40, 41 are switched as shown by the solid line in FIG. 7, and the pressurized gas conduit 42 communicated with the inert gas source Inert gas is introduced into the cleaning vessel 43, the cleaning solution 44 contained in the vessel 43 is sent out to the pressurized gas conduit 23, and this is moved to the first and second reservoirs 6, 7 and the liquid delivery pipe 5 for cleaning. And discharge the washing liquid 44 after washing to the discharge container 18.

  In this embodiment, the first and second reservoirs 6, 7 are wound in a loop, but the present invention is not limited to this. But it is good.

The method and apparatus for transferring the internal standard solution configured as described above arranges the purge / trap portion 3 so as to be able to communicate with and shut off the liquid feed pipe 5 to which the aqueous solution 16 can be introduced. The 1 and 2nd storage parts 6 and 7 are spaced apart and arranged.
In the first and second reservoirs 6 and 7 of the embodiment, a thin tube is wound to form a loop having a predetermined volume, and both ends thereof are fitted and attached to the midstream portion of the liquid delivery tube 5, or The thin tubes are wound to form an integral structure, and the internal mark introduction valve 8 is disposed so as to be able to open and close between them.

The internal mark introduction valve 8 is controlled by the control device to open and close, and the internal mark introduction valve 8 is arranged to be able to communicate with and shut off the internal mark conduit 9.
That is, the internal mark introduction valve 8 is rotatably inserted in the liquid feed pipe 5 and the internal mark conduit 9, and the operation is controlled by a control device (not shown) using a personal computer, and the groove hole 8a and The communication with the liquid feed pipe 5 or the internal mark conduit 9 can be switched.
The inner mark introduction valve 8 is formed as a filling space for the inner mark 13 inside the cylindrical shaft, and the slot hole 8 a is formed to penetrate in the direction perpendicular to the axial direction. It functions as a weighing means and does not require a complicated and expensive weighing mechanism as in the prior art.

One end of the internal mark conduit 9 is inserted into the internal mark storage container 11, and the pressurized gas conduit 12 communicating with the inert gas source is inserted into the container 11, and the inert gas introduced from the conduit 12 The internal mark 13 in the container 11 is pushed to the internal mark conduit 9 and can be supplied to the internal mark introduction valve 8.
The internal mark conduit 9 is disposed on the circumferential surface of the internal mark introduction valve 8 in a direction perpendicular to the liquid feed pipe 5, and the upstream portion thereof is communicated with the pressurizing portion 45 such as the inert gas source, and the downstream end The part is inserted into the discharge container 10, and the surplus portion of the internal mark 13 supplied to the discharge container 10 can be discharged.

The aqueous solution 16 uses water or the like containing a VOC component, and the internal standard 13 is a component not included in the target component in the aqueous solution, has similar physical properties, and is eluted at a position close to the analyte and, must be a high purity component, fluorobenzene in embodiments, 1,4-dioxane-d8, toluene-d8, using a p- Bed Romo fluorobenzene and the like.
Among these, fluorobenzene, toluene-d8, p-Bed Romo fluorobenzene, aims to correct the sensitivity of the detector, 1,4-dioxane-d8 is to achieve a correction of 1,4-dioxane.

The fluorobenzene, p- Bed Romo fluorobenzene, toluene -d8 is a high component recovery, while being adsorbed to the trap pipe 25 to evaporate the substantially whole amount by performing the purge, 1,4-dioxane -d8 hydrophilic Since the component is a component having a high degree of recovery and a low recovery rate, the rate of adsorption to the trap tube 25 is low even after purging.

