JP2002181673A - Pretreatment method in concentration measurement of pcb and sampling device and refining device used in this pretreatment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method with easy extracting and refining operation of PCB and simplifying pretreatment for analyzing PCB, and a sampling device and a purifier capable of providing continuous sampling and purification. SOLUTION: This method is characterized by that a sampling process of particularly sampling mainly PCB from a substance to be measured such as exhaust gas and an extracting process of selectively extracting PCB from the sample are carried out in a sampling location of the substance to be measured.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pretreatment method for measuring the concentration of PCB, a sampling device used in the pretreatment, and a purification device.

[0002]

2. Description of the Related Art Conventionally, no effective method has been established for measuring the concentration of PCB contained in exhaust gas or the like. Therefore, there is a need for a method for simplifying the measurement of the concentration of PCB contained in exhaust gas or the like.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has a simple operation of extracting and purifying a PCB.
It is an object of the present invention to provide a method for simplifying a pre-processing for performing an analysis of an object. It is another object of the present invention to provide a collection device and a purification device capable of continuously performing collection and purification operations.

[0004]

Means for Solving the Problems The present invention has been made to solve the above-mentioned problems, and the invention according to claim 1 is a method for mainly extracting PCB from an object to be measured such as exhaust gas. And a step of selectively extracting a PCB from the sampled material at a place where the object to be measured is sampled.

[0005] The invention according to claim 2 is characterized in that a purification step of removing impurities from the extract extracted in the extraction step is performed at the sampling place.

According to a third aspect of the present invention, there is provided a collecting apparatus used in the collecting step according to the first aspect, wherein a plurality of switchable adsorbent cartridges are provided.

According to a fourth aspect of the present invention, there is provided a purification apparatus used in the purification step according to the second aspect, wherein a plurality of switchable multilayer silica gel columns are provided.

[0008] Further, in claim 5, the refining apparatus is characterized by further comprising a plurality of switchable alumina columns.

[0009]

Next, an embodiment of the present invention will be described. INDUSTRIAL APPLICATION This invention can be implemented suitably for the density | concentration measurement of PCB in exhaust gas. The present invention provides a PCB which performs a sampling step of mainly extracting a PCB from an object to be measured such as exhaust gas and an extracting step of selectively extracting a PCB from the sample at a place where the object to be measured is collected.
This is a pretreatment method in the measurement of the concentration.

[0010] This pretreatment method is carried out by first mainly collecting a specific PCB at a collecting place. This specific collection can be suitably performed mainly by using a collecting device that specifically collects the PCB. This sampling device does not capture all gas components from low-boiling compounds to high-boiling compounds, but mainly captures PCB, and particularly does not capture impurities such as low-boiling hydrocarbons. As the sampling device used here, a sampling device provided with a plurality of switchable molded body cartridges appropriately molded with an inorganic adsorbent is preferable. That is, by providing a plurality of switchable molded body cartridges, the sampling step can be performed continuously. And, as the inorganic adsorbent, an alumina material is preferable. More preferably, it is a γ-alumina material or an activated alumina material.

Next, an extraction step for selectively extracting PCB from the collected matter will be described. This extraction process
This is performed to selectively extract PCBs contained in the harvest. Further, as an extraction device in this extraction step, an extraction solvent is supplied to the molded body cartridge by a pump or the like to selectively extract PCB. Further, since a plurality of switchable molded body cartridges are provided, the extraction step can be performed continuously.

Next, a description will be given of the concentration measurement for measuring the concentration of PCB after the extraction step. In this concentration measurement, the extract liquid selectively extracted in the above-mentioned extraction step is used for PCB concentration.
The concentration of is measured. The measurement of the concentration of PCB is suitable not only for a place where analysis equipment for measuring the concentration of PCB is completed, but also for a place where an actual sample is taken. GC / MS / MS or GC / ECD is used as an apparatus for measuring the concentration of PCB.
By using GC / MS / MS or the like, the concentration of PCB can be measured directly from the extract without requiring a purification step.

