JP3843977B2 - Sample extraction device for analysis of dioxins - Google Patents

Description

  The present invention relates to a sample extraction apparatus for analysis of dioxins, and more particularly to an apparatus for extracting a sample for analysis of dioxins from a filter obtained by capturing and collecting dioxins contained in a fluid sample.

  Dioxins may be contained in exhaust gas generated from incineration facilities for incinerating waste such as industrial waste and general household waste. Dioxins are a general term for polychlorinated dibenzo-para-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and the like, and as is well known, they are extremely toxic environmental pollutants. Establishing measures to remove wastewater and other fluids is an urgent issue, and at the same time, establishing a method for analyzing dioxins contained in such fluids is urgently required worldwide. Yes.

  By the way, when analyzing dioxins contained in a fluid, it is first necessary to obtain a sample for analysis of dioxins from the fluid to be analyzed. For example, when analyzing dioxins contained in exhaust gas, it is necessary to collect a certain amount of sample gas from the flue through which the exhaust gas passes, and to collect dioxins contained in this sample gas as a sample for analysis. is there.

  Therefore, Japanese Industrial Standard JIS K 0311: 1999 established on September 20, 1999 specifically illustrates a device for collecting dioxins contained in exhaust gas. The sampling apparatus includes a sampling tube for collecting a sample gas from a flue through which exhaust gas flows, a first trap with a filter material for allowing the sample gas collected by the sampling tube to pass through, and a first trap The second trap is mainly provided for further passing the sample gas that has passed through. The second trap mainly includes a liquid collector composed of a plurality of glass impingers filled with an absorbing solution and an adsorption collector disposed with an adsorbent (for example, XAD-2). The dioxins contained are configured to be captured by the absorbing solution and the adsorbent in the impinger.

  When collecting a sample for analysis of dioxins using such a sampling device, first, a certain amount of sample gas is sampled from the flue through the sampling tube, and this sample gas is collected from the first trap and the second trap. Pass in the order. At this time, dioxins contained in the sample gas are captured by the filter material of the first trap and the liquid collector and the adsorbent of the second trap and are removed from the sample gas. And when the dioxins trapped by the filter material, the liquid collection part and the adsorbent are extracted from these members using a solvent, a target sample for analysis is obtained. The obtained sample for analysis is appropriately subjected to pretreatment such as purification and concentration, and then applied to an analyzer such as GC / MS and analyzed qualitatively or quantitatively.

  In order to secure an analytical sample of dioxins collected by the analytical sample collection device as described above, it is necessary to perform an extraction operation manually. Complicated and cumbersome and takes a long time.

An object of the present invention is to easily and quickly secure a sample for analysis of dioxins contained in a sample gas .

The sample extraction device for analyzing dioxins according to the present invention is for extracting a sample for analysis of dioxins from a filter obtained by capturing and collecting dioxins contained in a sample gas, and is collected by the filter. The first extraction solvent supply unit for supplying the first extraction solvent for extracting the dioxins from the filter to the filter, the first extraction solvent supply unit supplying the filter to the filter, and the dioxin from the filter A first processing unit having a first column filled with a first stationary phase capable of capturing polar substances and allowing dioxins to pass through, which is set so as to be able to supply a first extraction solvent from which the species is extracted ; A second stationary phase capable of trapping dioxins, which is set so that it can pass through the first column and subsequently supply the first extraction solvent containing dioxins, is filled. A second extraction unit capable of extracting dioxins in a direction opposite to the supply direction of the first extraction solvent with respect to the second column, and a second processing unit having a second column opened in the vertical direction. A second extraction solvent supply unit capable of being supplied , and the second column is disposed below the first column .

In such an analytical sample extraction apparatus, the dioxins captured by the filter are extracted by the first extraction solvent supplied from the first extraction solvent supply unit to the filter, and secured as an analysis sample. Then, the first extraction solvent obtained by extracting dioxins from the filter is subsequently supplied to the first processing unit. When the first extraction solvent supplied to the first processing section passes through the first column, polar substances, that is, impurities other than dioxins are captured by the first stationary phase and purified. The first extraction solvent that passes through the first column and contains dioxins is subsequently supplied to the second processing section. When the first extraction solvent supplied to the second processing section passes through the second column, dioxins are captured by the second stationary phase and removed. And, when the second extraction solvent is supplied from the second extraction solvent supply unit in the direction opposite to the first extraction solvent supply direction, the dioxins captured in the second column are Extracted from the second column by the second extraction solvent and secured as an analytical sample dissolved in the second extraction solvent. Here, if the minimum necessary amount of the second extraction solvent is used, as a result, the analytical sample is in a concentrated state.

