JP2009168459A - Extractor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an extractor capable of preparing a hydrophilic extraction liquid of PCBs from an oily liquid sample containing PCBs in a short time by simple operation. <P>SOLUTION: The extractor X includes a first column 10 for housing a first filler which decomposes impurities contained in the oily liquid sample to adsorb them and a second filler for adsorbing the decomposed impurities, a second column 20 which houses a third filler for adsorbing PCBs, a connection means for connecting or disconnecting the first and second columns 10 and 20, a first storage part capable of supplying an aliphatic hydrocarbon solvent to the first column 10, a holding mechanism 90 with a sliding and fixing means 91 capable of sliding the second column 20 to make it detachable and a changeover means 92 capable of changing over the liquid passing direction in the second column 20 to a usual state or a reversal state and a second storage part 80 capable of supplying a hydrophilic solvent to the second column 20 of the reversal state. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an extraction apparatus for extracting polychlorinated biphenyls from an oily liquid containing polychlorinated biphenyls.

  Conventionally, oil containing polychlorinated biphenyls (hereinafter referred to as “PCBs”) excellent in electrical insulation has been used as electrical insulation oil for electrical equipment such as transformers. However, since the toxicity of PCBs to living organisms has been confirmed, the use of electrical insulating oil containing PCBs is substantially prohibited.

With the establishment of a safe chemical decomposition method for PCBs, the so-called PCB Special Measures Law was enacted in 2001, and PCBs that have been used or stored until July 2016 The disposal of all PCB wastes including the contained electrical insulation oil has become mandatory. PCB wastes subject to this law contain PCBs of 0.5 mg / kg or more.
Since existing electric devices have the above-mentioned deadlines in the PCB Special Measures Law, it is urgently requested to determine whether or not the electrical insulating oil falls under the PCB waste.

  Gas chromatograph mass spectrometry (GC / MS method) and gas chromatograph electron capture detection method (GC / ECD method) are known as methods for measuring PCBs contained in oily liquids such as electrical insulating oil. These methods are determined based on analysis results using a highly sensitive analyzer. However, since the oily liquid sample also includes interfering components that affect the analysis result, it is necessary to highly pretreat the oily liquid sample in order to improve the analysis accuracy.

  For example, in the pretreatment method described in Patent Document 1, an extract obtained by extracting an organic component in an oily liquid sample into an organic solvent is prepared, and this extract is applied to a silica gel column and an alumina column in this order by a chromatography method. Let it pass. At this time, a part of impure components other than PCBs contained in the extract is decomposed when passing through the silica gel column, and this decomposition product is captured by the silica gel column. When the developing solvent that has passed through the alumina column is collected, an PCB-containing extract from which impure components are separated is obtained. This PCB-containing extract is used as a sample for analysis by the GC / MS method or the GC / ECD method.

As a method for measuring PCBs contained in the oily liquid, it is known that there is a bioassay method such as an immunoassay method in addition to a gas chromatography method such as a GC / MS method (for example, Patent Document 2).
The gas chromatography method requires at least about 1 hour for measurement of PCBs. However, since the bioassay method can usually measure PCBs in a few tens of minutes, it is advantageous in reducing the measurement time of PCBs.
In addition, the gas chromatography method requires a wide space for installing the equipment, and it is necessary to manage the temperature and humidity of the installation environment of the equipment. However, the bioassay method is advantageous over the gas chromatography method in that the device is small and management of the installation environment is substantially unnecessary.
Therefore, as a method for measuring PCBs contained in the oily liquid, it may be preferable to apply a bioassay method rather than a gas chromatography method such as a GC / MS method.

JP 2003-114222 A (paragraph 0004, paragraph 0007) JP 2006-292654 A

In the pretreatment method described in Patent Document 1, since PCBs are extracted from the determination target for the purpose of measuring PCBs by the GC / MS method or the GC / ECD method, the obtained PCBs-containing extract is toluene. It becomes a hydrophobic solvent solution. Therefore, the extract obtained by the pretreatment method described in Patent Document 1 is difficult to apply to a bioassay method in which a hydrophilic solvent solution of PCBs needs to be used as an analysis sample.
Furthermore, it takes time and effort to prepare the extract from the oily liquid sample, and the time required for the treatment requires a long time of about 2 to 3 days.

  Accordingly, an object of the present invention is to provide an extraction apparatus capable of preparing a hydrophilic extract of PCBs in a short time by a simple operation from an oily liquid sample containing PCBs.