As described above, the transfer device of the internal standard solution of the embodiment can be easily coped with by modifying a part of the existing device and does not require any special measuring means or control mechanism of the internal mark 13, so that the internal standard as in the prior art A mass flow controller for automatically controlling the flow rate of gas and a three-way valve for controlling the open / close time are not required, and the configuration is simple, and it can be manufactured easily and inexpensively.
Moreover, in this embodiment, the aqueous solution 16 is disposed before and after the internal standard 13 as described later, and the internal standard 13 is sandwiched between the internal standard 13 and sent to the purge / trap portion 3. It adapts easily and quickly, and distributes them uniformly and precisely.
Therefore, for example, as compared with the method of disposing the aqueous solution 16 behind the internal standard 13 and extruding the internal standard by the aqueous solution 16, the internal standard 13 is distributed quickly and uniformly in the aqueous solution 16.

Next, when injecting the internal mark 13 into the aqueous solution using the transfer device, the needle 14 is pulled up from the discharge container 18 and its tip is pierced into the lid of the container 17 and inserted into the aqueous solution 16 inside. .
Then, switch the first, second, sixth and seventh switching valves 20, 21, 40 and 41 and the internal mark introduction valve 8 as shown by the solid line in FIG. 1, and shut off the internal mark introduction valve 8 and the internal mark conduit 9 Inert gas is fed into the pressurized gas conduit 23, and the gas is introduced into the outer passage (not shown) of the needle 14 through the gas conduit 15 and the aqueous solution 16 in the container 17 is in the inner passage of the needle 14. It pushes out to the liquid feeding pipe 5 from (illustration omitted).

The extruded aqueous solution 16 is guided to the liquid feed pipe 5 and moves to the first storage section 6, and after filling the storage section 6, flows through the inside of the internal mark introduction valve 8 to the second storage section 7. After being introduced and filling the storage portion 7, the surplus portion is discharged to the discharge container 19.
This situation is as shown in FIG. 1, and the aqueous solution 16 is filled in the first and second reservoirs 6 and 7 and the fluid delivery pipe 5 including the space between them.
In this case, the aqueous solution 16 containing the component to be analyzed is introduced into the first and second reservoirs 6 and 7, but the aqueous solution 16 containing the component to be analyzed is introduced into either one of the reservoirs, It is also possible to introduce an aqueous solution 16 which does not contain the component to be analyzed into the storage section of and measure it.
At that time, it is possible to first introduce the aqueous solution 16 not containing the component to be analyzed into the second storage section 7 first, and then introduce the aqueous solution 16 containing the component to be analyzed into the first storage section 6 It may be the opposite.

Thereafter, the needle 14 is pulled out of the container 17 and moved into the discharge container 18, and the first, second, and seventh switching valves 20, 21, 41 and the inner mark introduction valve 8 are switched as shown by solid lines in FIG. The introduction valve 8 and the internal mark conduit 9 are in communication.
Then, an inert gas is fed into the pressurized gas conduit 12, the gas is introduced into the internal mark storage container 11, the internal mark 13 is extruded into the internal mark conduit 9, and this is introduced into the internal mark introduction valve 8 to form the slot 8a. And discharge the surplus after introduction into the discharge container 10. This situation is as shown in FIG.

That is, when the internal mark 13 is injected into the internal mark introduction valve 8, the internal mark introduction valve 8 is rotated clockwise by 90 ° from the situation before the internal mark injection via the control device, and the groove hole 8a is The internal mark 13 is introduced into the interior by communicating with the internal mark conduit 9. This situation is as shown in FIG. 4 (b).

Then, the internal mark introduction valve 8 is rotated by 90 ° counterclockwise from the time of injection of the internal mark via the control device, and the groove hole 8a is disposed so as to be able to communicate with the liquid feed pipe 5, The entire amount of the internal standard 13 introduced into the inside is poured into the aqueous solution 16 in the liquid feeding pipe 5. This situation is as shown in FIG. 4 (c) and FIG. 5, and a predetermined amount of internal mark 13 is arranged in a sandwich form in the aqueous solution 16.
Therefore, the internal mark 13 of the liquid phase is closely arranged in three layers between the aqueous solution 16 of the liquid phase, and the internal mark 13 becomes hydrophilic to the aqueous solution 16 on both sides and becomes familiar and diffused.
In the embodiment, in order to obtain the desired effect of the present invention, when the internal standard 13 is 1 μL, 0.5 mL or more of the aqueous solution 16 is disposed before and after that, but it is not limited to this .