  Note that such an analytical sample extraction device may further include, for example, a heating device for heating the first column. Further, the first processing unit may have a plurality of first columns, for example, and may be set so that the first column can be switched for each filter. Further, the second processing unit may have a plurality of second columns, for example, and may be set so that the second column can be switched for each first column.

Since the sample extraction device for analysis of dioxins according to the present invention includes the first extraction solvent supply unit , the first processing unit, the second processing unit, and the second extraction solvent supply unit as described above, the sample gas A sample for analysis of dioxins can be easily and quickly secured from a filter that captures dioxins contained therein.

With reference to FIG. 1, a dioxin analysis sample collection device employing a dioxin analysis sample extraction device will be described. In the figure, an analytical sample collecting device 30 is for collecting an analytical sample for analyzing dioxins contained in exhaust gas flowing through the flue 2 of the waste incinerator. The guide unit 4, the first extraction solvent supply unit 5, and the analysis sample purification unit 31 are mainly provided.

The sampling unit 3 includes a filter holder 6 and a first driving device 7 for rotating the filter holder 6. The filter holder 6 is formed in a disk shape having a certain thickness, and is arranged so that the axial direction is horizontal. Further, as shown in FIG. 2A (viewed from the direction of arrow II in FIG. 1), the filter holder 6 has four through holes 6a at equal intervals on the same circumference. Each through-hole 6a is opened in the thickness direction of the filter holder 6 and every other filter 8 is mounted. In other words, two filters 8 are attached to the filter holder 6 .

  The filter 8 is for capturing and collecting dioxins contained in the exhaust gas, and is formed of a molded article having a three-dimensional network structure having fluid permeability (in this embodiment, air permeability). Incidentally, the filter 8 can collect dioxins in the same manner as the dioxin collection device exemplified in JIS K 0311: 1999, and can be used in place of the collection device exemplified in JIS K 0311: 1999. Is something.

  Such a filter 8 is already known, for example, in WO 01/91883, and is usually formed in a cylindrical shape with one end closed as shown in FIG. The filter 8 is inserted into the through hole 6a so that the opening side communicates with a first transfer pipe 10 described later.

The above-described molded body constituting the filter 8 includes a fiber material (a group of fiber materials) and an inorganic binder. The fiber material used here is a material that does not substantially chemically react with dioxins, and is usually among fibrous activated carbon, carbon fiber, glass fiber, alumina fiber (preferably activated alumina fiber), silica fiber, and Teflon fiber. Is at least one of On the other hand, an inorganic binder is a material that binds fiber materials together to integrate a group of fiber materials, and has a property of imparting a fixed shape to the group of fiber materials, that is, a group of fiber materials. It functions as a binder that maintains a fixed molding shape. More specifically, the group of fiber materials is for setting the shape of the filter 8, that is, a cylindrical shape with one end closed.

  The inorganic binder usable here is not particularly limited as long as it has the above-described performance and does not substantially chemically react with dioxins as in the case of the fiber material. What has the adsorption | suction performance with respect to dioxins is preferable. Examples of such inorganic binders include alumina (preferably activated alumina), zeolite (preferably synthetic zeolite), silicon dioxide (silica), acid clay, apatite, and the like. The materials may be used alone or in combination of two or more. Further, the form of the inorganic binder is not particularly limited, but usually a particulate one is used. Further, the inorganic binder is particularly preferably one having tar adsorptivity. When an inorganic binder having such characteristics is used, the filter 8 can effectively adsorb tar generated from, for example, carbon monoxide contained in the exhaust gas. Dioxins dissolved in it can be captured and collected more reliably. Examples of the inorganic binder capable of adsorbing tar include alumina, zeolite, and silicon dioxide. These inorganic binders capable of adsorbing tar may be used alone or in combination of two or more.