  In order to achieve the above object, the first characteristic configuration of the extraction apparatus according to the present invention is a polychlorinated biphenyl contained in the oily liquid sample in order to extract the polychlorinated biphenyls from the oily liquid sample containing the polychlorinated biphenyls. A first column containing a first filler that decomposes and adsorbs at least a part of impurities other than the first, a second column that adsorbs at least a part of the decomposed impurities, and polychlorinated biphenyls. A second column containing a third filler to be adsorbed; a connecting means capable of connecting or releasing the first column and the second column; and an aliphatic hydrocarbon solvent for dissolving the polychlorinated biphenyls. A first reservoir that can supply the aliphatic hydrocarbon solvent to the first column, a slide fixing means that is detachable by sliding the second column, and the second A holding mechanism having a switching means capable of switching the liquid flow direction inside the ram to a normal state or its reverse state, and a hydrophilic solvent that dissolves the polychlorinated biphenyls are stored, and the second column in the reverse state is stored. And a second reservoir capable of supplying the hydrophilic solvent.

Impure components other than polychlorinated biphenyls (PCBs) contained in the oily liquid sample added to the first column are rapidly decomposed by reaction with the first filler. This decomposition product is held in the first filler together with PCBs. Then, when the aliphatic hydrocarbon solvent stored in the first reservoir is supplied to the first column, the PCBs held in the first filler and some of the decomposition products are supplied to the supplied aliphatic hydrocarbon. It dissolves in the solvent and is discharged from the first column via the second filler from the first filler.
Here, a part of the decomposition product is adsorbed by the second filler and held in the first column. On the other hand, PCBs are discharged from the first column together with the aliphatic hydrocarbon solvent passing through the first column.

  When the aliphatic hydrocarbon solvent that has passed through the first column, that is, the aliphatic hydrocarbon solvent in which PCBs are dissolved, is supplied to the second column through the connecting means and passed through, it is dissolved in the aliphatic hydrocarbon solvent. PCBs that are present are trapped by the third filler. Impurity components other than PCBs remaining in the aliphatic hydrocarbon solvent pass through the second column together with the aliphatic hydrocarbon solvent without being captured by the third filler.

At this time, in the second column, most of PCBs are captured mainly by the third filler present at the end of the aliphatic hydrocarbon solvent on the supply side.
Here, the connection of the second column in the connecting means is released, and the second column is slid and mounted on the slide fixing means of the holding mechanism. At this time, since the second column can be attached to the holding mechanism by simply sliding, the attachment operation can be easily performed, and the process can be quickly transferred to the next step.

  With the second column attached to the slide fixing means, the liquid passing direction in the second column is switched from the normal state to the inverted state by the switching means. Thereby, the position of most PCBs captured by the third filler is changed from the end on the supply side, which is the upstream side of the aliphatic hydrocarbon solvent, in the third filler. It is changed to the end on the discharge side which is the downstream side in the direction.

  When the hydrophilic solvent stored in the second storage part in the inverted state is supplied to the second column and passed therethrough, the PCBs captured by the third filler are dissolved in the hydrophilic solvent and the second column. And is secured as a hydrophilic solvent solution.

In this way, since the hydrophilic solvent is supplied in a state where a high density portion of PCBs exists at the end portion on the discharge side, the second column captures the third filler near the end portion on the discharge side. By eluting the processed PCBs, most of the PCBs contained in the oily liquid sample can be extracted. Therefore, a desired amount of PCBs can be quickly extracted with a small amount of a hydrophilic solvent as compared with the case where the captured PCBs are eluted over the entire third filler.
Therefore, with the extraction device of this configuration, a hydrophilic extract of PCBs can be prepared in a short time with a simple operation, and the hydrophilic solvent solution of PCBs obtained by the extraction device is capable of decomposing PCBs (harmlessly Small amount that can be easily applied in various analyzes.

  The 2nd characteristic structure of the extraction apparatus which concerns on this invention exists in the point provided with the heating means which heats said 1st column and said 2nd column separately.

By heating the first column by the heating means, impurities other than PCBs contained in the oily liquid sample can be quickly decomposed by the first filler. Further, by heating the second column with a heating means, the PCBs can be quickly dissolved by the hydrophilic solvent.
Therefore, in this configuration, a hydrophilic extract of PCBs can be prepared in a shorter time.

  The third characteristic configuration of the extraction apparatus according to the present invention is that it comprises pressure adjusting means for adjusting the pressure inside the first column when the aliphatic hydrocarbon solvent is supplied to the first column. .

According to this configuration, by adjusting the pressure inside the first column by the pressure adjusting means, the flow rate of the aliphatic hydrocarbon solvent through the first column and the reaction rate in the first column are appropriately set. Can be adjusted to speed.
Therefore, in this configuration, the reaction with the aliphatic hydrocarbon solvent in the first column can be reliably performed.