Thus, when the internal standard 13 is injected into the aqueous solution 16 and then introduced into the purge / trap section 3, the first to seventh switching valves 20, 21, 34, 36, 38, 40, 41 are shown by solid lines in FIG. As a result, the pressure conduit 23 and the midstream portion of the liquid feed pipe 5 are communicated with the purge / trap introduction pipe 22, and the purge conduit 27 is communicated with the trap pipe 31.
Then, an inert gas is fed from the upstream side of the pressurizing conduit 23, and the gas is moved to the liquid feeding pipe 5, and the aqueous solution 16 and internal mark 13 filled in the introducing pipe 5 are purged and introduced into the pipe 22 side. Send to

Among them, the aqueous solution 16 in the second reservoir 7 is pressed by the gas and circulated along the loop of the reservoir 7 to move toward the internal mark introduction valve 8 side. A centrifugal force acts on the aqueous solution 16 in the loop.
At that time, the centrifugal force acting on 16 parts of the aqueous solution is larger than that acting on the small aqueous solution 16 parts near the inner wall of the pipe in the central part of the conduit where the flow rate is high. It is pushed to the outside of the tube, and the aqueous solution 16 near the inner wall of the tube wraps around the inside of the loop tube along the inner wall.

On the other hand, the pressure distribution in the cross section of the second reservoir 7 is not uniform, and is high at the outer inner wall of the loop tube and low at the inner inner wall, so that the pressure distribution in the cross section perpendicular to the tube axis of the second reservoir 7 is There is a secondary flow which is a pair of circulating flows.
That is, one of the pair of secondary flows circulates from the inside to the outside of the loop tube, and the other circulates from the outside to the inside of the loop tube.
Therefore, in the second reservoir 7, the flow velocity and pressure of the aqueous solution 16 fluctuate irregularly to present a flow resembling a turbulent flow, and a large and small vortex movement is formed, and mixing or stirring of the aqueous solution 16 is performed. Is actively conducted.

Thereafter, the aqueous solution 16 flows out of the second reservoir 7 and is guided to the internal mark introduction valve 8, but the flow similar to the aforementioned turbulent flow of the aqueous solution 16 is propagated to the intervening aqueous solution 16. It spreads to one end of the injected internal mark 13 and promotes their mixing or stirring.
Thereafter, the internal mark 13 is pressed by the gas and moves together with the aqueous solution 16 toward the first reservoir 6 to move in the loop of the reservoir 6.
At that time, in the loop in the first reservoir 6, the flow velocity and the pressure of the aqueous solution 16 fluctuate irregularly to exhibit a flow resembling a turbulent flow as described above, and a large and small vortex movement is formed, The mixing or stirring of the aqueous solution 16 and the internal standard 13 is actively performed, and the internal standard 13 is uniformly distributed in the aqueous solution 16.

Thus, the aqueous solution 16 into which the internal mark 13 has been injected is introduced into the purge pipe 24 from the first switching valve 20 through the purge / trap inlet pipe 22, and after introduction, it is not supplied from the pressurizing conduit 28 at the other end of the purge pipe 24. The active gas is fed to forcibly purge the mixed solution of the aqueous solution 16 and the internal standard 13, and the purge component is sent to the purge conduit 27.
In this case, since the internal standard 13 is uniformly distributed in the aqueous solution 16 and introduced into the purge pipe 24 as described above, the purge efficiency according to the distribution situation of the internal standard 13, that is, the purge gas flows in the aqueous solution to achieve gas-liquid equilibrium. It is possible to eliminate the problem that the efficiency of recovering the volatile component is different and the recovery rate is different.

