JPH06300748A - Thermal analyzer - Google Patents

Abstract

PURPOSE:To provide a thermal analysis technique wherein not only a thermal analysis but also an efficient analytical operation including the analysis of a metal contained in a residue can be carried out by effectively utilizing the residue produced in the thermoanalysis. CONSTITUTION:The analyzer is composed of a sample container 5 installed at the inside of a furnace 3, of a thermogravimetric measuring device 6 which measures the weight of a sample 4 held at the inside of the sample container 5, of a pipe 14, of a valve 7, of a valve 10, of a sampling device 8, of a gas chromatograph 9, of a Fourier transform infrared spectrophotometer 11 and of a mass spectrometer 12. The gas chromatograph 9 is connected to the Fourier transform infrared spectrophotometer 11 via a pipe 9a, and an inert gas 1 and oxygen gas 2 are supplied to the furnace 3 via a pipe 1a, a valve 1b, a pipe 2a and a valve 2b. A system control part 13 unifies and control the whole, and it performs the data processing operation of an analyzed result, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal analysis technique, and more particularly to the analysis of volatile components and pyrolysis gas components of organic materials,
The present invention relates to a technique effectively applied to pretreatment for analysis of contained metals.

[0002]

2. Description of the Related Art Conventionally, for example, as disclosed in Japanese Patent Laid-Open No. 48-56497, thermal analysis having a structure for automatically performing qualitative and quantitative analysis of gas generated by thermal decomposition of a sample or the like. A device has been proposed.

Further, Japanese Patent Laid-Open No. 61-213655 discloses a thermal analysis of a structure in which a mode for separately identifying a direct coupling measurement mode and a mode for identification is switched by a switching valve, and the generated gas is correctly analyzed every moment. A device is disclosed.

[0004]

The above-mentioned prior art does not take into consideration the use and contamination of the residue after the thermal analysis, and there is a concern that the analysis accuracy may decrease due to the contamination in the analysis of the metal contained in the residue. To be done.

Further, there is a problem that the timing of introduction and analysis of the generated gas cannot be finely controlled and various analyzes of the generated gas cannot be performed.

The object of the present invention is not only thermal analysis but also the thermal analysis technology that enables efficient analysis work including effective analysis of the metal contained in the residue by effectively utilizing the residue generated in the thermal analysis. To provide.

Another object of the present invention is to provide a thermal analysis technique capable of performing various analyzes of gas generated from a sample at various timings.

[0008]

Among the inventions disclosed in the present application, a brief description will be given to the outline of typical ones.
It is as follows.

That is, the thermal analysis apparatus of the present invention comprises a heating mechanism for pretreatment of the sample for ashing and a gas analysis mechanism for analyzing the gas generated in the heating mechanism.

Further, according to the present invention, in the thermal analysis apparatus according to claim 1, the sample container in the heating mechanism is made of a material which does not contain a metal element to be analyzed in the sample, and is used in the metal analysis step as it is. It is a thing.

Further, according to the present invention, in the thermal analysis apparatus according to claim 1 or 2, the gas analysis mechanism comprises a mass analysis part for taking in gas from the heating mechanism via the first valve, and a second aspect.
The gas chromatograph comprises a sampling unit and a gas chromatograph which take in gas from the heating mechanism via the valve of (1), isolate the gas and supply it to the mass spectrometric unit.

Further, the present invention provides the thermal analyzer according to the first, second or third aspect, wherein opening / closing control of the first and second valves is performed by at least one of weight change and temperature of the sample in the heating mechanism, or mass. The control means is provided according to the gas analysis result in the analysis section.

Further, the present invention provides the thermal analysis apparatus according to claim 1, 2, 3 or 4, wherein the sampling section is provided with a storage mechanism for storing a plurality of gases generated in the heating mechanism, It can be supplied to the mass spectrometric section via a gas chromatograph.

Further, according to the present invention, in the thermal analyzer according to the first, second, third, fourth or fifth aspect, a Fourier transform infrared spectrophotometer is arranged in front of the mass spectrometric section.

[0015]

According to the above-described thermal analysis apparatus of the present invention, for example, pretreatment for ashing an organic sample and thermal analysis can be performed simultaneously, and the analysis process can be made efficient. In addition, the sample container in the heating mechanism is made of a material that does not contain the metal element to be analyzed in the sample, and the sample container is used as it is for the metal analysis step. Therefore, a highly accurate metal that effectively uses the residue of thermal analysis. Analysis can be performed.

