JPH0875719A - Device and method for analyzing gas generated by heating - Google Patents

Abstract

PURPOSE: To supply an optional gas to a sample heating gas line and a separation and analysis gas line by providing the sample heating gas line to a sample heating part via a pressure adjustor from a container filled with the optional gas. CONSTITUTION: An optional gas 6 is made to flow into a sample heating gas line to a sample tube 2 and a trap 3 via a pressure adjustor 1 from a container filled with the optional gas 6 during the heating of a sample. The tube 2 is heated and the gas generated is trapped into a trap 3. In the analysis of the sample, an inert gas 7 is made to flow into a separating and analysis gas line to a transfer line/analyzer 5 via a pressure adjustor 9 and a changeover valve 4 from a container filled with the inert gas 7. Then, the trap 3 is heated and the gas separated is supplied to the analyzer 5 together with the inert gas 7. Thus, for example, when oxygen is supplied as the optional gas 6, a polymer can be heated in an atmosphere the same as that in molding and working.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat generation gas analysis device and a heat generation gas analysis method.

[0002]

2. Description of the Related Art Conventionally, various samples are heated under an inert gas stream such as helium or nitrogen at an arbitrary temperature and time condition, and the generated gas is trapped at a room temperature or in a trap using a hollow or an appropriate packing material. A method of collecting components at low temperature and rapidly heating the trap (thermal desorption method) and introducing the components into a gas chromatograph (GC) or a gas chromatograph-mass spectrometer (GC-MS) for analysis. Are known, Perkin Elmer Japan Co .: product name "ATD400 type thermal desorption GC system" and GL Sciences Co .: product name "PTI & TC
A heat generation gas analyzer such as "T" is commercially available from several companies.

4 and 5 are block diagrams of a conventional device. The “during sample heating” of the present invention means the step of heating the sample tube 2 to generate gas from the sample in the tube and collect it in the trap 3. “At the time of sample analysis” means a step of heating the trap 3 to desorb the collected gas and introducing the desorbed gas to the transfer line / analyzer 5. The "sample heating gas line" means
It means a flow path passing through a sample heating portion (sample tube 2). The “sample analysis gas line” means a flow path to the transfer line / analyzer 5. The gas line passing through the trap 3 is a sample heating gas line when the sample is heated and a sample analysis gas line when the sample is analyzed.

FIG. 4 is a block diagram of a conventional apparatus when heating a sample. The inert gas 7 is controlled by the pressure regulator 1 and introduced into the trap 3 via the sample tube 2.
The sample existing in the sample tube 2 is heated in the atmosphere of the inert gas 7, and the generated gas is guided to the trap 3 to be collected. On the other hand, the inert gas 7 is introduced into the transfer line and / or the analyzer 5 via the switching valve 4.

Next, at the time of sample analysis, the heating valve 10 is used.
And the switching valve 4 is switched as shown in FIG. FIG. 5 is a block diagram of the conventional apparatus during sample analysis. The inert gas 7 is introduced into the trap 3 via the switching valve 4. At the same time, the trap 3 is rapidly heated. Trap 3
The generated gas collected in the
It is introduced into the transfer line and / or the analyzer 5 together with the inert gas 7.

[0006]

However, in the conventional apparatus having the configuration shown in FIGS. 4 and 5, the sample heating gas line and the analyzer gas line are controlled by one pressure regulator, and each line is controlled. It was not possible to supply any gas for each. That is, the trap 3 and the transfer line and / or the analyzer 5 can be supplied with only the same kind of gas. Further, the types of gas that can be passed through the sample heating gas line are limited to those that can be supplied to the analyzer gas line side. That is, the type of gas that can be used in the conventional device is limited to the inert gas such as helium and nitrogen that can be used in the analyzer.

When the gas generated during heating of the polymer material is to be analyzed by using the conventional apparatus having the above-mentioned structure, there is a problem that an arbitrary condition cannot be selected as a gas atmosphere condition during heating. For example, polymer molding and processing is
Usually, it is carried out in an air atmosphere, but when analyzing the gas generated at this time, it was not possible to heat the polymer in a gas atmosphere containing oxygen such as air composition. Therefore, there is a problem that the gas generated during the actual molding process cannot be analyzed by the conventional apparatus.

[0008]

SUMMARY OF THE INVENTION The present invention has been made to overcome the above-mentioned drawbacks of conventional devices. That is, the present invention is characterized in that, in the heating generated gas analyzer, a sample heating gas line is provided from a container filled with an arbitrary gas to a sample heating site via a pressure regulator for adjusting the arbitrary gas. The present invention relates to a heat generation gas analysis device and a heat generation gas analysis method.