Further, the molded body above is usually preferable bulk density is set to 0.1 to 1 g / cm ^3, and more preferably set to 0.3 to 0.7 g / cm ^3. When the bulk density of the molded body is less than 0.1 g / cm ³ , some of the dioxins contained in the exhaust gas may pass through the filter 8, and the dioxins contained in the exhaust gas are stabilized. May be difficult to collect. Conversely, when the bulk density exceeds 1 g / cm ³ , pressure loss may increase when the particulate matter contained in the exhaust gas is captured in the filter 8, and as a result, the exhaust gas does not easily pass. Therefore, it may be difficult to perform uniform suction as defined in the JIS standard (JIS K 0311: 1999). Further, when extracting dioxins collected by the filter 8, there is a possibility that the extraction rate is lowered.

What is preferable as the molded body constituting the filter 8 is one using activated alumina fibers as the fiber material and using particulate activated alumina as the inorganic binder. In particular, such a molded body having a bulk density set in a range of 0.3 to 0.7 g / cm ³ is most preferable.

  The method for manufacturing the filter 8 as described above is as described in the above-mentioned WO01 / 91883.

  The first driving device 7 is for rotating the filter holder 6 in the clockwise direction of FIG. 2, and mainly includes a rotating shaft 9 a and a motor 9 mounted at the center of the filter holder 6. . The motor 9 is capable of intermittently rotating the rotary shaft 9a by 90 degrees.

The guide unit 4 is for collecting a part of the exhaust gas flowing through the flue 2 ( which is an example of a sample gas, hereinafter referred to as a sample gas ) and guiding it to the collection unit 3. A first transfer pipe 10 and a second transfer pipe 11 are provided with the filter holder 6 interposed therebetween. One end of the first transfer pipe 10 is arranged in the flue 2 and the other end is one of the through holes 6a provided in the filter holder 6 (in FIG. 1 and FIG. It communicates with a through hole 6a) located at the top of the body 6. Moreover, the 1st transfer pipe 10 has the temperature control apparatus 12 for setting so that the temperature of sample gas may be 100-120 degreeC. On the other hand, one end of the second transfer pipe 11 communicates with the opposite side of the through hole 6a with which the first transfer pipe 10 communicates, and a drain trap 13 and a suction pump 14 are arranged in this order on the other end. Have. Here, the drain trap 13 is for collecting moisture in the sample gas, and the suction pump 14 is for sucking the exhaust gas flowing through the flue 2 stably at a constant speed. .

  Further, the second transfer pipe 11 has a temperature sensor 15. The temperature sensor 15 is for measuring the temperature of the sample gas flowing in the second transfer pipe 11 and communicates with the temperature adjustment device 12. The temperature adjusting device 12 is set so that the temperature of the sample gas flowing in the first transfer pipe 10 can be adjusted based on the measurement result by the temperature sensor 15. Further, a cleaning nitrogen gas supply path 17 extending from the cleaning nitrogen gas cylinder 16 communicates with the second transfer pipe 11. The cleaning nitrogen gas supply path 17 has a first check valve 18.

  The first extraction solvent supply unit 5 is for supplying a dioxin extraction solvent (first extraction solvent) to the filter 8 held by the filter holder 6. A first extraction solvent supply path 19 and a first extraction solvent discharge path 20 are disposed so as to be sandwiched therebetween. The first extraction solvent supply path 19 has a first supply pump 21, one end of which is separated from the through hole 6 a provided in the filter holder 6 with the guide portion 4 communicating therewith. It communicates with another through-hole 6a (the through-hole 6a located in the lower part of the filter holder 6 in FIG. 1 and FIG. 2A). The first extraction solvent supply path 19 communicates with the through hole 6a from the opposite side of the first transfer pipe 10 (that is, the communication side of the second transfer pipe 11).

  The other end of the first extraction solvent supply path 19 is disposed in a first solvent tank 22 in which a dioxin extraction solvent is stored. The extraction solvent stored in the first solvent tank 22 is not particularly limited as long as it can extract dioxins captured by the filter 8, but various kinds of dioxins usually containing dioxins are used. It is preferable to use one that can efficiently extract the hydrocarbon compound, for example, hexane. The first solvent tank 22 communicates with a first pressurization nitrogen gas supply path 25 extending from the first pressurization nitrogen gas cylinder 23 and having a second check valve 24. As a result, the internal pressure of the first solvent tank 22 is kept constant by the nitrogen gas supplied from the first pressurization nitrogen gas supply path 25.

