JP2006226746A - Heat treatment apparatus for gas chromatography - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat treatment apparatus that gasifies solid or liquid and performs gas chromatography analysis, allows continuous multi-stage analysis in a saved space, and facilitates treatment such as derivatization. <P>SOLUTION: In the heat treatment apparatus, three or more shutters for preventing approach of a sample cup are disposed between a sample introduction port and a heating tube, a shutter nearest to the sample introduction port and a shutter nearest to the heating tube are sealable shutters, at least one shutter located between them is a special ventilating shutter, a plurality of gas introduction ports and gas exhaust ports are disposed, at least two introduction ports of an introduction port for putting a sample into the sample introduction port and an introduction port for putting liquid are provided, and these mechanisms are individually and automatically controlled. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a heat treatment apparatus for gas chromatography analysis for degassing analysis of solid and liquid, and further analysis of decomposition products and secondary reactants.

  In gas chromatography, the septum used for the sample inlet (injection) is plastic, and its heat resistant temperature is about 300 ° C. In addition, organic compounds that volatilize at about 300 ° C. and those that ionize positively to obtain a mass spectrum are not all. Methods other than these include methylation, silylation, bromination, etc. Is derivatized. In recent years, analysis is often carried out by reducing the molecular weight by thermal decomposition.

However, organic substances such as plastic products are rarely a single component, and when analyzing a mixture of various components, it is customary to save labor in analysis of analysis results by changing the heating temperature. It has been proposed to have a plurality of heating furnaces (Patent Document 1). In addition, there has been proposed an apparatus that performs such heating continuously and fully automatically.
JP 2000-28597 A

  However, these methods have a problem in that multi-stage continuous analysis with derivatization of a sample after low-temperature analysis cannot be performed, and there is no choice but to analyze independently depending on the heating temperature and the presence or absence of derivatization. Moreover, there existed a problem that an apparatus enlarged by having several heating furnaces. The present invention has been made in consideration of the technical background as described above, and an object of the present invention is to provide a heat treatment apparatus that can perform continuous multistage analysis in a small space and can be easily processed such as derivatization. To do.

  In order to solve the above-described problems in the present invention, the invention according to claim 1 is a heat treatment apparatus for performing gas chromatography analysis by gasifying a solid or liquid contained in a sample cup, and comprising a sample inlet and a heating In a heat treatment apparatus comprising a tube and an analysis gas hollow needle, and the heating tube is connected to a gas chromatography analyzer through the analysis gas hollow needle, a sample cup is placed between the sample introduction port and the heating tube at a predetermined position. The heat treatment apparatus is characterized in that it has three or more shutters for holding.

  The invention according to claim 2 is a hermetic shutter capable of sealing the shutter closest to the sample introduction port and the shutter closest to the heating tube, and is a ventilated shutter capable of venting at least one shutter positioned therebetween. A heat treatment apparatus according to claim 1.

  Further, the invention according to claim 3 is provided between the closed shutter closest to the sample inlet and the closed shutter closest to the heating tube, between the closed shutter and the heating tube closest to the heating tube, between the heating tube and the analysis gas injection needle. The heat treatment apparatus according to claim 1 or 2, wherein there are gas inlets at least at three locations.

  In the invention according to claim 4, the gas is provided in at least two places between the closed shutter closest to the sample inlet and the closed shutter closest to the heating tube, and between the closed shutter closest to the heating tube and the analysis gas injection needle. It was set as the heat processing apparatus in any one of Claim 1 thru | or 3 with a discharge port.

  The invention according to claim 5 is characterized in that there are at least two inlets for introducing a sample and an inlet for introducing a liquid at the sample inlet. It was set as the heat processing apparatus as described above.

  Further, the invention according to claim 6 is characterized in that the liquid can be introduced into the front chamber including the ventilation shutter and the closed shutter closest to the gas injection side through the introduction port for containing the liquid. The heat treatment apparatus according to Item 5 was used.

  The invention according to claim 7 has a mechanism in which the sample introduction port can automatically introduce a plurality of samples and liquids, and the sealing shutter, the ventilation shutter, the gas introduction port, and the gas discharge port are individually provided. The heat treatment apparatus according to any one of claims 1 to 6, which can be automatically controlled.