  Therefore, the uneven distribution of the internal standard 13 in the aqueous solution 16 can prevent the purge efficiency from changing and changing. In particular, the same purge efficiency can be obtained for 1,4-dioxane and 1,4-dioxane-d8 which are components with low recovery rates in the aqueous solution 16 and the internal standard 13, so that the variation in recovery rates is reduced.

The purge component is introduced into the fifth switching valve 38 through the third switching valve 34, moved from the switching valve 38 to the trap conduit 31, and trapped in the adsorbent 30 of the trap pipe 25 interposed in the conduit 31. , And discharge the surplus from the fourth switching valve 36 to the outside. This situation is as shown in FIG.
Thereafter, when analyzing the trap component, the fourth and fifth switching valves 36, 38 are switched as shown by the solid line in FIG. 6, and the trap conduit 31 is communicated with the analysis conduit 32 to heat the trap tube 25. Thus, the trap component trapped in the adsorbent 30 is desorbed.

Then, an inert gas is fed from the pressurizing conduit 37, led to the trap pipe 25, and the desorbed component is sent out to the analysis conduit 32 through the fifth switching valve 38, and further introduced to the analyzer 26 to detect the desorbed component. Analyze.
At that time, since the internal standard 13 is uniformly distributed in the aqueous solution 16 as described above, and the same purge efficiency can be obtained for each component in the aqueous solution 16 and internal standard 13, it is a component having a low recovery rate. The same purge efficiency can be obtained from 1,4-dioxane and the internal standard 13, 1,4-dioxane-d8, and the variation in recovery rate is reduced, so that the reliability of analytical accuracy can be obtained.

After analyzing each component of the aqueous solution 16 in this manner, for example, when cleaning the first and second reservoirs 6 and 7, the first, second, sixth, and seventh switching valves 20, 21, 40, and 41 The valve 8 is switched as shown by the solid line in FIG. 7 to feed inert gas into the pressurization conduit 42 and introduce it into the cleaning vessel 43.
Then, the cleaning liquid 44 is pushed out of the cleaning container 43, sent out to the pressurizing conduit 23 through the sixth switching valve 40, and moved to the second reservoir 7 through the seventh and second switching valves 41 and 21, Then, it moves from the internal mark introduction valve 8 to the first reservoir 6 to wash them.
Then, the cleaning liquid 44 is moved to the end portion side of the liquid feeding pipe 5 and introduced into the nozzle 14, and after cleaning the nozzle 14, the cleaning liquid 44 is discharged to the discharge container 18. This situation is as shown in FIG.

  As described above, according to the present invention, when the aqueous solution 16 containing the VOC component is purged and trapped, the internal mark 13 of the liquid is injected into the aqueous solution 16, and these are arranged in a sandwich and introduced into the purge and trap portion 3. Because the internal standard 13 conforms to the aqueous solution 16 and is uniformly distributed, the target component in the aqueous solution 16 and the purge efficiency of the internal standard 13 are made identical to obtain the reliability of the analysis accuracy. .

8 to 10 show the application form and other embodiments of the present invention, and the same reference numerals are used for components corresponding to the above-described embodiments. Of these, FIG. 8 shows a modified embodiment of the embodiment of the present invention, this application mode is obtained after injection Uchishirube 13 in an aqueous solution 16, a uniform distribution of internal standard 13 thereof was further stirred Two forms are shown.
Among them, in (a), a mixer 46 is disposed in the purge / trap introduction pipe 22 between the first switching valve 20 and the purge pipe 24, and the mixer 46 chops a thin tube made of fluorocarbon resin into a loop of a predetermined diameter. It is turned to form a predetermined volume, and the tube ends on both sides thereof are fitted and attached to the introduction tube 22.