  One end of the first extraction solvent discharge path 20 communicates with the opposite side of the through hole 6a with which the first extraction solvent supply path 19 communicates, and the other end opens.

The purification unit 31 mainly includes a first column holder 32 and a second drive device 33 for rotating the first column holder 32. The first column holder 32 is formed in a disk shape having a constant thickness, and is disposed below the first extraction solvent discharge path 20 of the first extraction solvent supply unit 5 so that the axial direction is vertical. Has been. In addition, as shown in FIG. 4A (viewed from the direction of arrow IV in FIG. 1), the first column holder 32 has two through holes 32a facing each other across the center on the same circumference. Have. Each through-hole 32a opens in the thickness direction of the first column holder 32, and the first column 34 is attached to each through-hole 32a. That is, two first columns 34 are mounted on the first column holder 32 .

  The first column 34 is a cylindrical body that opens in the vertical direction and is filled with a stationary phase (first stationary phase). The stationary phase used here is capable of capturing polar substances and not capturing dioxins. As such a stationary phase, for example, silica gel can be used. The silica gel used as the stationary phase may be one in which different types of silica gel are arranged in multiple layers, for example, one in which silver nitrate silica gel and sulfuric acid silica gel are arranged in multiple layers. When such a stationary phase is used, the purification treatment described later can be carried out more effectively and quickly.

One of the two through holes 32 a provided in the first column holder 32 is disposed above the opening end side of the first extraction solvent discharge path 20. A second extraction solvent discharge path 35 is disposed below the through hole 32a .

  The second drive device 33 is for rotating the first column holder 32 in the clockwise direction of FIG. 4. The second drive device 33 mainly includes a rotary shaft 36 and a motor 37 mounted at the center of the first column holder 32. In preparation. The motor 37 is capable of intermittently rotating the rotary shaft 36 by 180 degrees.

  The analytical sampling device 30 operates in the order described below by sequence control or computer control.

Next, the operation of the above-described analytical sampling device 30 will be described.
First, in the sampling unit 3, the motor 9 is operated and the filter holder 6 is rotated. Accordingly, one of the two filters 8 held in the through hole 6 a of the filter holder 6 is arranged so as to be sandwiched between the first transfer pipe 10 and the second transfer pipe 11 of the guide portion 4. . At this time, the other filter 8 held by the filter holder 6 is sandwiched between the first extraction solvent supply path 19 and the first extraction solvent discharge path 20 of the first extraction solvent supply section 5. Placed in. (State A in FIGS. 1 and 2)

  After the filter holder 6 is set as described above, the suction pump 14 is activated. As a result, a part of the exhaust gas in the flue 2 is continuously sucked into the first transfer pipe 10 as a sample gas at a constant speed, and after the temperature is adjusted to the above temperature range in the temperature adjusting device 12, It passes through the filter 8 and moves into the second transfer pipe 11. At this time, dioxins contained in the sample gas are captured by the filter 8 and removed from the sample gas. The sample gas that has moved into the second transfer pipe 11 is subsequently sucked by the suction pump 14 and is discharged after moisture is collected by the drain trap 13.

  The sampling of the sample gas as described above is performed by operating the suction pump 14 for a predetermined time. As a result, a certain amount of sample gas passes through the filter 8, and dioxins contained in the certain amount of sample gas are captured and collected. In addition, it is preferable to set suitably the fixed time here according to the kind of waste incinerated in an incinerator, and it is preferable to usually set to the time prescribed | regulated in the above-mentioned JISK0311: 1999.