  The invention according to claim 8 is a gas chromatography apparatus provided with the heat treatment apparatus according to any one of claims 1 to 7.

  According to the present invention, a space-saving heat treatment apparatus can be provided as a heat treatment apparatus, a space for collecting an introduction cup and a space for temporarily storing a sample cup, and two or more stages of heat treatment are possible with a single sample introduction. It became. In addition, the environment between the shutter and the heating tube closest to the sample introduction port in the heat treatment apparatus can be set to a target atmosphere, and the pressure of the heating tube can be controlled. In addition, it is possible to introduce a liquid sample at any time, and it is possible to perform a heat treatment including a secondary reaction process by a single sample introduction. Moreover, it became possible to perform a heat processing and a secondary reaction process continuously with respect to several samples.

  By performing gas analysis using a gas chromatography apparatus equipped with the heat treatment apparatus of the present invention, the generated gas from a sample heated at two or more temperatures in a single sample introduction is analyzed stepwise. Became possible. In addition, it is possible to perform analysis step by step including the secondary reaction of the analysis gas generated from the sample heated at two or more temperatures by one sample introduction. As described above, it is possible to perform a gas chromatography analysis with a high throughput and excluding the influence of other components other than the target component. In addition, it is possible to continuously perform gas chromatography analysis on analysis gases generated by heat treatment and secondary reaction treatment on a plurality of samples.

  Below, the structure of the heat processing apparatus of this invention is demonstrated based on FIG. It should be noted that the idea of the present invention is not limited to this, but covers all technical scopes that can be considered from the specification. FIG. 1 is a schematic view of a cross section of the heat treatment apparatus of the present invention.

  In FIG. 1, the upper side of the drawing is the sample introduction side, and there is a sample introduction port 233. The sample introduction port 233 may have a rotary sample holder 101 and a liquid introduction syringe 112 capable of automatically introducing a plurality of sample cups 111. The sealing shutter X211 includes a valve that can be sealed and opened, the sealing shutter Y212 includes a valve that can be sealed and opened, and the ventilation shutter Z213 includes a valve that can be opened and has a hole that allows ventilation. The shutter X, the closed shutter Y, and the ventilation shutter Z can be individually controlled.

  A space constituted by the sealing shutter X211 and the ventilation shutter Z213 is a preliminary chamber 232, and a space constituted by the ventilation shutter Z213 and the sealing shutter Y212 is a front chamber 231. The heating tube 251 needs to keep the sample cup 111 in the heating tube, and the heating tube has a mechanism whose diameter is smaller than the diameter of the sample cup 111 on the analysis gas injection needle 271 side. The sample cup 111 is heated in a heating tube by a heating furnace (not shown).

  The gas inlet A301 is provided between the sealed shutter X211 and the sealed shutter Y212 for the purpose of replacing the preliminary chamber and the front chamber with carrier gas. The gas inlet B302 is provided between the closed shutter Y212 and the heating tube 251 for the purpose of introducing the carrier gas for analysis. The gas inlet C is provided between the heating tube 251 and the analysis gas injection needle 271 for the purpose of collecting the sample cup. The carrier gases introduced from the gas inlets A, B, and C may be different from each other, but are usually the same and an inert gas such as helium is used.

  The gas discharge port D311 is provided for discharging a replacement gas between the sealed shutter X301 and the sealed shutter Y212. The gas discharge port E312 is provided for discharging a surplus amount of the heat generation gas between the hermetic shutter Y212 and the heating tube 251. These gas inlets and gas outlets can be individually controlled.

  The analysis gas injection needle 271 is attached under the heating tube 251 and can be inserted into the septum 401 of the gas chromatography device. The analysis gas generated from the sample by the heat treatment device of the present invention is analyzed by gas chromatography and gas chromatography. Graphical mass spectrometry and the like are possible.

  Since the sample cup 111 is heated in the heating tube, it is desirable that the sample cup 111 be made of a material that is not easily deformed or deteriorated by heating, and a carbon-based organic material, metal, or glass can be used. The rotary sample cup holder 101 capable of setting a plurality of sample cups only needs to have a mechanism that can arrange a plurality of sample cups 111 and can introduce only a specific sample cup from the sample introduction port 233 into the heating tube 251. A commercially available autosampler can be used without any particular problem with a mechanism in which the sample cup 111 is dropped by gravity at a specific place having a hole.