  A fourth characteristic configuration of the extraction apparatus according to the present invention is that a drying means for drying the inside of the second column is provided.

  As in this configuration, by drying the inside of the second column before supplying the hydrophilic solvent to the second column, when the PCBs are dissolved with the hydrophilic solvent, the supplied hydrophilic solvent is Dilution can be prevented. Therefore, PCBs can be efficiently dissolved as compared with a diluted hydrophilic solvent.

  The fifth characteristic configuration of the extraction apparatus according to the present invention is that it includes a bubble removing means for removing bubbles present in the second column.

  As in this configuration, before supplying the hydrophilic solvent to the second column, the bubbles present inside the second column are removed by the bubble removing means, thereby bringing the third filler into contact with the hydrophilic solvent. It is possible to prevent the area from decreasing. Therefore, it is possible to prevent the contact opportunity between the third filler and the hydrophilic solvent from being lowered, so that PCBs can be efficiently dissolved.

  A sixth characteristic configuration of the extraction apparatus according to the present invention is that the first filler is silica gel sulfate.

  If sulfated silica gel is applied as the first filler as in this configuration, for example, when the oily liquid sample is an electrical insulating oil made of mineral oil, aromatic compounds that are impurities other than PCBs are reliably decomposed. Can be adsorbed.

  A seventh characteristic configuration of the extraction device according to the present invention is that the second filler is silver nitrate silica gel.

  If silver nitrate silica gel is applied as the second filler as in this configuration, for example, when an oily liquid sample is an electrical insulating oil made of mineral oil, it is generated by decomposing aromatic compounds that are impurities other than PCBs. Degradation products can be reliably captured.

  An eighth characteristic configuration of the extraction apparatus according to the present invention is that the third filler is alumina.

If alumina is applied as the third filler as in this configuration, the PCBs contained in the oily liquid sample are captured, and paraffins, which are impure components other than the aromatic compound contained in the oily liquid sample, It can be dissolved in an aliphatic hydrocarbon solvent and discharged through the second column together with the aliphatic hydrocarbon solvent.
Therefore, in this configuration, the purity of PCBs captured by the third filler can be increased.

  A ninth characteristic configuration of the extraction device according to the present invention includes a plurality of column units having the first column and the second column, and each of the column units is arranged at equal intervals on the same circumference in a top view. In the point.

By arranging a plurality of column units on the same circumference as in this configuration, when each column unit is held on the frame, in each column unit, the column unit from the outer circumference of the frame or the center of the circle Can be set equally. Further, by arranging a plurality of column units at equal intervals, the space around each column unit can be ensured equally.
Therefore, for example, even if the ambient temperature changes, it becomes easy to process each column unit under the same conditions, for example, the influence of the temperature acting on each column unit becomes the same. Therefore, in this configuration, it is possible to prepare a hydrophilic extract of PCBs by processing a plurality of specimens simultaneously in a short time.

Embodiments of the present invention will be described below with reference to the drawings.
The present invention relates to an extraction apparatus for extracting PCBs from an oily liquid containing PCBs.

  Examples of oily liquids containing PCBs include electrical insulating oils used in electrical equipment such as transformers, waste organic solvents containing PCBs produced in chemical experiments and chemical factories, and PCBs for analysis. These include an extract obtained by extracting PCBs from a sample with an organic solvent, and a decomposition treatment solution and a cleaning solution generated in a decomposition treatment facility for PCBs.

  Electrical insulating oil is usually composed of mineral oil mainly composed of paraffin, naphthene or aromatic compound having a relatively high boiling point obtained by rectifying petroleum, for the purpose of enhancing electrical insulation. There are cases where PCBs are contained when PCBs are added or when PCBs are mixed in during the production process.

  As shown in FIGS. 1 to 5, the extraction apparatus X of the present invention includes a first column 10 as a purification column, a second column 20 as an extraction column, and a connection between the first column 10 and the second column 20. And connecting means 30 that can be released.

  In addition, the extraction device X slides the first storage section 60 capable of storing an aliphatic hydrocarbon solvent that dissolves PCBs and supplying the aliphatic hydrocarbon solvent to the first column 10 and the second column 20. Detachable slide fixing means 91, a holding mechanism 90 provided with a switching means 92 that can switch the liquid passage direction inside the second column 20 to a normal state or its reverse state, and hydrophilicity that dissolves PCBs And a second reservoir 80 capable of storing the solvent and supplying the hydrophilic solvent to the inverted second column 20.

  In addition, the extraction device X of the present embodiment includes heating means 40 and 70 for heating the first column 10 and the second column 20 separately, a pressure adjusting means 55 for adjusting the pressure inside the first column 10, and a second column. 20 is provided with a drying means 110 for drying the inside of the 20 and a bubble removing means 120 for removing the bubbles existing inside the second column 20.