Next, a purification step for removing impurities from the extract will be described. This purification step is performed to remove impurities contained in the extract. Further, as a device for removing the impurities, a modified silica gel such as silica gel, sulfate silica gel, silver nitrate silica gel or the like, that is, a multilayer silica gel column is used. By providing a plurality of these components in a switchable manner, the purification process can be performed continuously. In other words, it is not only possible to simplify the impurity removal operation such as omitting the sulfuric acid treatment step and the purification step using two or more types of column chromatography,
Since a plurality of switchable units are provided, the purification step can be performed continuously.

When the concentration is measured using a purified solution purified using a multilayer silica gel column, GC / H
It is common to use RMS. As a method of use, the purified solution is concentrated, and the concentration of PCB in the concentrated solution is measured using GC / HRMS. This GC / HRMS
Has good measurement sensitivity and can measure the concentration of PCB even when some impurities are present.

[0015] The purification apparatus further includes a plurality of switchable alumina columns, so that a more purified liquid can be continuously produced. That is, by further providing an alumina column after the multilayer silica gel column, a more purified liquid can be obtained. Thus, when measuring the concentration of PCB, it is common to use GC / LRMS. As for the method of use, the extract is concentrated and subjected to GC / LRMS.
Is used to determine the concentration of PCB in the concentrate. This GC
/ LRMS indicates that if an impurity is present,
It is sensed as the concentration of CB, making accurate measurement difficult. Therefore, in this case, the concentration of PCB can be measured only in the case of a purified solution further purified by an alumina column.

As described above, the present invention comprises a switchable plurality of adsorbent cartridges for the collecting device and a plurality of multi-layer silica gel columns, alumina columns, etc. for the purifying device. A series of operations up to the processing can be continuously performed at the sampling place.

[0017]

Next, a specific embodiment of the present invention will be described in detail with reference to the drawings. FIG. 1 is an explanatory diagram schematically showing a pretreatment system as a first embodiment of the present invention.

In FIG. 1, the PCB pre-processing system of the present invention includes a sampling device 1 and an extraction device 2 as basic components.

First, the sampling device 1 includes a transfer pipe 5 for transferring the exhaust gas collected from the exhaust gas discharge passage 3 to the adsorbent mounting body 4. The adsorbent mounting body 4 includes a plurality of adsorbent cartridges 6 for mainly picking up PCBs inside. The transfer pipe 5 is provided with a temperature control device 7 for heating or cooling, and the temperature of the exhaust gas supplied to the adsorbent cartridge 6 is 100 ° C. to 120 ° C.
It has been adjusted to be ° C. As a means for detecting this temperature, a temperature sensor 8 is provided at a subsequent stage of the adsorbent mounting body 4, and the temperature adjusting device 7 is controlled based on a measured value of the temperature sensor 8. In addition, a first pump 9 is provided for stably transferring the exhaust gas collected from the exhaust gas discharge passage 3 to the adsorbent cartridge 6 from the transfer pipe 5. A drain trap 10 for collecting exhaust gas passing through the adsorbent cartridge 6 is provided. Further, a purging cylinder 11 storing nitrogen gas for cleaning the inside of the transfer pipe 5 after collection and a purging line 12 connecting the transfer pipe 5.
Is provided with a first check valve 13.