  After the elapse of the above-mentioned fixed time, next, the motor 9 operates to rotate the filter holder 6 by 90 degrees clockwise as shown in FIG. Thereby, the 1st transfer pipe 10 and the 2nd transfer pipe 11 will mutually communicate by the through-hole 6a which is not holding the filter 8. FIG. When nitrogen gas is supplied from the cleaning nitrogen gas cylinder 16 in this state, the nitrogen gas flows into the second transfer pipe 11 through the cleaning nitrogen gas supply path 17 and also passes through the through-hole 6a to the first. After flowing into the transfer pipe 10, it is continuously discharged into the flue 2. As a result, the inside of the first transfer pipe 10 is cleaned with nitrogen gas. At this time, the first transfer pipe 10 is preferably heated to 300 to 400 ° C. by the temperature control device 12. If it does in this way, the inside of the 1st transfer pipe 10 will be in a reducing atmosphere, and will be effectively washed in a shorter time.

  Next, after completion of the above-described cleaning operation, the motor 9 is actuated again, and the filter holder 6 is rotated 90 degrees clockwise as shown in FIG. Accordingly, the filter 8 from which the dioxins are collected is disposed so as to be sandwiched between the first extraction solvent supply path 19 and the first extraction solvent discharge path 20 of the first extraction solvent supply section 5. At the same time, the other filter 8 is disposed so as to be sandwiched between the first transfer pipe 10 and the second transfer pipe 11 of the guide portion 4. That is, the collection unit 3 is set so that the other filter 8 can guide the sample gas, and at the same time, the filter 8 that collects the dioxins can supply the extraction solvent from the first extraction solvent supply path 19. Will be set. In other words, the collection unit 3 is set to a state in which the filter 8 is switched in order to collect different sample gases from the flue 2.

  Further, in the purification unit 31, the motor 37 is operated, and one of the two first columns 34 attached to the first column holder 32 is located below the first extraction solvent discharge path 20 and the second column 34. It arrange | positions so that it may be located above the solvent discharge path 35 for extraction.

  In such a state, the suction pump 14 operates again for the above-mentioned fixed time. As a result, different sample gas from the flue 2 passes through the other filter 8, and dioxins contained in the sample gas can be collected.

  On the other hand, in such a state, the first supply pump 21 operates simultaneously. As a result, the extraction solvent stored in the first solvent tank 22 is continuously supplied to the filter 8 from which the dioxins have been previously collected through the first extraction solvent supply path 19. The extraction solvent supplied to the filter 8 passes through the filter 8 in the direction of the first extraction solvent discharge path 20 and is discharged from the first extraction solvent discharge path 20. At this time, the dioxins captured by the filter 8 are extracted into the extraction solvent passing through the filter 8 and discharged from the first extraction solvent discharge path 20 together with the extraction solvent.

  Then, the analysis sample discharged from the first extraction solvent discharge path 20, that is, the extraction solvent containing dioxins, is supplied to the first column 34 mounted on the first column holder 32 with respect to the first column 34. It is continuously supplied from the extraction solvent discharge path 20. The analytical sample supplied to the first column 34 passes through the stationary phase packed in the first column 34 and is collected through the second extraction solvent discharge path 35. At this time, impurities other than dioxins contained in the analysis sample, that is, various polar substances captured together with the dioxins from the above-described sample gas by the filter 8 are captured in the stationary phase, and from the analysis sample. Removed. Therefore, according to this analytical sample collection device 30, it is possible to secure a purified analytical sample of dioxins contained in the sample gas.

  The analytical sample secured in this manner can be analyzed qualitatively or quantitatively when applied to an analytical instrument such as GC / MS after performing a concentration operation as necessary.

As described above, in the analytical sample collection device 30, the dioxins contained in the sample gas are collected in the collection unit 3, and the extraction solvent is supplied from the first extraction solvent supply unit 5 to the collection unit 3. Since the collected dioxins can be quickly extracted by supplying, a sample for analysis of dioxins contained in the sample gas can be easily and quickly secured.

  Further, in this analytical sample collection device 30, the filter holder 6 of the collection unit 3 is configured to be rotatable as described above and has two filters 8, so that the collection unit 3 uses the filter 8. The collection of dioxins from the sample gas and the extraction of dioxins collected by the other filter 8 can be efficiently performed in parallel.

  Further, after the analysis sample from the extraction solvent discharge path 20 is purified as described above, the motor 37 rotates the first column holder 32 clockwise by 180 degrees as shown in FIG. Let Accordingly, another first column 34 is disposed between the first extraction solvent discharge path 20 and the second extraction solvent discharge path 35, and the other first column 34 is collected. An analytical sample derived from another filter 8 in part 3 can subsequently be purified. That is, in this analytical sample collection device 30, the first column 34 can be switched for each filter 8.