(First column)
The first column 10 includes a first filler 14 that decomposes and adsorbs at least part of impurities other than PCBs contained in the oily liquid sample, and a second filler that adsorbs at least part of the decomposed impurities. 15 is accommodated.
In the present embodiment, the upper layer has the first filler 14 and the lower layer has the second filler 15, which form the multilayer filler structure 13.

The first column 10 has a cylindrical shape in which the outer diameter and inner diameter of the lower end 10a are reduced, and has openings 11 and 12 at the upper end and the lower end, respectively. The first column 10 is formed using, for example, glass or plastic having solvent resistance and heat resistance.
The size of the first column 10 (the size of the portion that can be filled with the multilayer filler structure 13) is preferably about 10 to 20 mm in inner diameter and about 30 to 110 mm in length.

As the first filler 14, for example, silica gel sulfate can be applied. The sulfuric acid silica gel is prepared by uniformly adding concentrated sulfuric acid to the silica gel surface. The packing density of the sulfuric acid silica gel is not particularly limited, it is preferable to set the 0.3~1.1g / cm ^3, to set the 0.5 to 1.0 g / cm ³ More preferred.

For example, silver nitrate silica gel can be used as the second filler 15. Silver nitrate silica gel is prepared by uniformly adding an aqueous silver nitrate solution to the surface of the silica gel and then removing moisture by heating under reduced pressure. The packing density of the silver nitrate silica gel is not particularly limited, it is preferably set to 0.3 to 0.8 g / cm ^3, to set the 0.4 to 0.7 g / cm ³ More preferred.

  The ratio between the first filler 14 and the second filler 15 is preferably set to 1.0 to 50 times the weight ratio of the silica gel sulfate to the silver nitrate silica gel, and is set to 3.0 to 30 times. Is more preferable. When the weight ratio of the sulfuric acid silica gel exceeds 50 times, the ratio of the silver nitrate silica gel becomes small, so that the purification of the oily liquid by the adsorption action may be insufficient. On the contrary, when the weight ratio of the silica gel sulfate is less than 1.0 times, there is a possibility that the oily liquid is not sufficiently purified by the decomposition action.

(Second column)
The second column 20 accommodates a third filler 23 that adsorbs PCBs.
The second column 20 has a cylindrical shape whose outer diameter and inner diameter are set to be substantially the same as the lower end portion 10a of the first column 10, and has openings 21 and 22 at the upper end portion and the lower end portion, respectively. The second column 20 is formed using, for example, glass or plastic having solvent resistance and heat resistance.
The size of the second column 20 (the size of the portion that can be filled with the third filler 23) is preferably about 2.0 to 5.0 mm in inner diameter and about 10 to 200 mm in length.

  For example, alumina can be used as the third filler 23. Alumina having various activities can be used. The alumina is not particularly limited as long as it can adsorb PCBs, and may be any of basic alumina, neutral alumina, and acidic alumina.

Packing density of alumina is not particularly limited, is preferably set to 0.5 to 1.2 g / cm ^3, more to set the 0.8~1.1g / cm ³ preferable.

  The connection means 30 is formed so that the lower end portion 10a of the first column 10 and the upper end portion of the second column 20 are detachable, and the lower end portion 10a of the first column 10 and the upper end portion of the second column 20 are inserted. It is a possible cylindrical member. The connecting means 30 is formed using a material that is stable with respect to the aliphatic hydrocarbon solvent, for example, a plastic having solvent resistance and heat resistance.

(First reservoir)
The first storage unit 60 stores an aliphatic hydrocarbon solvent that dissolves PCBs held in the first column 10. The first reservoir 60 is connected to the first column 10 by a flexible tube or the like so that the aliphatic hydrocarbon solvent can be supplied to the first column 10.
The aliphatic hydrocarbon solvent is not particularly limited as long as it can dissolve PCBs. For example, n-pentane, n-hexane, n-heptane, n- which is an aliphatic saturated hydrocarbon solvent. Octane, isooctane, cyclohexane, etc. can be applied. In particular, n-hexane is preferable.

(Holding mechanism)
The holding mechanism 90 includes a slide fixing means 91 that can be detachably attached by sliding the second column 20, and a switching means 92 that can switch the liquid passing direction inside the second column 20 to a normal state or an inverted state thereof.
The slide fixing means 91 is constituted by, for example, a rail groove that slides the second column 20.
The switching unit 92 is configured to invert the vertical direction of the second column 20, for example. In this embodiment, the 2nd column 20 is rotated by rotating the switching means 92 connected with the 2nd column 20 of the state fixed at the edge part of a rail groove | channel. Thereby, the liquid flow direction in the inside of the 2nd column 20 can be switched to a normal state or its inversion state.
The normal state is a liquid passing direction when the solvent is passed in a state where the third filler 23 packed in the second column 20 is arranged on the upper side. On the other hand, the said inversion state is a liquid flow direction when letting a solvent pass in the state arrange | positioned so that the 3rd filler 23 with which the 2nd column 20 was filled may become the lower side.