Here, the operation of the adsorbent mounting body 4 will be described with reference to FIG.
It will be described in detail based on. The case of the revolver method as the adsorbent mounting body 4 will be described. The adsorbent mounting body 4 includes a plurality of storage sections 14, 14,... For loading the adsorbent cartridge 6. Then, every other one of the adsorbent cartridges 6 is loaded into each of the storage sections 14. Therefore, the accommodation section 14 in which the adsorbent cartridge 6 is not loaded is in a state of penetrating the adsorbent mounting body 4 (through the left-right direction in FIG. 1). That is, in the embodiment of FIG. 2, four accommodation sections 14 are formed in the adsorbent mounting body 4, and every other two of the first adsorbent cartridge A and the second adsorbent cartridge B are provided. It is loaded. By the way, at the time of the first sampling, the first pump 9 is operated in a state where the first adsorbent cartridge A is positioned so as to communicate with the transfer pipe 5, and the exhaust gas collected from the exhaust gas discharge passage 3 is discharged. It is introduced into the first adsorbent cartridge A and passed therethrough. During this passage, PCBs are mainly collected from the exhaust gas.
That is, the PCB is specifically collected in the state of “first collection” in FIG. The specific sampling here is performed for a predetermined time, and specifically, is performed for a time predetermined according to the type of the exhaust gas or the like.

Next, when the specific sampling is completed, that is, when the predetermined time has been reached, the first pump 9 is stopped, and the adsorbent mounting body 4 is rotated to shift to a cleaning operation. In this cleaning operation, the inside of the transfer pipe 5 is cleaned. First, the storage section 14 (hereinafter, referred to as an “empty storage section”) in which the adsorbent cartridge 6 is not loaded is communicated with the transfer pipe 5. To be performed, that is, in a state where the adsorbent mounting body 4 is penetrated. In this state, when a valve (not shown) of the purging cylinder 11 is opened, nitrogen gas from the purging cylinder 11 enters the adsorbent mounting body 4 through the purging line 12 and is emptied. And flows into the transfer pipe 5 through the storage section 14. Then, at the time of this passage, the inside of the transfer pipe 5 is washed, and thereafter, flows into the exhaust gas discharge path 3. That is, FIG.
The inside of the transfer pipe 5 is washed in the state of “washing”. The cleaning operation here is performed by using the temperature adjusting device 7 for 3 times.
By performing an operation of blowing nitrogen gas while heating to 00 to 400 ° C., that is, in a reducing atmosphere, complete cleaning can be performed in about one hour.

When the washing operation is completed, the process proceeds to the next collecting / extracting step. This collection and extraction process
The adsorbent mounting body 4 is rotated so that the first adsorbent cartridge A is connected to the extraction device 2 and the second adsorbent cartridge B is connected to the transfer pipe 5. And In this state, the extraction operation of the first cartridge A and the specific collection of the second adsorbent cartridge B are simultaneously performed.

Therefore, the extraction operation of the first adsorbent cartridge A will be described first. The extraction solvent supplied from the extraction device 2 is passed through the first adsorbent cartridge A, whereby the first adsorbent cartridge A is extracted. A
Is extracted into the extraction solvent. Thereby, the first adsorbent cartridge A can be one obtained by extracting and removing PCB. That is, it can be set to a state where it can be used for the next specific collection.

Next, the specific sampling of the second adsorbent cartridge B will be described. In the second adsorbent cartridge B, the same operation as in the "first extraction" is performed. Here, since the extraction operation of the first adsorbent cartridge A ends at the same time or earlier than the specific collection of the second adsorbent cartridge B, the adsorbent mounting body 4
Is performed according to the predetermined time in the specific sampling.

Further, when the collecting / extracting step is completed, the process proceeds to the washing step, and the washing operation is performed. That is, starting from the "first time of collection", thereafter, the "time of washing" and the "time of collection / extraction" are repeatedly performed, so that the collection step and the extraction step are continuously performed.

Next, the extraction device 2 includes an extraction solvent tank 15, a nitrogen gas cylinder 16 for pressurization, and a second pump 17. The extraction solvent tank 15 and the nitrogen gas cylinder for pressurization 16 are connected by a pressure line 19 having a second check valve 18, thereby keeping the pressure in the extraction solvent tank 15 constant. Then, using the second pump 17, the extraction solvent in the extraction solvent tank 15 passes through the adsorbent cartridge 6, which is located at the extraction position, that is, the inside of the first adsorbent cartridge A at the time of extraction in FIG. Pass through and selectively extract the PCB.