  Then, after injecting the internal standard 13 into the aqueous solution 16, when introducing them into the purge / trap portion 3, the aqueous solution 16 into which the internal standard 13 is injected is introduced into the mixer 46, and the mixer 46 similarly to the above. The flow velocity and pressure of the aqueous solution 16 fluctuate irregularly to exhibit a turbulent flow, and a large and small vortex movement is formed, and the mixing or stirring of the aqueous solution 16 and the internal mark 13 is actively performed. The distribution of the internal standard 13 and the aqueous solution 16 is further homogenized and introduced into the purge pipe 24 so that the same purge efficiency can be obtained for each component.

  As another form of the mixer 46, FIG. 8 (b) interposes a straight tubular mixing tube 47 of a predetermined length, accommodates a large number of glass beads 48 in the tube 47, and a water system in the beads 48. The solution 16 and the internal standard 13 are brought into contact with each other, and the contact area thereof is increased to further improve the stirring accuracy and to make the distribution of the internal standard 13 and the aqueous solution 16 more uniform and introduce them into the purge pipe 24. However, the same purge efficiency can be obtained.

9 and 10 show a second embodiment of the present invention, in which the resistance portion 49 is disposed downstream or upstream of the internal symbol introduction valve 8 of the internal symbol conduit 9, in the embodiment downstream of the internal symbol introduction valve 8. The internal standard quantity in the injection mechanism can be metered by the resistance portion 49.
That is, the resistance portion 49 increases or decreases the inner diameter of the conduit of the portion than that of the internal mark conduit 9, or lengthens or reduces the length of the conduit of the portion to adjust the resistance of the conduit, thereby improving the internal mark introduction valve. The injection amount of the internal standard 13 with respect to 8 can be metered.
Resistance portion 49 of the embodiment, a reduced diameter than the internal standard line 9 the internal diameter of the conduit, and / or the length of the conduit of the part pipeline resistance increases in the long, internal standard induction valve 8 The injection amount or introduction amount of the internal standard 13 with respect to

The injection condition of the internal mark 13 of the internal mark introduction valve 8 by the resistance part 49 is as shown in FIG. 10, and before the injection of the internal mark 13, the groove hole 8 a can be communicated with the liquid feeding pipe 5 via the control device It is arranged, and the aqueous solution 16 introduced into the liquid feed pipe 5 can be introduced into the inside. This situation is as shown in FIG. 10 (a).
Next, at the time of injection of the internal mark 13, the internal mark introduction valve 8 is rotated by 90 ° clockwise before injecting the internal mark, and the groove hole 8a is arranged to be able to communicate with the internal mark conduit 9, Make the internal mark 13 installable.
At that time, the introduction speed of the internal standard 13 is decelerated and the injection amount is decreased by the pipe resistance by the resistance portion 49. In the embodiment, the injection amount of the internal mark 13 is metered to about 1/2 of the volume equivalent of the slot 8a. This situation is as shown in FIG. 10 (b).

After the injection of the internal mark 13, the internal mark introduction valve 8 is switched to close and the internal mark introduction valve 8 and the internal mark conduit 9 are shut off, and instead, the first and second reservoirs 6, 7 are communicated. , Restore the internal symbol introduction valve 8.
That is, the internal mark introduction valve 8 is rotated by 90 ° counterclockwise from the time of injection of the internal mark through the control device, and the groove hole 8a is communicated with the liquid feed pipe 5 to enter the groove hole 8a. The tip of the introduced internal standard 13 is brought into close contact with the aqueous solution 16 in the liquid feed pipe 5 and injected. This situation is as shown in FIG. 10 (c).
As described above, in this embodiment, the injection amount of the internal standard 13 to the internal standard introduction valve 8 is adjusted by the resistance section 49, and the measured internal standard 13 is introduced into the aqueous solution 16, and the analysis conditions of the aqueous solution 16 The injection of the internal standard 13 of the optimal amount according to is implemented, and the appropriate use and effective use of the internal standard 13 are aimed at.