(Second reservoir)
The second storage unit 80 stores a hydrophilic solvent that dissolves PCBs. In the present embodiment, the space portion of the second column 20 in the inverted state is used as the second storage portion 80. A hydrophilic solvent that dissolves PCBs is supplied to the second reservoir 80 using a pipette or the like.
The hydrophilic solvent is not particularly limited as long as it can dissolve PCBs. For example, dimethyl sulfoxide, acetonitrile, dimethylformamide, methanol, ethanol, propanol and the like can be applied. Of these, dimethyl sulfoxide, which can extract PCBs with a smaller amount of use, is preferred.

(Column unit)
The extraction device X can include a plurality of column units 1 having the first column 10 and the second column 20. In this embodiment, the case where the six column units 1 are provided is illustrated. Each of the plurality of column units 1 is arranged at equal intervals on the same circumference in a top view.
For example, when performing the heat treatment by the heating means, if the column units 1 are arranged at equal intervals on the same circumference, the column units 1 can be easily heat-treated under the same conditions.

The size of the column unit 1 can be appropriately set according to the purpose of extracting PCBs from an oily liquid sample to be described later. For example, when the purpose of pretreatment is to extract PCBs from an oily liquid sample in order to measure the concentration of PCBs contained in the oily liquid sample, a small or trace amount of the sample is collected from the oily liquid sample. Therefore, the column unit 1 can be set to be small in size accordingly.
On the other hand, when a PCB is extracted from an oily liquid sample contaminated with PCBs and a PCB is decomposed (detoxification process) in this extract, a relatively large amount of the oily liquid sample is processed. Since it is necessary, the column unit 1 is set to a large size according to the amount of oily liquid to be processed.

  For example, when measuring the concentration of PCBs contained in an electrical insulating oil made of mineral oil by a bioassay method, the PCBs are usually extracted from an oily liquid sample of about 1.0 to 500 mg collected from the electrical insulating oil. To do.

(Heating means)
The first column 10 and the second column 20 are respectively provided with a first heating means 40 and a second heating means 70 for heating them separately. The 1st heating means 40 and the 2nd heating means 70 are comprised by the heater, the Peltier device, etc.
For example, the 1st heating means 40 is the position (1st column) in which the 1st filler 14 is filled in the 1st column 10 so that the whole 1st filler 14 of the 1st column 10 may be heated to required temperature. 10 upper layer).
Further, the second heating means 70 is arranged around a position where the third filler 23 is packed in the second column 20 so as to heat the entire third filler 23 of the second column 20 to a required temperature. Deploy.

(Pressure adjustment means)
The pressure adjusting means 55 adjusts the pressure inside the first column 10.
When the aliphatic hydrocarbon solvent is supplied to the first column 10, the aliphatic hydrocarbon solvent can be rapidly passed by adjusting the pressure inside the first column 10.
FIG. 5 shows a state in which the pressure adjusting means 55 is arranged downstream of the pressure pump 52 that pressurizes and supplies the aliphatic hydrocarbon solvent to the first column 10.
In addition to such a configuration, the pressure adjusting means 55 can be configured by arranging a suction device at the lower end of the second column 20. The suction device includes, for example, a container that can hermetically accommodate the lower end portion of the second column 20 and a pump for decompressing the inside of the container. In this container, a solvent container for receiving the aliphatic hydrocarbon solvent passing through the column unit 1 is arranged.

(Drying means)
The drying unit 110 dries the inside of the second column 20. The drying means 110 is constituted by a blower or the like capable of supplying an inert gas such as dry air or nitrogen gas. The drying means 110 includes a cap-shaped connecting portion so that it can be connected to the upper end of the second column 20. Furthermore, the drying means 110 includes a fluid source such as a cylinder filled with the inert gas.

(Bubble removal means)
The bubble removing unit 120 removes bubbles present in the second column 20. The bubble removing means 120 is constituted by an ultrasonic vibration device that removes the bubbles by ultrasonic waves, for example.

<Method for extracting PCBs>
A method for extracting PCBs using the extraction apparatus X of the present invention will be described. Here, a case will be described in which PCBs are extracted from the electrical insulating oil in order to measure the concentration of PCBs contained in the electrical insulating oil made of mineral oil used in electrical equipment such as a transformer by a bioassay method. (FIG. 6).