Further, since the control means for switching the valve according to the change of the weight of the sample or the change of the analysis signal strength is provided, the valve can be automatically switched according to the set value, and various analytical operations can be performed at various timings. it can.

Further, since a plurality of samplings can be automatically performed for introducing the gas chromatograph and a gas chromatograph can be automatically introduced, a plurality of mixed gases that need to be separated can be automatically analyzed.

[0018]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A thermal analysis apparatus according to an embodiment of the present invention will be described in detail below with reference to the drawings. FIG. 1 is a conceptual diagram showing an example of the configuration of the thermal analysis apparatus of this embodiment,
FIG. 2 is a flowchart showing an example of the operation,
FIG. 3 is a conceptual diagram showing an example of a part of the configuration in more detail.

The thermal analyzer of the present embodiment is a thermogravimetric measurement for measuring the weight of a furnace 3, a sample container 5 provided inside the furnace 3, and a sample 4 held inside the sample container 5. And a device 6. In the furnace 3, a sampling device 8 and a gas chromatograph 9 and a Fourier transform infrared spectrophotometer 1 through a pipe 14 and a valve 7 and a valve 10.
1 (FT-IR) and mass spectrometer 12 (MS) are connected. In addition, the gas chromatograph 9 is a pipe 9
It is connected to the Fourier transform infrared spectrophotometer 11 via a.

An inert gas 1 and an oxygen gas 2 are supplied to the furnace 3 through a pipe 1a, a valve 1b, a pipe 2a and a valve 2b.

Thermogravimetric measuring device 6, sampling device 8,
Gas chromatograph 9, Fourier transform infrared spectrophotometer 1
1, the mass spectrometer 12, the valves 1b and 2b, and the valves 7 and 10 are collectively controlled by the system control unit 13, and the system control unit 13 processes data such as analysis results.

The sampling device 8 has a plurality of sampling columns 8a, as shown in FIG.
Generated gas 4 for each of the sampling columns 8a
an introduction control valve 8b for individually controlling the introduction of a, a supply control valve 8c for selectively supplying the generated gas retained in each sampling column 8a to the gas chromatograph 9, and an upstream side of the introduction control valve 8b. In addition, a carrier gas pipe 8e for supplying a carrier gas, a carrier gas valve 8d, and the like are configured to individually hold a plurality of generated gases 4a collected at a plurality of timings,
The generated gas 4a thus held is sequentially analyzed by the gas chromatograph 9
It is possible to supply to.

High-purity gases are used as the inert gas 1 and the oxygen gas 2, and they are led to the furnace 3 through pipes 1a and 2a free from metal contamination. By using, for example, high-purity quartz, the sample container 5 can eliminate the concern of contamination by metal elements and the like and can be directly used in the subsequent metal analysis step.

First, the measurement is carried out with an inert gas 1 and an oxygen gas 2
The gas flow rate such as the above and the heating temperature profile of the sample 4 are set in the system controller 13 (step 21). Then, the sample 4 is set, the inside of the furnace 3 is sufficiently replaced with the inert gas 1, and then the temperature rise is started (step 22). When the temperature rise starts, a volatile component and a thermal decomposition component are generated from the sample 4, and the valve 10 is opened by the weight change of the thermogravimetric measuring device 6 or at any timing of the heating temperature profile (step 23: step 24), The generated gas 4a flows to the Fourier transform infrared spectrophotometer 11 and the mass spectrometer 12 (step 25).

When it is determined from the measurement signal results of the Fourier transform infrared spectrophotometer 11 and the mass spectrometer 12 that the generated gas 4a is a mixed gas (step 26), the valve 7 is opened because it is not suitable for mass spectrometry as it is. A plurality of generated gases 4a are sampled by the sampling device 8 and held individually (step 27: step 28).

In the case of a single gas, the analysis result is recorded (step 29).

When the generation of volatile components and pyrolyzed components is completed (step 30), the valves 7 and 10 are closed (step 31), oxygen gas 2 is introduced, and the sample is incinerated (step). 32).

During this period, a plurality of gases sampled and held by the sampling device 8 are individually introduced into the gas chromatograph 9, the mixed gas is separated into a single component, and the Fourier transform infrared spectrophotometer 11 and the mass spectrometric analyzer are used. Device 1
2, and mass spectrometry and the like are performed (step 35:
Step 36: Step 37).

