JP2005083968A - Sample heating device, chromatographic analysis pretreatment method using device, and chromatographic analysis method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sample heating device capable of heating simply and safely a sample enclosed in a sample tube, and suppressing to the utmost influence caused by deterioration of a sealing member of the sample tube or the like. <P>SOLUTION: This sample heating device 1 is equipped with case members 10, 20, a metal heating block 30 stored or placed in the case members 10, 20, and a heater disposed in the case members 10, 20 in the heatable state of the heating block 30. In the device, at least one sample tube loading hole part 31 capable of loading the sample tube 4 formed by sealing an opening part of a vial 43 into which the sample is inputted by a resin sealing member 41 and a cap 42 is formed on the surface of the heating block 30, and the depth of the sample tube loading hole part 31 is formed to be such a depth that the resin sealing member 41 does not penetrate inside the sample tube loading hole part 31 when loading the sample tube 4, and the sample in the sample tube 4 is heated up to at least 200°C or higher, and thereby a high-boiling-point component existing in the sample is volatilized and/or the sample is pyrolytically decomposed at a high temperature. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a sample heating device, a chromatographic analysis pretreatment method using the same, and a chromatographic analysis method.

Conventionally, in gas chromatographic analysis or the like, various components such as a high boiling point component generated from a sample exposed to a high temperature and a thermal decomposition product have been measured.
As a sample tube used for these analytical methods, a glass vial is generally covered with a resin sealing member, and further covered with an aluminum cap, which is crimped and sealed. It is used (see Patent Documents 1 and 2 and Non-Patent Document 1).

In this case, although a material excellent in heat resistance and sealing properties such as a fluororesin-coated silicone resin is used as the sealing member, the sealing member deteriorates sufficiently when exposed to a high temperature exceeding 200 ° C. Not only can sealing performance not be maintained, but there are also cases where the analysis is adversely affected by impurities being released from the sealing material.
For this reason, in order to analyze pyrolyzate generated at a high temperature exceeding 200 ° C., a sample is sealed in an ampoule, heated at a high temperature, the ampoule is opened, and the high-temperature decomposition generated inside Methods such as measuring components and the like, or introducing a sample directly into a high-temperature furnace under an inert gas stream to measure high-temperature decomposition components have been adopted.

JP-A-8-122313 Japanese Patent Laid-Open No. 2002-40006 Supervised by Tomoyuki Hobo, “Purification Technology System Volume 1, Analytical Technology”, Fuji Techno System, 1996, p. 878-880, p. 885-891

However, the method using an ampoule is not only troublesome in measuring, but also requires work such as heating and melting the glass to seal it, or cutting and opening the glass. was there.
On the other hand, the method of directly introducing a sample into a high-temperature furnace and heating it in an inert gas atmosphere is simpler and safer than the method using an ampoule, but the sample is usually used in an atmospheric atmosphere (the presence of oxygen). In spite of the above), since the heating is performed at high temperature in an inert gas atmosphere, it cannot be said that it accurately reflects the thermal decomposition products generated under the actual use conditions.

  The present invention has been made in view of such circumstances, and is capable of heating the measurement sample enclosed in the sample tube easily and safely, and further suppressing the influence of deterioration of the seal member of the sample tube as much as possible. It is an object of the present invention to provide an apparatus, a chromatographic analysis pretreatment method and a chromatographic analysis method using the same.

  In order to solve the above-mentioned problems, a sample heating apparatus according to the present invention is provided with a case member, a metal heating block housed or placed in the case member, and the heating block disposed in the case member so as to be heated. In the sample heating apparatus including the heater, at least one sample tube loading hole that can be loaded with a sample tube formed by sealing the opening of the vial into which the sample is charged with a resin seal member and a cap is provided on the surface of the heating block. At the same time, the depth of the sample tube loading hole is formed such that the resin seal member does not enter the sample tube loading hole when the sample tube is loaded, and the sample in the sample tube is at least 200 ° C. Heating as described above volatilizes high boiling point components present in the sample and / or causes the sample to be thermally decomposed at high temperature.

  By setting the depth of the sample tube loading hole formed in the metal heating block to such a depth, the resin seal member is not directly heated by the heating block, and therefore the resin seal at a high temperature of 200 ° C. or higher. Deterioration of the member can be prevented, and as a result, problems such as deterioration of the sealing performance of the sample tube and difficulty in analysis due to the influence of impurities generated due to deterioration of the resin seal member are minimized. Can be suppressed.