First, the first column (purification column) 10 and the second column (extraction column) 20 are set to the first heating means 40 and the second heating means 70, respectively (FIG. 6: steps A and B). Thereafter, the first column 10 and the second column 20 are connected by the connecting means 30.
A small amount of oily liquid sample of about 1.0 to 500 mg is collected from the electrical insulating oil, and the oily liquid sample is added to the upper first filler (sulfuric acid silica gel) 14 from the opening 11 at the upper end of the first column 10. To do. And the 1st heating means 40 is operated and it maintains for the predetermined time, heating the upper layer of the 1st column 10 (FIG. 6: process C). Since the added oily liquid sample is held in the first filler 14, impurities other than PCBs contained in the oily liquid sample, in particular aromatic compounds, react with the silica gel sulfate of the first filler 14 to quickly Is broken down into The decomposition product of this reaction is captured by the first filler 14 and the second filler (silver nitrate silica gel) 15 and held in the first column 10.

The heating temperature by the first heating means 40 is set to at least 35 ° C., preferably 50 ° C. or higher, more preferably 60 ° C. or higher. When the heating temperature is less than 35 ° C., the reaction between the aforementioned impurities contained in the oily liquid sample and the silica gel sulfate does not proceed easily, so that it is difficult to extract PCBs from the oily liquid sample in a short time.
Usually, the heating time is preferably set to 10 minutes to 8 hours. When the heating time is less than 10 minutes, the above-described impurities contained in the oily liquid sample are not sufficiently decomposed, and there is a possibility that impurities other than PCBs may be mixed in the finally obtained extract.

  If the oily liquid sample contains a large amount of impure components other than PCBs, or if there is such a possibility, in this step, the oily liquid sample is added to the first filler 14 of the first column 10 and the hydrocarbon solvent Is preferably added (FIG. 6: Steps D and E). In this way, the oily liquid sample is diluted with the hydrocarbon solvent, the contact efficiency between the oily liquid sample and the silica gel sulfate is improved, and the reaction efficiency is increased. Therefore, impure components other than PCBs contained in the sample in a shorter time In particular, aromatic compounds can be efficiently decomposed in a short time.

  Available hydrocarbon solvents are usually aliphatic saturated hydrocarbon solvents having 5 to 8 carbon atoms, such as n-pentane, n-hexane, n-heptane, n-octane, isooctane and cyclohexane. However, it is necessary to select a hydrocarbon solvent having a boiling point equal to or higher than the heating temperature by the first heating means 40. When the boiling point of the hydrocarbon solvent does not satisfy this condition, the hydrocarbon solvent is quickly volatilized when the first column 10 is heated, so that the above-described reaction efficiency is hardly increased.

  The hydrocarbon solvent may be added continuously immediately after the oily liquid sample is added to the first filler 14 of the first column 10 or may be added to the oily liquid sample in advance.

  The first column 10 heated for a predetermined time in the above process is cooled to room temperature (usually room temperature of about 10 to 30 ° C.) after stopping the first heating means 40 (FIG. 6: process F).

Next, the first reservoir 60 for supplying the solvent to the first column 10 is attached to the opening 11 on the upper end side of the first column 10, and the aliphatic hydrocarbon solvent is stored in the first reservoir 60. . When the pump 52 is operated, the aliphatic hydrocarbon solvent stored in the first reservoir 60 is gradually and continuously supplied into the first column 10 (FIGS. 1, 5A, and 6). Process G, H).
The aliphatic hydrocarbon solvent supplied into the first column 10 flows in the first column 10 from the first filler 14 in the upper layer to the second filler 15 in the lower layer, and is connected from the opening 12 of the first column 10. It flows into the second column 20 from the opening 21 via the means 30.

  At this time, the PCBs held in the first filler 14 are dissolved in the aliphatic hydrocarbon solvent and flow into the second column 20. On the other hand, a part of the decomposition product held in the first filler 14 is dissolved in the aliphatic hydrocarbon solvent, moves to the second filler 15 in the lower layer, and is adsorbed on the silver nitrate silica gel to be absorbed in the first column 10. Retained.

  The aliphatic hydrocarbon solvent that has flowed into the second column 20 passes through the second column 20 and is discharged from the opening 22 to the solvent receiving container 53 (FIGS. 1 and 5A). At this time, PCBs dissolved in the aliphatic hydrocarbon solvent from the first column 10 are captured by the third filler (alumina) 23 of the second column 20 and held in the second column 20. .