  The syringe 112 for introducing the liquid, which is the liquid inlet, is a normal microsyringe, but needs a needle length that can introduce the liquid into the sample cup 111 existing in the front chamber 231. In addition, the liquid introduction syringe 112 is preferably provided with a mechanism that can inject a plurality of liquids.

  The sealing mechanism of the sealing shutter X211 and the sealing shutter Y212 is not particularly limited, but a ball valve or the like can be used. Further, the ventilation shutter Z213 may have a structure having holes in order to allow ventilation, but is not particularly limited. In addition, a hole can respond only by making a hole, and it can respond also with a pin. However, it is necessary that the sample cup does not pass through the ventilation portion. The sample introduction port 233, the preliminary chamber 232, and the front chamber 231 need a hollow structure having a diameter larger than that of the sample cup 111.

  The heating tube 251 needs to be hollow enough to contain the sample cup 111, and it is necessary to squeeze the hollow in order to keep the sample cup in the heating tube. Since this heating tube is heated from about 50 ° C. to about 1000 ° C. by a heating furnace (not shown), it is desirable that the heating tube is made of metal or quartz glass. Further, an insert for gas chromatography can also be used.

  The kind of the heating furnace (not shown) is not particularly limited, but it is better not to warm the wide area by a heater method. In addition, a heat insulating cover is also required so that the ambient temperature is difficult to cool.

  The material of the analysis gas injection needle 271 is not particularly limited as long as it is a metal, but it is necessary to prevent the analysis gas injection needle 271 from having such a length that the heat generation gas adheres.

  The materials for the gas inlets 301, 302, 303 and the gas outlets 311 and 312 are not particularly limited, but a stainless steel tube is convenient and convenient.

  It is desirable to control these members collectively by computer. The position of the introduction cup in the sample holder, the presence or absence of multistage control, the presence or absence of liquid sample introduction, the temperature of the heating furnace, the temperature program of the heating furnace, the shutter opening It is also necessary to control the timing of closing, the introduction time of the introduction amount of the carrier gas, etc. and the operation control of the gas chromatography simultaneously.

  Next, the usage pattern of the heat treatment apparatus of the present invention will be described.

(Two-stage heating / decomposition method)
The sample is placed in the sample cup 111 and covered with glass wool, and then set in the rotary sample cup holder 101. At this time, the hermetic shutter X211, the hermetic shutter Y212, and the ventilation shutter Z213 are all closed, and a very small amount of carrier gas is allowed to flow through the gas inlet A301 and the gas inlet C303, and the gas inlet B302 has a gas flow rate higher than the flow rate. Flow carrier gas.

  The sample cup is introduced from the predetermined number of the rotary sample cup holder 101 by opening the sealed shutter X211 and immediately after the introduction, the sealed shutter X211 is closed. After sufficiently flowing the carrier gas from the carrier gas inlet A301, the sealed shutter Z213 is opened, then the sealed shutter Y212 is opened, and the sample cup 111 is introduced into the heating tube 251. At this time, the heating tube 251 is set to a predetermined heating (decomposition) temperature. Further, it is necessary to input a measurement start signal to the gas chromatography apparatus when the sample cup 111 is introduced into the heating tube 251.

  During heating, the front chamber 231 and the preliminary chamber 232 are expected to be contaminated by the analysis gas generated from the sample. Therefore, the sealed shutter Y212 is closed immediately after the sample cup is introduced into the heating tube. The analysis gas is injected into the gas chromatography device through the analysis gas injection needle 271 and the gas chromatography side septum 401, and the gas chromatography analysis can be performed (first analysis).

  After heating the sample cup 111 for a predetermined time, the hermetic shutter Y212 is opened with the ventilation shutter Z213 closed, and a large amount of carrier gas is introduced from the gas inlet C303. At this time, the sample cup 111 is blown up by the carrier gas and discharged into the front chamber 231 below the ventilation shutter Z213. Immediately after this, the hermetic shutter Y212 is closed, and the mass supply of the carrier gas from the carrier gas inlet C303 is terminated. Next, the temperature of the heating tube 251 is raised to the heating (decomposition) temperature, and the sample cup is kept waiting in the front chamber 231 until the temperature reaches a predetermined temperature.