  In this case, it is particularly preferable that the depth of the sample tube loading hole is set so that the distance from the uppermost surface of the sample tube to the heating block surface is 1 cm or more, particularly 2 cm or more when the sample tube is loaded. . In this way, it is possible to reliably prevent deterioration of the seal member due to heat while reliably heating the sample in the sample tube at 200 ° C. or higher. The upper limit of the distance from the uppermost surface of the sample tube to the surface of the heating block is usually such that the lower half of the vial fits in the sample tube loading hole, but the amount of sample put into the sample tube, the volume of the vial, etc. It cannot be specified in general because it is a substitute.

  The shape of the sample tube loading hole is not particularly limited as long as it can be loaded into the heating block by inserting a sample tube or the like, and the cut surface perpendicular to the sample tube loading (insertion) direction is a rectangular recess or the like. Although the cut surface can adopt a circular recess or the like, since the generally used vial has a substantially cylindrical shape, the cut surface is adapted so that it can be adapted and the sample can be heated efficiently. It is preferable to adopt a circular recess. Note that the number of sample tube loading holes formed in the heating block is also arbitrary, and may be determined as appropriate.

The heating block may include a plurality of types of sample tube loading holes having different depths. In other words, when measuring by changing the amount of sample and the volume of the vial by using a heating block with sample tube loading holes of various depths according to the amount of sample to be added and the volume of the vial to be used, etc. However, it is possible to cope with one type of heating block.
In addition, the heating block may be fixed to a case member that accommodates the heating block or a sample heating device constituting member such as a heater by appropriate fixing means such as bolting or welding, but this is a detachable structure. You can also.

  In this way, the heating block can be removed and replaced, so even if continuous analysis is performed, if the heated heating block is replaced with another heating block, the heated heating block is heated to a high temperature. Since no time is required for cooling, continuous and efficient analysis is possible. In this case, one heating block may be formed with a single depth sample tube loading hole, and as described above, a plurality of types of sample tube loading holes with different depths are formed. It may be.

The heating block of the present invention can be manufactured by forming a sample tube loading hole in a metal block by cutting using a drilling machine or the like, and creating a mold corresponding to the shape of the heating block required. The mold can also be formed by pouring molten metal into the mold.
The metal material constituting the heating block is not particularly limited as long as it does not cause deformation due to heat even when heated to 200 ° C. or higher, preferably 300 ° C. or higher. In view of the properties and production costs, aluminum, copper, brass and the like are preferable, and aluminum is particularly preferable.
The shape of the heating block is not particularly limited, and any shape such as a prismatic shape, a cylindrical shape, or a truncated cone shape can be adopted.

  The case member in the sample heating apparatus of the present invention is not particularly limited as long as it can accommodate a heating block, a heater, etc. For example, a metal case member formed in a box shape or the like is used. Can do. In this case, a mode in which the heating block is housed or placed in the case member is not particularly limited, and examples thereof include a mode in which the heating block is fitted into a recess formed in the case member.

The heater is not particularly limited as long as it can be heated to 200 ° C. or higher, and a heater used in a conventionally known heating dry bath can be used. For example, an electric heater, a ceramic heater, or the like can be used. Can be used. This heater can be disposed in the sample heating apparatus at an arbitrary position where the heating block can be heated. For example, the heater may be disposed on the bottom surface side of the heating block or on the side surface thereof. These may be combined. The temperature of the heater can be adjusted with a known thermostat or the like.
In addition, the sample heating apparatus of this invention can also divert the structural member of a well-known heating dry as it is as structural members other than the metal heating block mentioned above.

  The sample tube is not particularly limited as long as it is composed of a vial, a resin seal member and a cap, and a conventionally known tube used for headspace gas chromatographic analysis or the like is appropriately selected and used. be able to. In this case, as a material of the seal member, a known seal member obtained by applying a heat resistant coating such as butyl rubber, silicone rubber, or a fluororesin such as polytetrafluoroethylene may be appropriately selected and used.

In the sample heating apparatus of the present invention, as described above, since the seal member is located outside the sample tube loading hole of the heating block, even if a seal member that is susceptible to thermal deterioration is used, it is directly heated. There is no. However, since the sample is heated at a high temperature of 200 ° C. or higher and, depending on the sample, at a high temperature of 300 ° C. or higher, it is preferable to use a seal member having excellent heat resistance obtained by applying a fluororesin coating to silicone rubber.
As the cap, a metal cap such as a commonly used aluminum cap or a resin cap such as a polyethylene cap may be appropriately selected and used, but an aluminum cap having excellent heat resistance is preferably used. .