After the analysis is completed, the sample 4 is taken out together with the sample container 5 (step 33), an acid solution for dissolving the residue is directly added, and after dissolution, metal element analysis is performed by atomic absorption method or the like (step 34).

As described above, according to the thermal analysis apparatus of this embodiment, for example, an organic material is subjected to an ashing treatment as a pretreatment for the analysis of contained metals and a volatile component and a thermal decomposition component in a single measurement operation. The qualitative analysis, the thermal decomposition temperature and the decomposition amount can be measured, and the sample 4 can be efficiently analyzed.

The timing of opening and closing the valve 7 for guiding the generated gas 4a to the sampling device 8 and the gas chromatograph 9, the Fourier transform infrared spectrophotometer 11, and the valve 10 for guiding the generated gas 4a to the mass spectrometer 12 are controlled by the system. Since the control unit 13 controls according to the weight change of the sample 4 and the analysis result, various analyzes can be performed at various timings.

In the above description, first the valve 10
The case has been described where the analysis is performed while opening the valve to determine whether the generated gas 4a is a mixed gas or not, but the valves 7 and 10 are simultaneously opened to hold the sampling of the generated gas 4a in the sampling device 8 and perform mass spectrometry. May be performed in parallel.

Although the invention made by the present inventor has been specifically described based on the embodiments, the invention is not limited to the above embodiments, and various modifications can be made without departing from the scope of the invention. Needless to say.

[0034]

The effects obtained by the typical ones of the inventions disclosed in the present application will be briefly described as follows.
It is as follows.

That is, according to the thermal analysis apparatus of the present invention,
Not only the thermal analysis, but also the residue generated in the thermal analysis can be effectively used, and the effect that the efficient analysis work including the analysis of the metal contained in the residue can be performed is obtained.

Further, there is an effect that various analyzes of gas generated from the sample can be performed at various timings.

[Brief description of drawings]

FIG. 1 is a conceptual diagram showing an example of the configuration of a thermal analysis apparatus that is an embodiment of the present invention.

FIG. 2 is a flowchart showing an example of the operation.

FIG. 3 is a conceptual diagram showing an example of a part of the configuration in more detail.

[Explanation of symbols]

 1 inert gas 1a pipe 1b valve 2 oxygen gas 2a pipe 2b valve 3 furnace (heating mechanism) 4 sample 4a generated gas 5 sample container 6 thermogravimetric measuring device (heating mechanism) 7 valve (second valve) 8 sampling device ( Gas analysis mechanism 8a Sampling column (storage mechanism) 8b Introduction control valve (storage mechanism) 8c Supply control valve (storage mechanism) 8d Carrier gas valve (storage mechanism) 8e Carrier gas pipe (storage mechanism) 9 Gas chromatograph (gas analysis mechanism) 9a piping 10 valve (first valve) 11 Fourier transform infrared spectrophotometer (gas analysis mechanism) 12 mass spectrometer (gas analysis mechanism) 13 system control unit (control means) 14 piping

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location G01N 31/00 Y 7132-2J 31/12 Z 7132-2J

Claims (6)

[Claims] 1. A thermal analysis apparatus comprising: a heating mechanism for performing pre-ashing treatment of a sample; and a gas analysis mechanism for analyzing a gas generated in the heating mechanism. 2. The heat according to claim 1, wherein the sample container in the heating mechanism is made of a material that does not contain a metal element to be analyzed in the sample, and is used in the metal analysis step as it is. Analysis equipment. 3. The gas analyzing mechanism takes in the gas from the heating mechanism via a second valve, and a mass spectrometric unit that takes in the gas from the heating mechanism via a first valve. The thermal analysis apparatus according to claim 1, comprising a sampling section and a gas chromatograph which are isolated and supplied to the mass spectrometric section. 4. A control means for controlling the opening and closing of the first and second valves according to at least one of a weight change and a temperature of the sample in the heating mechanism or an analysis result of the gas in the mass spectrometric section. The thermal analysis apparatus according to claim 1, further comprising: 5. The sampling unit includes a storage mechanism for storing a plurality of the gases generated in the heating mechanism, and the gas can be supplied to the mass spectrometric unit via the gas chromatograph at any time. The thermal analyzer according to claim 1, 2, 3, or 4. 6. The thermal analysis device according to claim 1, wherein a Fourier transform infrared spectrophotometer is arranged in the preceding stage of the mass spectrometric section.