  When the heating tube 251 reaches a predetermined temperature, the hermetic shutter Y212 is opened, the sample cup 111 is again introduced into the heating tube 251, and a measurement start signal is input to the gas chromatography apparatus (second analysis). After the heating is completed, the sealed shutter Y212, the ventilation shutter Z213, and the sealed shutter X211 are opened, and the sample cup is discharged from the heat treatment apparatus by supplying a large amount of carrier gas from the carrier gas inlet C303.

(Two-stage heating / derivatization decomposition method)
The same process is performed until the first analysis shown in (Two-stage heating / decomposition method). After the heating, the sample cup 111 is held in the front chamber 231 and a predetermined amount of liquid is introduced from the liquid introduction syringe under a gas atmosphere. Next, the temperature of the heating tube is raised to the decomposition temperature, and the sample cup is kept waiting in the front chamber 231 until the temperature reaches a predetermined temperature. When the heating tube 251 reaches a predetermined heating (temperature), the hermetic shutter Y212 is opened, the sample cup 111 is again introduced into the heating tube 251, and the second analysis is performed as before.

  As described above, two examples of (two-stage heating / decomposition method) and (two-stage heating / derivatization decomposition method) have been described. By combining these two examples, multi-stage processing can be performed. Moreover, continuous automatic operation becomes possible by computer-controlling all of these. By starting the rotary sample cup holder 101 from a signal on the gas chromatography device side, continuous automatic operation is possible for a plurality of samples. The actual gas chromatographic analysis is started by opening the sealed shutter Y212 when the sealed shutter X211 is closed. The gas chromatographic analysis is completed at the end of the oven program of the gas chromatographic apparatus, and the gas chromatographic analysis sequence and the autosampler sequence can be synchronized by first collecting the introduction cup with the ready signal of the next measurement.

  Examples are shown below. The heat processing apparatus of this invention and the gas chromatography analyzer were connected. As gas chromatography, Agilent Technologies 6890 / 5973N and HP-5MS were used for the column. The insert was 280 ° C., He was used as the carrier gas, and was controlled in a constant flow rate mode (1.0 ml / min). In addition, a temperature raising program was applied to the gas chromatography oven, and analysis was performed with 285 ° C. being the maximum temperature. As a sample, polyethylene terephthalate resin added with 1% tributyl acetylcitrate was used. As a first analysis, gas chromatography analysis is performed on the analysis gas generated by heating the sample in a heat treatment apparatus at 200 ° C. for 60 seconds. As a second analysis, after the first analysis is completed, a sample cup is placed in the front chamber. Gas chromatography analysis was performed on the analysis gas generated by moving and heating the heated tube at 600 ° C. for 10 seconds.

  The same apparatus and sample as in Example 1 were used, and as a first analysis, the sample was heated in a heat treatment apparatus at 200 ° C. for 60 seconds, and a gas chromatography analysis was performed on the analysis gas generated. After completion of the first analysis, the sample cup was moved to the front chamber, and tetramethylammonium hydroxide was added to the sample through a liquid introduction syringe. Thereafter, a sample was introduced into a heating tube heated to 450 ° C., and gas chromatography analysis was performed on the analysis gas generated by heating for 10 seconds.

(Comparative Example 1)
In the same heat treatment apparatus as in Example 1, the sealing shutter X and the ventilation shutter Z were opened, and only the sealing shutter Y was opened and the sealing operation was possible. The gas inlet A and the gas outlet D were closed, and only the gas inlet B and the gas outlet C were operable. Moreover, the liquid introduction syringe was removed. This heat treatment apparatus was connected to the same gas chromatography apparatus as in Example 1, the same sample as in Example 1 was heated in the heat treatment apparatus at 200 ° C. for 60 seconds, and the generated analysis gas was subjected to gas chromatography analysis. .