Note that the filter 8 used in the analytical sample collection device 30 is substantially washed when the collected dioxins are extracted with the extraction solvent. Therefore, the filter 8 after the dioxins are extracted can be reused repeatedly to collect dioxins contained in different sample gases.

(1) In the analytical sampling device 30 described above, the filter holder 6 may have a built-in heater 6b for heating the filter 8 around the through-hole 6a, as shown by a one-dot chain line in FIG. Good. When supplying the extraction solvent from the first extraction solvent supply unit 5 to the filter 8, if the filter 8 is heated by the heater 6 b, the dioxins captured by the filter 8 are extracted with a smaller amount of the extraction solvent. can do.

(2) In the analytical sampling device 30 described above, the first column holder 32 is provided with a heater 38 for heating the first column 34 around each through-hole 32a, as shown by a one-dot chain line in FIG. An example of a heating device) may be incorporated. When the first column 34 is heated by the heater 38, impurities contained in the analysis sample from the first extraction solvent discharge channel 20 are more effectively captured in the stationary phase. The purification efficiency of the sample can be further increased.

(3) FIG. 5 shows a modified example of the analytical sampling device 30 described above. In FIG. 5, the same members as those shown in FIG. An analytical sample collection device 40 according to this modification is according to the embodiment of the present invention, and further includes an analytical sample concentration unit 41 (an example of a second processing unit).

  The concentration unit 41 mainly includes a second column holder 42, a third driving device 43 for rotating the second column holder 42, and a second extraction solvent supply unit 44. The second column holder 42 is formed in a disk shape having a certain thickness, and is disposed below the second extraction solvent discharge path 35 of the purification unit 31 so that the axial direction is vertical. Further, as shown in FIG. 6A (viewed from the direction of arrow VI in FIG. 5), the second column holder 42 has three through holes 42a arranged at equal intervals on the same circumference. Have. Each through-hole 42a opens in the thickness direction of the second column holder 42, and a second column 45 is attached to each through-hole 42a. That is, in this embodiment, the second column holder 42 is equipped with three second columns 45.

  The second column 45 is a cylindrical body that opens in the vertical direction and is filled with a stationary phase (second stationary phase). The stationary phase used here is capable of capturing dioxins. As such a stationary phase, a material having a high dioxin adsorption performance, for example, a carbon material such as activated carbon or graphite can be used.

  Note that one of the three through holes 42 a provided in the second column holder 42 has a second extraction solvent discharge path 35 disposed above it.

  The third drive unit 43 is for rotating the second column holder 42 in the clockwise direction of FIG. 6. The third drive unit 43 mainly includes a rotating shaft 46 and a motor 47 mounted at the center of the second column holder 42. In preparation. The motor 47 can rotate the rotating shaft 46 intermittently by 120 degrees.

  The second extraction solvent supply unit 44 is for supplying a dioxin extraction solvent (second extraction solvent) to the second column 45 held by the second column holder 42. A second extraction solvent supply path 50 and a third extraction solvent discharge path 51 are disposed with the two-column holder 42 interposed therebetween. The second extraction solvent supply path 50 includes a second supply pump 52, and the second extraction solvent discharge path 35 is disposed in one of the through holes 42 a provided at one end of the second column holder 42. However, it is connected to the lower part of the one provided in the counterclockwise direction. The other end of the second extraction solvent supply path 50 is disposed in a second solvent tank 53 in which a dioxin extraction solvent is stored. The extraction solvent stored in the second solvent tank 53 is not particularly limited as long as it can extract dioxins trapped in the stationary phase of the second column 45. For example, toluene Is preferably used. Further, a second pressurization nitrogen gas supply path 56 extending from the second pressurization nitrogen gas cylinder 54 and having a third check valve 55 communicates with the second solvent tank 53. As a result, the internal pressure of the second solvent tank 53 is kept constant by the nitrogen gas supplied from the second pressurization nitrogen gas supply path 56.

  The third extraction solvent discharge path 51 has one end communicating with the upper side of the through hole 42 a with which the second extraction solvent supply path 50 communicates and the other end under the second column holder 42. It extends and is open.