  In particular, since PCBs are easily captured by alumina, they are mainly held near the opening 21 at the upper end in the second column 20. On the other hand, paraffins and the like, which are impure components other than the aromatic compound contained in the sample, dissolve in the aliphatic hydrocarbon solvent from the first reservoir 60 and pass through the second column 20 together with the aliphatic hydrocarbon solvent. It is discharged into the solvent receiving container 53.

  The amount of the aliphatic hydrocarbon solvent stored in the first reservoir 60, that is, the total amount of the aliphatic hydrocarbon solvent supplied to the first column 10 is usually preferably set to 10 to 120 ml. In addition, the supply rate of the aliphatic hydrocarbon solvent from the first reservoir 60 is usually preferably set to 0.2 to 3.0 ml / min by adjusting the pressure by the pump 52.

Next, the connecting means 30 is removed, the first column 10 and the second column 20 are separated, and the second column 20 is fixed to the slide fixing means 91 of the holding mechanism 90 (FIG. 6: Step I).
The second column 20 is heated to about 35 to 90 ° C. by the second heating means 70 disposed around the second column 20 (FIG. 6: step J).
The drying means 110 is attached to the opening 21 of the second column 20, the pump 52 is operated, and an inert gas such as dry air is supplied from the opening 21 at the upper end into the second column 20 by the drying means 110 (FIG. 2, FIG. 5 (b), FIG. 6: Steps K and L). Thereby, the aliphatic hydrocarbon solvent remaining in the second column 20 is discharged from the opening 22 at the lower end of the second column 20 together with the inert gas, and the aliphatic hydrocarbon solvent is removed from the second column 20. Is done. As a result, the alumina in the second column 20 is dried.

  The drying means 110 is removed from the second column 20, and the upper and lower sides of the second column 20 are inverted together with the second heating means 70 by the switching means 92 of the holding mechanism 90 (FIGS. 3, 5 (c), FIG. 6: Step M). . Then, a predetermined amount of hydrophilic solvent is supplied to the second reservoir 80 from the opening 22 moved to the upper end side of the second column 20 due to inversion (FIG. 6: Step N).

The hydrophilic solvent supplied to the second reservoir 80 naturally flows from the second reservoir 80 into the second column 20 due to its own weight, and is discharged to the solvent receiving container 54 from the opening 21 moved to the lower end side of the second column 20. (FIG. 5C, FIG. 6: Step O). At this time, the hydrophilic solvent dissolves the PCBs captured by the alumina of the second column 20 and discharges the PCBs from the opening 21.
At this time, bubbles existing inside the second column 20 are removed by the bubble removing means 120.

  Here, since PCBs are mainly captured by alumina in the vicinity of the opening 21, the amount of movement in the second column 20 is small when discharged from the second column 20. For this reason, substantially the total amount of PCBs captured by alumina is in a state of being mainly dissolved in the hydrophilic solvent in the first flow portion discharged from the second column 20. Accordingly, the hydrophilic solvent solution of PCBs obtained here, that is, the extracted solution of PCBs becomes a small amount that can be easily used in the analytical operation described later. Further, the PCBs obtained here are obtained by removing the aliphatic hydrocarbon solvent from the second column 20 and then supplying the hydrophilic solvent to the second column 20. It becomes a high-purity extract with little mixing of hydrocarbon solvent and impure components dissolved therein.

  According to the extraction method according to the present embodiment, the above-described extract can be obtained in a short time of about 2 to 10 hours from the work start process (sample addition process to the first column 10).

  In such an extraction step, the second column 20 is preferably supplied with a hydrophilic solvent while being heated by the second heating means 70. In general, the heating temperature of the second column 20 is preferably set to at least 35 ° C, more preferably set to 60 ° C or higher. If it does in this way, PCBs capture | acquired by the alumina of the 2nd column 20 will become easy to extract the whole quantity with a smaller amount of hydrophilic solvent. For this reason, the amount of PCBs extract can be set to a smaller amount that can be more easily used in an analysis operation by a bioassay method described later, particularly an analysis operation by a bioassay method using a low-sensitivity detector.

  When measuring the concentration of PCBs contained in electrical insulating oil, the extract obtained in the above extraction operation, that is, a hydrophilic solvent solution of PCBs is secured, and this assay is used as a sample for bioassay. Analyze by law. Bioassay methods include immunoassay methods such as enzyme-linked immunosorbent assay (ELISA method) and binding equilibrium exclusion method (KinexA method), and reporter gene responsiveness assay. : A method suitable for measurement of PCBs such as CALUX method).

[Another embodiment]
(1) In the above-described embodiment, the first column 10 is constituted by a single column, and the multilayer filler structure 13 is formed therein, but the first column 10 has two columns arranged vertically. They may be connected, and the upper column may be filled with silica gel and the lower column may be filled with silver nitrate silica gel.
Since the structure in which the first column 10 is separated in this way can save the trouble of filling the first column 10 with the first filler 14 and the second filler 15, the first column 10 is easily prepared. be able to.