  The transfer method and transfer device of the internal standard solution of the present invention realize automatic injection of the internal standard solution to the sample easily and inexpensively, and uniformly distribute the internal standard solution to the sample to obtain uniform purge efficiency. Since the reliability of the analysis can be obtained by suppressing the variation in the recovery rate of the component having a low recovery rate and the internal standard substance, it is suitable, for example, for quantitative analysis of volatile organic compounds contained in water.

3 Gas phase extraction unit (purge and trap unit)
5 liquid feed pipe 6 first reservoir 7 second reservoir 8 switching valve (internal mark valve)
13 Internal standard solution

46, 47 mixer 48 glass bead 49 resistor

Claims (9)

An internal standard solution is injected into the aqueous solution, the internal standard solution contains an internal standard substance having hydrophilicity and volatility, and the internal standard solution is placed before and after the internal standard solution and introduced into the gas phase extraction unit. in the transfer method of the liquid, the internal standard of the internal standard solution, method of transferring an internal standard solution, wherein Rukoto include 1,4-dioxane-d8. A predetermined amount of internal standard solution is introduced into the inside of the internal mark introduction valve in communication with the water supply tube of the aqueous solution and the internal standard conduit that supplies the internal standard solution, and the injection amount of the internal standard solution to the aqueous solution is adjusted. The method of transferring an internal standard solution according to claim 1, wherein The injection space inside the internal mark introduction valve communicates with the internal mark conduit, and after introducing the internal standard solution into the injection space, the internal mark introduction valve is pivoted around the axis to communicate the injection space with the liquid delivery pipe, the injection 3. The method of transferring an internal standard solution according to claim 2 , wherein the internal standard solution contained in the space is introduced into the liquid feed pipe . 4. The method of transferring an internal standard solution according to claim 3, wherein the amount of introduction of the internal standard solution into the liquid feed pipe is metered through a resistance portion provided in the internal symbol conduit downstream or upstream of the internal symbol introduction valve . After analysis of each component of the aqueous solution, the injection space of the internal standard introduction valve is communicated with the liquid feed pipe, inert gas is introduced from the downstream side of the liquid feed pipe, and the injection space and liquid feed pipe are cleaned. The transfer method of the internal standard solution of Claim 3 . In the aqueous solution, an internal standard solution containing an internal standard substance having hydrophilicity and volatility is injectably provided.
In the transfer device of the internal standard solution in which the aqueous solution is disposed before and after the internal standard solution and the liquid can be sent to the gas phase extraction unit, the internal standard substance of the internal standard solution contains 1,4-dioxane-d8 In addition, an internal mark introduction valve is rotatably provided at the intersection where the water supply pipe of the aqueous solution and the internal mark conduit for supplying the internal standard liquid can communicate with each other, and the liquid is supplied to the inside of the internal mark introduction valve An injection space which can selectively communicate with the pipe and the internal standard conduit is provided, the injection space is in communication with the internal standard conduit, and a predetermined amount of internal standard solution can be introduced into the injection space. An internal standard solution characterized in that the internal standard introduction valve is turned to communicate the injection space with the liquid feed pipe so that the internal standard liquid introduced into the injection space can be introduced into the aqueous solution of the liquid feed pipe. Transport device. The transfer device for the internal standard solution according to claim 6, wherein the injection space is a slot formed in a direction perpendicular to the axial direction of the internal mark introduction valve . The transfer device for the internal standard solution according to claim 6 , wherein a resistance portion is provided on the downstream side or the upstream side of the internal symbol introduction valve of the internal symbol introduction valve so that the introduction amount of the internal standard solution to the liquid feed pipe can be metered . After analyzing each component of the aqueous solution, the infusion space communicating with the liquid feed tube, claim an inert gas is introduced from the downstream side of said transmission liquid pipe and allows cleaning the injection space and liquid supply tube 6 Transfer device for internal standard solution as described.

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