The present invention will be described below with reference to the drawings. FIG. 1A and FIG. 1B are basic block diagrams of the present invention. Of these, [A] is a block diagram during sample heating, and [B] is a block diagram during sample analysis. The “during sample heating” of the present invention means a step of heating the sample tube 2 to generate gas from the sample in the tube and collect the gas in the trap 3. “At the time of sample analysis” means a step of heating the trap 3 to desorb the collected gas and introducing the desorbed gas to the transfer line / analyzer 5.
Further, the “sample heating gas line” means a flow path passing through the sample heating portion (sample tube 2). The “sample analysis gas line” means a flow path to the transfer line / analyzer 5. The gas line passing through the trap 3 is a sample heating gas line when the sample is heated and a sample analysis gas line when the sample is analyzed.

The heating generated gas analyzer of the present invention is a sample heating gas line from a container filled with an arbitrary gas 6 to a sample tube 2 (sample heating portion) via a pressure regulator 1 for adjusting the arbitrary gas. Is provided.

More specifically, according to the present invention, a sample heating part 2 for heating a sample to generate a heated gas, a trap 3 for collecting the heated gas sent from the sample heating part 2,
An analyzer 5 for analyzing the heat-generated gas sent from the trap 3, a line for supplying an inert gas to the trap 3, a line for supplying an inert gas from the trap 3 to the analyzer 5, and a transfer line / analysis when heating a sample. In the heating generated gas analyzer which supplies the inert gas 7 to the total 5 and has a switching valve for sending the inert gas 7 together with the heating generated gas from the trap 3 to the analyzer 5 during sample analysis, By providing a sample heating gas line from the container filled with the gas 6 to the sample heating portion 2, it is possible to analyze the heat generated gas generated by heating the sample in an arbitrary gas atmosphere during the heating of the sample. It is characterized by

In the present invention, it is possible to supply an arbitrary gas 6 to the sample heating portion 2 when heating the sample.
Further, the inert gas 7 can be supplied to the analyzer gas line during heating of the sample and during analysis of the sample. In practice, the sample heating gas line is provided with a pressure regulator 1 for controlling an arbitrary gas 6, while the sample analysis gas line is independently provided with a pressure regulator 9 for controlling an inert gas 7,
Control each gas line separately.

Further, FIG. 1 will be described in detail. The heating generated gas analyzer of FIG. 1 according to the present invention comprises a pressure regulator 1, a sample heating portion 2, a trap 3, and a gas line connecting these in order from a container filled with an arbitrary gas 6. , And a gas line from the container filled with the inert gas 7 to the pressure regulator 9 for adjusting the inert gas, the switching valve 4, and the gas from the switching valve 4 to the transfer line / analyzer 5 via the trap 3 A line and a gas line from the switching valve 4 to the transfer line / analyzer 5 are provided. The switching valve 4 is for heating the sample ([A])
Is switched to the gas line from the switching valve 4 to the transfer line / analyzer 5 and to the gas line from the switching valve 4 to the transfer line / analyzer 5 via the trap 3 during sample analysis ([B]).

According to the heat generation gas analyzer of the present invention,
When heating the sample, by supplying an arbitrary gas to the sample heating gas line, the gas generated by heating the sample in an arbitrary gas atmosphere is collected, and at the time of sample analysis, it is analyzed from the collected part of the heated gas. By supplying an inert gas to the gas line leading to the apparatus, the heat-generated gas can be analyzed.

That is, at the time of heating the sample ([A]), the arbitrary gas 6 is caused to flow through the gas line from the container filled with the arbitrary gas 6 to the sample heating portion 2 and the trap 3, and at the same time, the arbitrary gas 6 is heated. The gas generated by heating the sample heating portion 2 is collected in the trap 3, and at the time of sample analysis ([B]),
The inert gas 7 is caused to flow from the container filled with the inert gas 7 to the gas line extending from the trap 3 to the transfer line / analyzer 5, and at the same time, the gas desorbed by heating the trap 3 is transferred together with the inert gas. line/
By supplying to the analyzer 5, the heated gas can be analyzed.

Incidentally, in FIG.
The gas flows in the opposite directions (backflush mode) at the time of heating the sample and at the time of analyzing the sample, but it is also possible to set up a line so that the gas flows in the same direction (forward flow mode).