(2) In the above-described embodiment, the hydrophilic solvent supplied to the second reservoir 80 is naturally supplied to the second column 20 by its own weight, but the hydrophilic solvent is a metering pump such as a syringe pump. Can also be supplied to the second column 20.
Thereby, extraction in the 2nd column 20 can be performed rapidly.

(3) In the above-described embodiment, the switching unit 92 illustrated the case where the second column 20 is turned upside down, but is not limited thereto. For example, the switching means can be configured to translate the second column 20 to a position where the liquid flow direction inside the second column 20 is in a normal state or a position where the liquid flow direction is reversed. . In this case, the solvent is supplied to the second column 20 from above at a position where the liquid passing direction is in a normal state. On the other hand, the solvent is supplied to the second column 20 from below at the position where the liquid flow direction is reversed.
In this configuration, since it is not necessary to reverse the second column 20, the holding mechanism 90 can be simplified if the second column 20 is configured to be translated by the slide fixing means 91, for example.

(4) In the above-described embodiment, the present invention focuses on the case where PCBs are extracted from a sample collected from the electrical insulating oil in order to measure the concentration of PCBs contained in the electrical insulating oil made of mineral oil. However, the present invention can also be used for other purposes. For example, electrical insulating oil and waste organic solvents containing PCBs need to be detoxified by decomposing PCBs at the time of disposal, but if the amount of disposal is large, such detoxification treatment is smoothly promoted. It can be difficult. Therefore, if the extraction device of the present invention is applied to electrical insulating oil or the like to be disposed of, PCBs contained in the electrical insulating oil or the like can be converted into a small amount of a hydrophilic solvent solution. It becomes easy to carry out.

  INDUSTRIAL APPLICATION This invention can be utilized for the extraction apparatus which extracts PCBs from the oily liquid containing PCBs.

Schematic of the extraction device of the present invention Schematic diagram of the extraction device when the first column and the second column are separated and the drying means is attached to the second column Schematic of the extraction device when the top and bottom of the second column is inverted by the holding mechanism switching means Schematic diagram of the essential parts of the extraction device when the first column and the second column are connected by a connecting means Schematic diagram schematically showing the extraction device in each extraction step Flow chart outlining each extraction process

Explanation of symbols

X Extractor 1 Column unit 10 First column 14 First filler 15 Second filler 20 Second column 23 Third filler 30 Connecting means 40 First heating means 55 Pressure adjusting means 60 First reservoir 70 Second heating Means 80 Second reservoir 90 Holding mechanism 91 Slide fixing means 92 Switching means 110 Drying means 120 Bubble removing means

Claims (9)

In order to extract the polychlorinated biphenyls from an oily liquid sample containing polychlorinated biphenyls,
A first filler that decomposes and adsorbs at least a part of impurities other than polychlorinated biphenyls contained in the oily liquid sample and a second filler that adsorbs at least a part of the decomposed impurities are accommodated. A first column;
A second column containing a third filler that adsorbs polychlorinated biphenyls;
A connecting means capable of connecting or releasing the first column and the second column;
Storing an aliphatic hydrocarbon solvent that dissolves the polychlorinated biphenyls, and a first storage section capable of supplying the aliphatic hydrocarbon solvent to the first column;
A slide fixing means that can be detachably mounted by sliding the second column, and a holding mechanism comprising a switching means that can switch the liquid flow direction inside the second column to a normal state or its reverse state;
Storing a hydrophilic solvent that dissolves the polychlorinated biphenyls, and a second storage section capable of supplying the hydrophilic solvent to the inverted second column;
Extraction device with.   The extraction apparatus according to claim 1, further comprising heating means for heating the first column and the second column separately.   The extraction apparatus according to claim 1, further comprising a pressure adjusting unit configured to adjust a pressure inside the first column when the aliphatic hydrocarbon solvent is supplied to the first column.   The extraction device according to any one of claims 1 to 3, further comprising a drying unit that dries the inside of the second column.   The extraction device according to any one of claims 1 to 4, further comprising a bubble removing unit that removes bubbles existing inside the second column.   The extraction device according to any one of claims 1 to 5, wherein the first filler is silica gel sulfate.   The extraction device according to any one of claims 1 to 6, wherein the second filler is silver nitrate silica gel.   The extraction device according to any one of claims 1 to 7, wherein the third filler is alumina.   A plurality of column units having the first column and the second column are provided, and each of the column units is arranged at equal intervals on the same circumference in a top view. The extraction device described.

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