The chromatographic analysis method according to the present invention is to measure a heat-treated sample with a chromatographic analyzer after subjecting the sample to high-temperature heat treatment (pretreatment) with the above-described sample heating apparatus.
In this case, as the pretreatment by the sample heating device, after the sample is put into the vial, the opening of the vial is sealed with a resin seal member and a cap to prepare a sample tube. The sample is loaded into the sample tube loading hole of the heating block provided in the heating device, and then the heating block is heated to at least 200 ° C. or more by the heater to volatilize the high boiling point component in the sample and / or the sample is pyrolyzed. It is something to be made.
When preparing the sample tube, air is enclosed so that it is possible to examine the behavior of the measurement sample in an atmosphere with oxygen, which is a general use condition, and at high temperatures. It is preferable to keep it.

At this time, the heat treatment temperature is 200 ° C. or higher, and varies depending on the type of sample to be measured, but is preferably 250 ° C. or higher, more preferably 300 ° C. or higher, and the upper limit is usually 350 ° C. It is about -400 degreeC. Also, the heating time varies depending on the type of sample and the like, but is usually about 1 minute to 24 hours.
Examples of the sample to be measured include resin materials used under conditions exposed to high temperatures, and examples thereof include silicone oil, silicone rubber, silicone resin, fluororubber, and epoxy resin.

When measuring a sample pretreated with the sample heating device with a chromatographic analyzer, the heat-treated sample tube is loaded into the heating furnace of the chromatographic analyzer and the high-boiling components and / or pyrolysis generated by the pretreatment are performed. A method of detecting a component can be employed.
Measurement can also be performed by extracting a gas component such as a decomposition product generated from a sample by heating with a syringe or the like and directly injecting it into a gas chromatograph analyzer.
Further, after pretreatment, the contents of the sample tube are extracted with an organic solvent or water, and the extracted components are injected into a chromatographic analyzer to detect a high boiling point component and / or a pyrolysis component. You can also.

Here, as a chromatograph analyzer, various conventionally known chromatograph analyzers can be used, for example, a gas chromatograph analyzer (GC), a gas chromatograph mass spectrometer (GC-MS), an ion chromatograph analysis. Equipment (IC), high performance liquid chromatograph analyzer (HPLC), gel filtration chromatograph analyzer (GPC), etc., which are appropriately selected according to the sample to be measured, components generated by pretreatment, etc. be able to.
If there is a vial dedicated to the chromatographic analyzer to be used, a sample tube may be prepared using the vial and pretreated by the sample heating device described above. In this case, a heating block having a sample tube loading hole corresponding to the shape, size, etc. of the dedicated vial may be formed in advance.

  As described above, according to the present invention, there is provided a sample heating apparatus that can easily and safely heat a measurement sample enclosed in a sample tube and suppress the influence of deterioration of a seal member of the sample tube as much as possible. be able to. This heating device is commonly used for gas chromatographic analysis (GC), gas chromatograph mass spectrometry (GC-MS), ion chromatographic analysis (IC), high performance liquid chromatographic analysis (HPLC), gel filtration chromatographic analysis (GPC), etc. Therefore, it is possible to easily analyze a high-temperature decomposition product in the presence of oxygen, which has been difficult or impossible to analyze conventionally.

Hereinafter, an embodiment of the present invention will be described.
FIG. 1 shows a sample heating apparatus 1 according to an embodiment of the present invention. The heating device 1 is mounted on a plastic lower case member 10 provided with a temperature setting unit 11, a thermometer 12, and a switch 13 including a digital display unit 11 </ b> A and operation buttons 11 </ b> B, and the lower case member 10. A metal upper case member 20 that is placed and fixed and has a concave heating block fitting portion 21 formed on the upper surface thereof, and a substantially rectangular parallelepiped aluminum member that is detachably fitted and accommodated in the fitting portion 21. And a heating block 30.

The lower case member 10 includes a heater and a thermostat (not shown) therein.
The upper case member 20 fixed to the lower case member 10 by bolting or the like includes a plurality of radiating slits 22A formed at predetermined intervals in the circumferential direction of the upper case member 20 at the lower portion of the side surface 22 thereof. ing.
A plurality of sample tube loading holes 31 are formed in the heating block 30, and the depth of the sample tube loading holes 31 is determined by the resin seal member 41 when the sample tube 4 is loaded. However, in this embodiment, as shown in FIG. 2, the depth D of the sample tube loading hole 31 is set so that the sample tube 4 is inserted when the sample tube 4 is inserted. The distance H between the uppermost surface A of the tube 4 and the surface B of the heating block 30 is set to 2 cm.