That is, according to the configuration of the present invention, it is possible to supply an arbitrary gas to the sample tube 2 when the sample is heated. Also, transfer line / analyzer 5
In addition, an inert gas can be supplied at any time of heating the sample and analyzing the sample.

The gas 6 in the present invention can be selected from any gas desired to be selected as a gas atmosphere when heating the sample. For example, oxygen, argon, a gas mixed in an arbitrary ratio, and compressed air in the room may be used.

Further, a three-way valve 8 is provided between the container 6 filled with an arbitrary gas and the pressure regulator 1 for adjusting the arbitrary gas so that the gas from the inert gas 7 flows through the three-way valve 8. You may form a line. According to the configuration, the sample can be heated under the gas atmosphere condition of the inert gas 7 only by switching the three-way valve 8, and it is easy to perform the measurement under the same condition as the conventional device and compare the results. is there.

The inert gas 7 is not particularly limited as long as it can be supplied to the transfer line / analyzer 5. Usually, nitrogen, helium, argon or the like is used, and nitrogen or helium is preferable. Further, hydrogen or the like may be used depending on the purpose.

Furthermore, if the number of three-way valves 8 is three or more, the arbitrary gas supplied to the sample heating gas line can be selected from three or more kinds. Further, when it is desired to use the arbitrary gas as a gas having an arbitrary composition, the arbitrary gas may be a gas whose composition is adjusted in advance. Furthermore, it is also possible to prepare one of the three-way valves with a fixed volume thin tube and use it as a device for introducing a fixed volume of standard gas or a fixed volume of sample gas.

In the apparatus of the present invention, it is preferable to use the heating valve 10 as shown in FIGS. 2 and 3 for switching the gas line of the trap 3 because the switching operation becomes easy. FIG. 2 is a block diagram when the sample of the present invention is heated using the heating valve 10, and FIG. 3 is a block diagram when the sample of the present invention is analyzed using the heating valve 10. When the heating valve 10 is switched after heating the sample, the inert gas 7 flows from the switching valve 4 to the transfer line / analyzer 5 through the trap 3. At the same time, the connection between the sample tube 2 and the trap 3 is cut. Although the trap 3 is in the backflush mode in FIGS. 4 and 5, it is also possible to form a line so that the gas flows in the forward mode.

The transfer line / analyzer 5 of the apparatus of the present invention is not particularly limited. For example, analyzers such as gas chromatograph (GC), gas chromatograph-mass spectrometer (GC / MS), infrared absorption spectrometer (IR), gas chromatograph-ultraviolet absorption analyzer (GC / IR), and analyzers thereof. Transfer line.

The sample that can be analyzed by the apparatus of the present invention is not particularly limited. For example, environmental pollutants, pharmaceuticals, foods, chemicals, paints, polymers and the like can be exemplified. Of these, when various polymers are selected as the analysis sample, there is an advantage that the gas generated when the polymer is heated under the heating conditions during the actual work can be analyzed.
Generally, a polymer is molded and processed by heating, but it is important to analyze the gas and the like generated at this time in order to know the safety at the time of work, the influence on the environment and the like. However, as described above, the conventional apparatus has a problem that the kind of gas is limited due to the circumstances of the analyzer side and only thermal decomposition in a limited gas atmosphere is possible. The decomposition mechanism of the polymer differs depending on the presence or absence of oxygen, and there may be a large difference in the decomposition amount, the generated gas amount and the generated gas type. Since the atmosphere during actual molding and processing is usually an air atmosphere, the invention of this device, which can measure in the presence of oxygen, is an important invention not only from an analytical point of view, but also from the viewpoint of environment and safety. is there.

As a concrete analysis example, there is an example in which the gas 6 is oxygen or a gas containing oxygen such as compressed air, the gas 7 is helium, and the analyzer 5 is a gas chromatograph. According to this method, , Actually polymer molding
Gas generated during processing can be analyzed by gas chromatography. Furthermore, the result can be utilized for environmental safety measures during actual work.

[0026]

In the heating generated gas analyzer, by providing a sample heating gas line from a container filled with an arbitrary gas to a sample heating portion via a pressure controller for adjusting the arbitrary gas, Arbitrary gas can be supplied to the analyzer gas line. The gas supplied to the sample heating gas line can be easily selected from any gas by switching the valve. Further, since a gas containing oxygen can be supplied to the sample heating gas line, the sample can be thermally decomposed in an actual air atmosphere.