After the extract extracted by the extractor 2 is concentrated by the concentrator 20, the PCB is measured using GC / MS / MS21. Here, the concentrator 2
0 and the GC / MS / MS 21 may be performed in a place where an analytical instrument for measuring the concentration of PCB is completed.
It is also preferable to perform the measurement at the sampling place depending on the implementation.

Next, a second embodiment of the present invention will be described in detail with reference to FIG. In FIG. 3 showing the second embodiment, the same reference numerals as those used in FIGS. 1 and 2 showing the first embodiment denote the same member names, and a detailed description thereof will be omitted.

The second embodiment has a configuration in which a purification device 22 for removing impurities extracted in the extraction step is further added to the system of the first embodiment. The purification device 22 includes a multilayer silica gel column mounting body 24 having a plurality of switchable multilayer silica gel columns 23 mounted thereon.

First, the purifying device 22 is a device for transferring an extract containing PCB extracted from the extractor 2 to the multilayer silica gel column-mounted body 24 and removing impurities from the extract. The multilayer silica gel column mounting body 24 includes a plurality of multilayer silica gel columns 23 for mainly removing impurities from the extract.

Here, the operation of the multilayer silica gel column mounted body 24 will be described in detail with reference to FIG. The case of the revolver method as the multilayer silica gel column mounting body 24 will be described. The multi-layer silica gel column mounting body 24 includes a plurality of multi-layer silica gel column accommodating sections 25, 25, ... for loading the multi-layer silica gel column 23. The multilayer silica gel column 23 is loaded in each of the multilayer silica gel column accommodating sections 25. That is, in the embodiment shown in FIG. 4, four multilayer silica gel column accommodating portions 25 are formed in the multilayer silica gel column mounting body 24, and the first multilayer silica gel column C, the second multilayer silica gel column D and Three third multilayer silica gel columns E are loaded.

Now, the operation at the time of purification will be described.
First, the first multilayer silica gel column C is connected to the extraction device 2.
And operating the extraction device 2 in a state where the extraction device 2 is positioned so as to communicate with the adsorbent cartridge 6 (that is, either the first adsorbent cartridge A or the second adsorbent cartridge B), and The extract extracted from the cartridge 6 is introduced into the first multilayer silica gel column C and passed therethrough. During this passage, impurities are adsorbed and removed from the extract. That is, the impurities are adsorbed and removed in the state of the “purification position” in FIG. The adsorption and removal of impurities here is performed continuously with the extraction operation. Specifically, one multilayer silica gel column 23 is used for one adsorbent cartridge 6 and the extraction operation is performed at the same time. Performed over.

Next, when the refining operation is completed, that is, when the extraction operation of one of the adsorbent cartridges 6 is completed, the refining operation is also concomitantly completed, and the multi-layer silica gel column mounting body 24 is rotated, and the next operation is performed. Wait for purification operation. Here, the first multi-layer silica gel column C used for the purification operation is moved to the “removal position” in FIG. 4 by rotating the multi-layer silica gel column mounting body 24, and is retrieved at this position. Further, the second multilayer silica gel column D moves to the “purification position” in FIG. 4 and stands by for the next purification operation.

When the next extraction operation is started, a purification operation is performed using the second multilayer silica gel column D. When the purification operation of the second multilayer silica gel column D is completed, the multilayer silica gel column mounting body 24 is rotated, and the third multilayer silica gel column E is moved to the “purification position” in FIG. The two-layer silica gel column D is moved to the “removal position” in FIG. 4, and is further stored in the empty multilayer silica gel column accommodating portion 25 after the first multilayer silica gel column C is removed. A silica gel column (not shown) is loaded and prepared so that the purification operation can be performed continuously.

In the second embodiment, the "unloading position" and the "loading position" in FIG. 4 are separately provided, but it is also possible to unload and load the multilayer silica gel column 23 at the same position. It is suitable accordingly.