A method of using the sample heating apparatus 1 configured as described above will be described.
First, the heating temperature is set with the operation button 11B of the temperature setting unit 11 provided on the lower case member 10 of the sample heating apparatus 1 (this set temperature is displayed on the digital display unit 11A), and then the sample is set. 5 is covered with a silicone sealing member 41 (resin sealing member) coated with polytetrafluoroethylene, and further covered with an aluminum cap 42 (cap) and caulked. The sample tube 4 formed by sealing is inserted into the sample tube loading hole 31 of the heating block 30. Thereafter, the switch 13 provided in the lower case member 10 is turned on, and the sample 5 in the sample tube 4 is heated at the target 300 ° C. for 1 minute to 24 hours to volatilize the high boiling point component in the sample 5 and / or Alternatively, the sample 5 is thermally decomposed.

  As shown in FIG. 3, the heated sample tube 4 is put into a heating furnace 61 of a head space gas chromatograph analyzer 6 (hereinafter abbreviated as head space GC), and then, in a head space sampler 62, A high boiling point component and a thermal decomposition component generated from the sample 5 are extracted and introduced into the gas chromatograph 63 for analysis and detection. In this case, the temperature in the heating furnace 61 of the head space GC6 is the heating temperature used in the sample heating apparatus 1 as much as possible so that the high boiling point components and pyrolysis components generated from the sample 5 can be extracted as they are. However, if the time for setting the sample tube 4 in the heating furnace 61 becomes long, the seal member 41 (see FIGS. 1 and 2) of the sample tube 4 deteriorates, and impurities are generated. Since there is a high possibility that the sealing performance is lowered, the temperature is preferably about 200 ° C.

In the above embodiment, the heating block 30 of the sample heating apparatus 1 is detachably fitted to the fitting portion 21 of the upper case member 20, but the present invention is not limited thereto, and a bolt or the like is attached to the upper case member. It may be fixed by the fixing means.
Further, the plurality of sample tube loading holes 31 formed in the heating block 30 are all set to the same depth D. However, the present invention is not limited to this, and as shown in FIG. First to third sample tube loading holes 31A, 31B, and 31C having different depths according to the capacities of 4B and 4C may be formed. Note that the depth of the sample tube loading hole may be appropriately determined according to the sample tube to be used, and the arrangement method and number thereof are also arbitrary.
Further, the depth of the sample tube loading hole 31 is formed such that the distance H between the uppermost surface A of the sample tube 4 and the surface B of the heating block 30 is 2 cm when the sample tube 4 is inserted. However, the present invention is not limited to this, and the resin seal member can have an appropriate depth as long as the resin seal member does not enter the sample tube loading hole.

In the above embodiment, the heating temperature by the sample heating apparatus 1 is 300 ° C., but is not limited to this, and can be set as appropriate depending on the type of the sample to be measured.
Further, although the head space GC6 is used as a measuring device capable of measuring the pyrolyzate generated from the sample 5 in the heating furnace or the like together with the sample tube 4, the head space gas chromatograph mass is not limited to this. An analyzer or the like can also be used. In addition, water or an organic solvent is introduced into the sample tube after heating using a syringe or the like, and the pyrolyzate generated from the sample is extracted. Then, the extracted components together with the solvent are ion chromatograph measuring device, high performance liquid chromatograph. By injecting into a graph measuring device, a gel filtration chromatograph measuring device, etc., detection by each measuring device can also be performed.
In addition, after extracting as needed, an extraction component can also be measured and analyzed using a high-speed liquid chromatograph measuring apparatus, a gel filtration chromatograph measuring apparatus, etc.

  In addition, the shape and material of each member constituting the sample heating apparatus, the shape of the vial constituting the sample tube, the material of the resin seal member and the cap are not limited to the above examples, and the object of the present invention is As long as it can be achieved, it can be changed as appropriate.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example.

[Example 1]
0.1 g of dimethylpolysiloxane having a viscosity of 1000 mm ² / s (1000 cSt) was collected in a 20 mL vial, and the vial opening was sealed with a fluororesin-coated silicone sealing member and an aluminum cap to prepare a sample tube. This sample tube was heated at 200 ° C. for 3 hours by the sample heating apparatus 1 provided with the above-described aluminum heating block. The gas generated at this time was analyzed by the head space GC. The analysis results are shown in FIG.

[Example 2]
A head space GC analysis was performed after heating with the sample heating apparatus 1 in the same manner as in Example 1 except that the heating temperature was 300 ° C. The analysis results are shown in FIG.
From these results, it was confirmed that the amount of low-molecular cyclic dimethylsiloxane gas generated was increased in the sample heated at 300 ° C. than in the sample heated at 200 ° C.