(Comparative Example 2)
In the same heat treatment apparatus as in Example 1, the sealing shutter X and the ventilation shutter Z were opened, and only the sealing shutter Y was opened and the sealing operation was possible. The gas inlet A and the gas outlet D were closed, and only the gas inlet B and the gas outlet C were operable. Moreover, the liquid introduction syringe was removed. This heat treatment apparatus was connected to the same gas chromatography apparatus as in Example 1, and the same sample as in Example 1 was heated in the heat treatment apparatus at 450 ° C. for 10 seconds, and a gas chromatography analysis was performed on the analysis gas generated.

(Comparative Example 3)
In the same heat treatment apparatus as in Example 1, the sealing shutter X and the ventilation shutter Z were opened, and only the ventilation shutter Y was opened and the sealing operation was possible. The gas inlet A and the gas outlet D were closed, and only the gas inlet B and the gas outlet C were operable. Moreover, the liquid introduction syringe was removed. This heat treatment apparatus was connected to the same gas chromatography apparatus as in Example 1. Analytical gas generated by adding tetramethylammonium hydroxide to the same sample as in Example 1 before introduction into the heat treatment apparatus, and then introducing the sample into the heat treatment apparatus and heating at 450 ° C. for 10 seconds. The gas chromatographic analysis was performed.

  Table 1 shows the fragments detected in the gas chromatography analysis of Examples 1 and 2 and Comparative Examples 1, 2 and 3.

  From the above, it was confirmed that the analysis gas generated from the sample heated at two or more temperatures by one sample introduction could be analyzed stepwise. Moreover, it was confirmed that the generated gas from the sample heated at two or more temperatures by one sample introduction could be analyzed step by step including the secondary reaction of the generated gas.

It is the schematic of the heat processing apparatus cross section of this invention.

Explanation of symbols

101 Rotating Sample Cup Holder 111 Sample Cup 112 Liquid Introducing Syringe 211 Sealed Shutter X
212 Sealed shutter Y
213 Ventilation shutter Z
231 Front chamber 232 Preliminary chamber 233 Sample inlet 251 Heating tube 271 Analysis gas injection needle 301 Carrier gas inlet A
302 Carrier gas inlet B
303 Carrier gas inlet C
311 Gas outlet D
312 Gas outlet E
401 Septum

Claims (8)

  A heat treatment apparatus for performing gas chromatography analysis by gasifying a solid or liquid contained in a sample cup, comprising a sample introduction port, a heating tube, and an analysis gas hollow needle, and the heating tube comprising the analysis gas hollow needle In the heat treatment apparatus connected to the gas chromatography analyzer via the heat treatment apparatus, the heat treatment apparatus has three or more shutters for holding a sample cup in a predetermined position between the sample introduction port and the heating tube. .   2. The heating according to claim 1, wherein the shutter closest to the sample introduction port and the shutter closest to the heating tube are hermetically sealed shutters, and at least one shutter positioned therebetween is a ventilated shutter capable of venting. Processing equipment.   There are gas inlets at least at three locations between the closed shutter closest to the sample inlet and the closed shutter closest to the heating tube, between the closed shutter and the heating tube closest to the heating tube, and between the heating tube and the analysis gas injection needle. The heat treatment apparatus according to claim 1, wherein the heat treatment apparatus is provided.   4. The gas discharge port according to claim 1, wherein there are gas discharge ports at least at two positions between the closed shutter closest to the sample introduction port and the closed shutter closest to the heating tube, and between the closed shutter closest to the heating tube side and the analysis gas injection needle. The heat processing apparatus in any one.   5. The heat treatment apparatus according to claim 1, wherein the sample introduction port includes at least two introduction ports, an introduction port for introducing a sample and an introduction port for introducing a liquid.   6. The heat treatment apparatus according to claim 5, wherein the liquid can be introduced into a front chamber comprising a ventilation shutter and a closed shutter closest to the gas injection side through the introduction port for introducing the liquid.   The sample introduction port has a mechanism capable of automatically introducing a plurality of samples and liquids, and the hermetic shutter, the ventilation shutter, the gas introduction port, and the gas discharge port can be individually automatically controlled. The heat processing apparatus in any one.   A gas chromatography apparatus comprising the heat treatment apparatus according to claim 1.

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