[0027]

【Example】

Using the apparatus of Example 1 same configuration as the apparatus shown in Figure 1, ethylene - sections 1mg pellets tetrafluoroethylene _{copolymer, N 2 / O 2 = 79} /21 ( volume ratio) mixed 1 at 350 ° C under a gas stream (70 cc / min)
Heat for 0 minutes. The generated gas was collected at -30 ° C in a trapping agent (trade name: Tenax GR manufactured by GL Sciences Inc.). The trap agent is 35 at -30 ° C to 40 ° C / sec.
The temperature that was raised to 0 ° C. and the gas desorbed from the trap agent was analyzed by a gas chromatograph under the following conditions. The gas in the transfer line / analyzer was He.

The obtained gas chromatogram is shown in FIG. In addition to the detection of five relatively large peaks, an extremely large number of minute peaks were detected, and it was found that a part of the polymer was decomposed in the air composition atmosphere.

[Gas chromatographic analysis conditions] Separation column: DB-1301 (inner diameter 0.25 mm × length 30 m, 6% cyanopropyl-phenyl-polysiloxane, film thickness 1.0 μm), 40 ° C. (3 minutes) to 240 ℃ (1
0 ° C./min) temperature rise. Detector: FID (260 ℃)

[Reference Example 1] Analysis was conducted under the same conditions except that He was used instead of the mixed gas of Example 1 as the gas for the sample heating section. The gas chromatogram is shown in FIG. 7. Since only a few minute peaks are detected,
It is thought that almost no decomposition has occurred. That is, it was found that the state at the time of thermal decomposition was significantly different from the state under the air composition atmosphere of Example 1.

[0031]

By using the apparatus of the present invention, it is possible to supply arbitrary gases to the sample heating gas line and the separation / analysis apparatus gas line, respectively. In particular, in the sample heating gas line, a mixed gas having a composition similar to that of air, such as N ₂ /
When the sample is heated by flowing O ₂ = 79/21 (volume ratio), the generated gas can be analyzed under the same conditions as during actual molding and processing. The result is an environmental safety measure during actual work. There is an advantage that can be used for.

[Brief description of drawings]

FIG. 1A is a block diagram when heating a sample according to the present invention,
[B] A block diagram during sample analysis of the present invention.

FIG. 2 is a block diagram when heating a sample of the present invention using a heating valve.

FIG. 3 is a block diagram during analysis of the present invention using a heating valve.

FIG. 4 is a block diagram of a conventional apparatus when heating a sample.

FIG. 5 is a block diagram of a conventional device during sample analysis.

FIG. 6 is a gas chromatogram of Example 1.

7 is a gas chromatogram of Reference Example 1. FIG.

[Explanation of symbols]

 1: Pressure regulator 2: Sample tube 3: Trap 4: Switching valve 5: Transfer line / analyzer 6: Arbitrary gas 7: Inert gas 8: Three-way valve 9: Pressure regulator 10: Heating valve

Claims (6)

[Claims] 1. A heating gas generating apparatus is characterized in that a sample heating gas line is provided from a container filled with an arbitrary gas to a sample heating site via a pressure controller for adjusting the arbitrary gas. Heating generated gas analyzer. 2. A sample heating part for heating a sample to generate a heated gas, a trap for collecting the heated gas sent from the sample heating part, an analyzer for analyzing the heated gas sent from the trap, A line that supplies active gas to the trap, a line that supplies inert gas from the trap to the analyzer, and supplies the inert gas to the analyzer when heating the sample, and at the time of sample analysis, heats the inert gas from the trap In the heating generated gas analyzer equipped with a switching valve for sending to the analyzer together with the gas, by providing a sample heating gas line from the container filled with any gas to the sample heating site, it is possible to prevent A heating generated gas analyzer characterized in that a heating generated gas generated by heating a sample in a gas atmosphere can be analyzed. 3. The heating generated gas analyzer according to claim 1, wherein the arbitrary gas is a gas containing oxygen. 4. The heat-generated gas analyzer according to claim 2, wherein the analyzer is a gas chromatograph or a gas chromatograph-mass spectrometer. 5. When heating a sample, an arbitrary gas is supplied from a container filled with an arbitrary gas to a gas line reaching a trap via a sample heating portion, and at the same time, the sample heating portion is heated in the arbitrary gas. Collects the generated gas in the trap,
During sample analysis, the inert gas is supplied from the container filled with the inert gas to the gas line through the trap to the transfer line / analyzer, and at the same time, the gas released from the trap by heating the trap is inert gas. A method for analyzing gas generated by heating, characterized in that it is supplied to a transfer line / analyzer together with the gas. 6. The heating evolved gas analysis method according to claim 5, wherein the arbitrary gas is a gas containing oxygen.