[Example 3]
0.1 g of dimethylpolysiloxane having a viscosity of 1000 mm ² / s (1000 cSt) was collected in a 20 mL vial, and the vial opening was sealed with a fluororesin-coated silicone sealing member and an aluminum cap to prepare a sample tube. The sample tube was heated at 200 ° C. for 3 hours by the sample heating apparatus 1 having the aluminum heating block described above, and then aldehydes were derivatized with 2,4-dinitrophenylhydrazine (DNPH), and HPLC was performed. Analysis was carried out. The analysis results are shown in FIG.

[Example 4]
The sample was heated by the sample heating apparatus 1 in the same manner as in Example 3 except that the heating temperature was 300 ° C., and then HPLC analysis was performed. The analysis results are shown in FIG.
From these results, aldehydes were not detected from the sample heated at 200 ° C., but formaldehyde was detected from the sample heated at 300 ° C.

It is a perspective view which shows the sample heating apparatus which concerns on one Embodiment of this invention. It is a schematic sectional drawing which shows the metal heating block and sample tube which concern on embodiment of FIG. It is a schematic diagram which shows the gas chromatograph analysis method which concerns on one Embodiment of this invention. It is a schematic sectional drawing which shows the metal heating block and sample tube which concern on the modification of this invention. 2 is a GC chromatogram showing the analysis result of Example 1. 6 is a GC chromatogram showing the analysis result of Example 2. 4 is an HPLC chromatogram showing the analysis results of Example 3. 6 is an HPLC chromatogram showing the analysis result of Example 4.

Explanation of symbols

1 Sample heating device 4 Sample tube 5 Sample 6 Headspace gas chromatograph analyzer (chromatograph analyzer)
10 Lower case member (case member)
20 Upper case member (case member)
30 Aluminum heating block (Metal heating block)
31 Sample tube loading hole 41 Resin sealing member 42 Cap 43 Vial 61 Heating furnace

Claims (7)

A sample heating apparatus comprising a case member, a metal heating block housed or placed in the case member, and a heater disposed in the case member so as to heat the heating block,
On the surface of the heating block, there is formed at least one sample tube loading hole that can be loaded with a sample tube formed by sealing the opening of a vial into which a sample has been charged with a resin seal member and a cap. The depth of the sample tube loading hole is formed such that the resin seal member does not enter the sample tube loading hole when the sample tube is loaded, and the sample in the sample tube is at least 200 ° C. or higher. The sample heating apparatus is characterized in that the high boiling point component present in the sample is volatilized by heating and / or the sample is pyrolyzed at high temperature.   The sample heating apparatus according to claim 1, wherein the metal heating block includes a plurality of types of sample tube loading holes having different depths.   The sample heating apparatus according to claim 1 or 2, wherein the metal heating block is detachable from the case member.   The depth of the sample tube loading hole is formed so that the distance from the uppermost surface of the sample tube to the surface of the heating block is 1 cm or more when the sample tube is loaded. Item 4. The sample heating apparatus according to any one of Items 1 to 3. A pretreatment method for chromatographic analysis using the sample heating apparatus according to claim 1,
After the sample is put into the vial, the opening of the vial is sealed with a resin seal member and a cap to prepare a sample tube, and this sample tube is loaded into the sample tube loading hole of the heating block, followed by A pretreatment method for chromatographic analysis, wherein the heating block is heated to at least 200 ° C. or more by the heater to volatilize a high-boiling component in the sample and / or the sample is thermally decomposed. A chromatographic analysis method using the sample heating apparatus according to claim 1,
After the sample is put into the vial, the opening of the vial is sealed with a resin seal member and a cap to prepare a sample tube, and this sample tube is loaded into the sample tube loading hole of the heating block, followed by The heating block is heated to at least 200 ° C. or more by the heater to volatilize high boiling point components in the sample and / or thermally decompose the sample, and then the sample tube is used as a heating furnace of a chromatographic analyzer. A chromatographic analysis method comprising loading and detecting the high boiling point component and / or the pyrolysis component. A chromatographic analysis method using the sample heating apparatus according to claim 1,
After the sample is put into the vial, the opening of the vial is sealed with a resin seal member and a cap to prepare a sample tube, and this sample tube is loaded into the sample tube loading hole of the heating block, followed by After the heating block is heated to at least 200 ° C. or more by the heater to volatilize high boiling point components in the sample and / or the sample is thermally decomposed, the contents of the sample tube are changed to an organic solvent or water And extracting the extracted component into a chromatographic analyzer and detecting the high boiling point component and / or the thermal decomposition component.

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