  Further, the second extraction solvent supply unit 44 has a cleaning unit 57 for the second column 45. The cleaning unit 57 includes a cleaning solvent supply path 58. The cleaning solvent supply path 58 includes a third supply pump 59, and the second extraction solvent discharge path 35 is disposed in one of the through holes 42 a provided at one end of the second column holder 42. It communicates above what is provided adjacent to the clockwise direction of the thing. The other end of the cleaning solvent supply path 58 is disposed in the third solvent tank 60 in which the cleaning solvent for the second column 45 is stored. The cleaning solvent stored in the third solvent tank 60 can extract impurities in the stationary phase of the second column 45 and does not extract dioxins. For example, hexane containing 25% by weight of dichloromethane is used. It is. The third solvent tank 60 includes a fourth check valve 61 that branches from the second pressurization nitrogen gas cylinder 54 side of the second pressurization nitrogen gas supply path 56 to the second pressurization nitrogen gas cylinder 54 side. A nitrogen gas supply path 62 for three pressurizations communicates. As a result, the internal pressure of the third solvent tank 60 is kept constant by the nitrogen gas supplied from the third pressurizing nitrogen gas supply path 62.

When the analysis sample collection device 40 is used to collect a sample for analysis of dioxins, the motor 47 is activated, and one of the three second columns 45 attached to the second column holder 42 is the first one. It arrange | positions so that it may be located under the solvent discharge path 35 for two extractions. At this time, the other two second columns 45, 45 are positioned between the second extraction solvent supply path 50 and the third extraction solvent discharge path 51 and below the cleaning solvent supply path 58, respectively. Be placed. Then, after the concentration unit 41 is set in such a state, when the analysis sample is collected in the same manner as the analysis sample collection device 30 described above, the analysis sample purified in the purification unit 31, that is, The extraction solvent containing dioxins and from which impurities are removed is continuously supplied from the second extraction solvent discharge path 35 to the second column 45 corresponding to the second extraction solvent discharge path 35.

  Here, the analytical sample supplied to the second column 45 passes through the stationary phase packed in the second column 45. At this time, dioxins contained in the analysis sample are captured by the stationary phase and remain in the second column 45. On the other hand, the extraction solvent in the analysis sample passes through the stationary phase and is discharged from the lower portion of the second column 45.

  After the entire amount of the sample for analysis from the purification unit 31 is supplied to the second column 45, the motor 47 rotates the second column holder 42 by 120 degrees clockwise as shown in FIG. 6 as shown in FIG. Let Thus, the second column 45 through which the analysis sample from the purification unit 31 has passed is disposed so as to be positioned below the cleaning solvent supply path 58. In this state, the third supply pump 59 is operated, and the cleaning solvent stored in the third solvent tank 60 is continuously supplied to the second column 45 through the cleaning solvent supply path 58. As a result, the impurities trapped in the second column 45 together with the dioxins are discharged from the second column 45 together with the cleaning solvent.

  After a certain amount of the cleaning solvent is supplied to the second column 45, the motor 47 rotates the second column holder 42 further 120 degrees clockwise as shown in FIG. 6 as shown in FIG. 6C. . Thus, the second column 45 washed with the washing solvent is disposed so as to be positioned between the second extraction solvent supply path 50 and the third extraction solvent discharge path 51. In this state, the second supply pump 52 is operated, and the extraction solvent in the second solvent tank 53 is continuously supplied from below the second column 45 through the second extraction solvent supply path 50. The extraction solvent supplied to the second column 45 extracts dioxins trapped in the stationary phase and is discharged through the third extraction solvent discharge path 51. Therefore, when the extraction solvent containing dioxins discharged from the third extraction solvent discharge passage 51 is collected, a sample for analysis of dioxins can be secured.

  Note that the analytical sample that can be secured here includes the minimum amount of extraction solvent necessary for extracting the dioxins captured in the second column 45, and therefore the analytical sample from the purification unit 31. The amount is smaller than that of, and as a result, dioxins are concentrated. Therefore, this analytical sample can be directly applied to an analytical instrument as it is or with a slight concentration as required.