After the purified liquid extracted by the purifying device 22 is concentrated by the concentrator 20, the GC / HRMS 26
Is used to measure the PCB. Here, the concentrator 20 and the GC / HRMS 26 may be performed at a place where analysis equipment for measuring the concentration of PCB is completed, or may be performed at a sampling place, depending on the implementation.

Next, a third embodiment of the present invention will be described in detail with reference to FIG. 5 showing the third embodiment, FIG. 1 showing the first embodiment and the second embodiment
The same reference numerals as those used in Nos. To 4 denote the same member names, and a detailed description thereof will be omitted.

The third embodiment has a structure in which an alumina column 27 is further added to the purification device 22 of the second embodiment. That is, the purification device 22 in the third embodiment includes a plurality of switchable multilayer silica gel columns 23 and a plurality of switchable alumina columns 27.

First, the purifying device 22 is equipped with the multilayer silica gel column-mounted body 24 used in the second embodiment and a PC.
B and an alumina column mounting body 28 provided with a plurality of the alumina columns 27 for adsorbing PCB from a purified liquid containing impurities not adsorbed on the multilayer silica gel column 23 such as hydrocarbons. The alumina column-mounted body 28 includes a D / H solution tank 29 storing a hexane solution of dichloromethane (hereinafter, simply referred to as a “D / H solution”) for eluting the PCB and a PCB elution line 30. Connected through. In addition, the D /
The H solution tank 29 is connected to a second pressurizing nitrogen gas cylinder 31 via a second pressurizing line 32, and the second pressurizing line 32 is provided with a check valve 33. The second nitrogen gas cylinder 31 is provided in the D / H solution tank 29.
By controlling the internal pressure, the D / H solution is stably supplied to the alumina column mounted body 28.

Further, the purified liquid that has passed through the multilayer silica gel column 23 contains impurities such as PCB and hydrocarbons that were not adsorbed by the multilayer silica gel column 23. Therefore, based on the knowledge that the alumina column 27 adsorbs PCB, but does not adsorb hydrocarbons, etc.,
Only B is obtained.

Here, the operation of the alumina column mounted body 28 will be described in detail with reference to FIG. The case of the revolver method as the alumina column mounting body 28 will be described. The alumina column mounting body 28 includes a plurality of alumina column housings 34, 34,... For loading the alumina column 27. The alumina column 27 is loaded into each of the alumina column accommodating sections 34. That is, in the embodiment shown in FIG. 6, four alumina column accommodating portions 34 are formed in the alumina column mounting body 28, and when the purification operation is started, the first alumina column F and the second alumina column G Two are loaded.

Now, the operation of the third embodiment will be described. First, up to the purification step, the extraction step and the purification step are performed in the same manner as in the second embodiment. Then, the extraction device 2 is placed in a state where the first alumina column F is positioned so as to communicate with the multilayer silica gel column 23 (that is, the first multilayer silica gel column C).
Is operated to introduce the extract extracted from the adsorbent cartridge 6 into the multilayer silica gel column 23, and further pass through the first alumina column F. During this passage, the multilayer silica gel column 23 adsorbs and removes impurities from the extract, and the first alumina column F
Adsorb CB. That is, PCB is adsorbed in the state of “alumina adsorbing position” in FIG. 6 and impurities are passed. Here, the adsorption of PCB is performed continuously with the extraction operation and the purification operation of the multilayer silica gel column 23. Specifically, one alumina column 27 is used for one multilayer silica gel column 23, The extraction operation is performed at the same time.

Next, when the adsorption operation of the first alumina column F is completed, the alumina column mounting body 28 is rotated, and the second alumina column G is put on standby for the next adsorption operation. In this case, the first alumina column F used for the alumina adsorption operation is rotated by rotating the alumina column mounting body 28 so as to obtain “P” in FIG.
To the “CB elution position”, and the PCB elution operation is performed. The second alumina column G moves to the “alumina adsorption position” in FIG. 6 and stands by for the next adsorption operation. Further, a third alumina column (not shown) is loaded at the “loading position” in FIG.

Here, the elution operation of the PCB will be described. The elution operation of the PCB is performed by the “PCB
The D / H solution is supplied from the D / H solution tank 29 to the first alumina column F moved to the “elution position” via the PCB elution line 30. In this operation, PCB is eluted from the first alumina column F using the property of eluting only PCB of the D / H solution.

Next, when the adsorption operation of the second alumina column G is completed, the alumina column mounting body 28 is rotated, and the third alumina column is put on standby for the next adsorption operation. Here, the first alumina column F eluted from the PCB is moved to the “extraction position” in FIG. 6 by rotating the alumina column mounting body 28, and the operation of extracting the first alumina column F is performed. The second alumina column G used for the alumina adsorption operation is moved to the “PCB elution position” in FIG. 6, and the elution operation of the PCB is performed. Further, the third alumina column moves to the “alumina adsorption position” in FIG. 6 and stands by for the next adsorption operation. Further, the “loading position” in FIG.
To load a fourth alumina column (not shown).

In the third embodiment, the "unloading position" and the "loading position" in FIG. 6 are separately provided, but it is also possible to unload and load the alumina column 27 at the same position. It is suitable.

After the purified liquid extracted by the purifying device 22 is concentrated by the concentrator 20, the GC / LRMS 35
Is used to measure the PCB. Here, the concentrator 20 and the GC / LRMS 35 may be performed in a place where analysis equipment for measuring the concentration of PCB is completed, or may be performed in a sampling place, depending on the implementation.

[0048]

As described above, according to the present invention, the PC
The extraction and purification operations of B are simple, and the pretreatment for analyzing the PCB can be simplified. In addition, the operations of collection and purification can be performed continuously.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram schematically showing a pretreatment system as a first embodiment of the present invention.

FIG. 2 is an explanatory view schematically showing a revolver structure of an adsorbent mounting body used in the present invention.

FIG. 3 is an explanatory view schematically showing a pretreatment system as a second embodiment of the present invention.

FIG. 4 is an explanatory view schematically showing a revolver structure of a multilayer silica gel column-mounted body used in the present invention.

FIG. 5 is an explanatory view schematically showing a preprocessing system as a third embodiment of the present invention.

FIG. 6 is an explanatory view schematically showing a revolver structure of an alumina column-mounted body used in the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Sampling apparatus 6 Adsorbent cartridge 22 Purification apparatus 23 Multilayer silica gel column 27 Alumina column

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G01N 30/48 G01N 30/48 H K 30/88 30/88 C (72) Inventor Masazumi Yamashita Matsuyama, Ehime 7 in Horie-cho, Ichimi Miura Kogyo Co., Ltd. (72) Inventor Soichi Matsuda 7 in Horie-cho, Matsuyama-shi, Ehime Miura Kogyo Co., Ltd. F term (reference) 2G052 AA02 AD04 AD46 ED03 GA24 GA27

Claims (5)

[Claims] An object to be measured, such as exhaust gas, is mainly composed of PCB
A pre-processing method in the concentration measurement of PCB, wherein a sampling step of specifically collecting the sample and an extraction step of selectively extracting PCB from the sample are performed at a sampling location of the object to be measured. 2. The pretreatment method according to claim 1, wherein a purification step of removing impurities from the extract extracted in the extraction step is performed at the sampling place. 3. The sampling apparatus 1 used in the sampling step according to claim 1, comprising a plurality of switchable adsorbent cartridges 6. 4. A purification apparatus 22 used in the purification step according to claim 2, comprising a plurality of switchable multilayer silica gel columns 23. 5. The purifying apparatus according to claim 4, wherein said purifying apparatus further includes a plurality of switchable alumina columns.