  Incidentally, at the time of the extraction operation as described above, one of the other two second columns 45, 45 held by the second column holder 42 is arranged below the second extraction solvent discharge path 35. Therefore, another sample for analysis containing dioxins collected by another filter 8 in the collection unit 3 can be received. That is, in this analytical sample collection device 40, the second column 45 can be switched for each first column 34 of the purification unit 31, the supply of the analytical sample from the purification unit 31 to the second column 45, and the other The extraction of the dioxins previously captured in the second column 45 can be performed in parallel.

(4) In the analytical sampling device 40 described above , the second column holder 42 is provided with a heater 63 for heating the second column 45 around each through-hole 42a, as shown by a one-dot chain line in FIG. It may be built in. When the second column 45 is heated by the heater 63, the dixins captured by the second column 45 can be extracted with a smaller amount of extraction solvent, and the concentration efficiency of the analytical sample can be increased.

(5) In the above-described analytical sample collection device 40 , the two filters 8 are attached to the collection unit 3. However, if necessary, three or more filters 8 may be attached to the collection unit 3. In this case, it is preferable that the numbers of the first column 34 and the second column 45 mounted in the purification unit 31 and the concentration unit 41 are set according to the number of the filters 8.

(6) In the above-described analytical sampling device 40 , the filter 8 is made of a molded body containing a fiber material and an inorganic binder, and the filter 8 is exemplified in JIS K 0311: 1999. Other types of dioxins may be used as long as they can collect dioxins in the same manner as the dioxins collection device. Incidentally, as another type of filter, for example, one disclosed in WO99 / 37987, for example, one made of a molded body containing inorganic fiber and activated carbon can be mentioned.

(7) In the above-described analytical sample collection device 40 , the case where the analysis sample of dioxins contained in the exhaust gas discharged from the waste incinerator is collected by the filter 8 has been described. The present invention can be used in the same manner when collecting a sample for analysis of dioxins contained in a sample gas other than exhaust gas. For example, the filter 8 can be used in the same manner when collecting a sample for analysis of dioxins contained in the ambient air .

Schematic of a sample collection device for analysis of dioxins employing a sample extraction device for analysis of dioxins . The figure which looked at the filter holder used in the said sample-collecting apparatus for analysis from the arrow II direction of FIG. Sectional drawing of the filter used in the said sampling device for analysis . The figure which looked at the 1st column holding body used in the said sample-collecting apparatus for analysis from the arrow IV direction of FIG. BRIEF DESCRIPTION OF THE DRAWINGS Schematic of the sample collection apparatus for dioxin analysis which employ | adopted the sample extraction apparatus for dioxin analysis which concerns on embodiment of this invention . The figure which looked at the 2nd column holding body used in the said embodiment from the arrow VI direction of FIG.

Explanation of symbols

30, 40 Analytical sample collection device 3 Collection unit 4 Guide unit 5 First extraction solvent supply unit 8 Filter 31 Purification unit 34 First column 38 Heater 41 Concentration unit 44 Second extraction solvent supply unit 45 Second column

Claims (4)

An apparatus for extracting a sample for analysis of dioxins from a filter obtained by capturing and collecting dioxins contained in a sample gas,
A first extraction solvent supply unit for supplying a first extraction solvent for extracting the dioxins collected by the filter from the filter to the filter;
The first extraction solvent supply unit is set to be able to supply the first extraction solvent supplied to the filter and extracted from the filter by extracting the dioxins. A first treatment section having a first column packed with a passable first stationary phase;
First opening in the vertical direction filled with a second stationary phase capable of capturing the dioxins, which is set so as to be able to continuously supply the first extraction solvent containing the dioxins through the first column. A second processing section having two columns;
A second extraction solvent supply unit capable of supplying a second extraction solvent capable of extracting the dioxins in a direction opposite to the first extraction solvent supply direction with respect to the second column;
The second column is disposed below the first column;
Sample extraction device for analysis of dioxins. The sample extraction device for analysis of dioxins according to claim 1 , further comprising a heating device for heating the first column. The dioxin analysis sample extraction device according to claim 1 , wherein the first processing unit includes a plurality of the first columns and is set so that the first column can be switched for each filter. The sample extraction apparatus for analysis of dioxins according to claim 3 , wherein the second processing unit includes a plurality of the second columns and is configured to be able to switch the second column for each first column.

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