JPH03255361A - Analyzing apparatus for hydrogen in sample - Google Patents

Abstract

PURPOSE:To detect the amount of oxygen which is generated in real time continuously by providing a high-temperature oxidizing device and a separating column in a flow path for gas generated in an extracting furnace, providing a bypass flow path in parallel with the oxidizing device and the separating column, and switching the flow paths in response to an analyzing mode. CONSTITUTION:A high-temperature oxidizing device 3 and a bypass flow path 5 are provided in parallel on the output side of an extracting path 1. A separating column 9 and a bypass flow path 11 are provided in parallel. When switching operations are performed with flow-path switching devices 4A and 4B and 10A and 10B, three analyzing modes can be performed. In non- temperature rising analysis, the high-temperature oxidizing device 3 is not used, and the generating gas is made to flow. Then the total amount of hydrogen is obtained. In temperature rising analysis, the effect of the nitrogen is removed by performing the analysis corresponding to the temperature region, and the amount of the hydrogen is obtained for every pattern. In this way, the amount of hydrogen generated in real time can be continuously detected.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention involves heating a metal or other sample in an extraction furnace and guiding the gas generated at that time to an analyzer via a separation column to extract the hydrogen contained in the sample. This invention relates to an apparatus for analyzing.

[Conventional technology]

Conventional hydrogen analyzer in a sample (hereinafter referred to as the analyzer)
is constructed as shown in FIG.
The gas generated at that time is led out from the extraction furnace 52 using an inert carrier gas such as Ar.
This generated gas is passed through a flow rate controller 53 to a room temperature oxidizer 54.
, a CO8 remover 55, and a H, O remover 56, and further, after separating H8 from a coexisting gas (this coexisting gas is mainly N!) in a separation column 57, a thermal conductivity analyzer ( (hereinafter referred to as TCD) 58 H,
I was trying to detect it.

By the way, in recent years, it has become necessary not only to measure the amount of hydrogen contained in a sample, but also to analyze the form of hydrogen contained in the sample. In response to this, a technology for power control for the graphite crucible 51 in the extraction furnace 52 has been developed, making it possible to control the extraction state from low to high temperatures, and analysis by form has become possible to some extent.

[Problem to be solved by the invention]

However, according to the above-mentioned conventional analyzer, H3 and N
, was separated by a so-called column separation method, and the separated gas extraction waveform at that time was as shown in Figure 9. Therefore, it was not possible to continuously detect the amount of H8 generated in real time. .

On the other hand, there is a research-level device that detects Hyo in ashes using vacuum extraction-Pd permeability method, but this device has problems with long-term stability, such as the difficulty of maintaining and managing the degree of vacuum. However, it has the disadvantage that it is not suitable for general analysis in terms of speed, workability, and cost, and its scope of application is limited.

The present invention has been made with the above-mentioned considerations in mind, and its purpose is to provide a versatile analytical device that can continuously detect the amount of H8 generated in real time in an extraction furnace. There is a particular thing.

[Means for Solving the Problems] In order to achieve the above-mentioned object, an analysis device according to the present invention is configured as follows.

One method is to install a high-temperature oxidizer on the exit side of the extraction furnace, provide a flow path switch on each of the inlet and outlet sides of this high-temperature oxidizer, and connect a bypass flow path between the flow path switchers. In addition, a flow path switching device is provided on each of the inlet side and the exit side of the separation column, a bypass flow path is connected between the flow path switching devices, and a flow path switching device located on the exit side of the separation column. It is characterized in that a flow rate controller is provided between the analyzer and the analyzer.

Another method is to provide a flow path switch on each of the inlet and outlet sides of the separation column, connect a bypass flow path between the flow path switchers, and connect the bypass flow path to the outlet side of the separation column. A feature is that a flow rate controller is provided between the flow path switching device and the analysis needle.

(Operation) According to the analyzer having the former configuration, desired hydrogen analysis can be performed by appropriately switching the flow path switching device.

First, when performing analysis that does not require morphological analysis, that is, total hydrogen content analysis (non-temperature raising analysis) (this is called 1st mode analysis), the gas generated from the extraction furnace is passed through a high-temperature oxidizer. A normal temperature oxidizer, C
It passes through an O8 remover and an H80 remover sequentially, and then is introduced into the TCD after passing through a separation column. Since the waveform representing the extracted signal at this time is as shown in FIG. 5, the total amount of hydrogen can be obtained by integrating the signals corresponding to Hl.

Although it is a temperature-programmed analysis, when performing an analysis in which the graphite crucible is heated at a relatively low temperature and Nt, which is a coexisting gas, can be ignored (this is called second mode analysis), the gas generated from the extraction furnace is , passed through a normal temperature oxidizer, CO□ remover, and H80 remover in sequence through a bypass flow path installed in parallel with the high-temperature oxidizer, and then introduced into the TCD through a bypass flow path installed in parallel with the separation column. do. Since the waveform representing the temperature-raising extraction signal at this time is as shown in FIG. 6, the hydrogen amount for each form can be obtained from the relationship with each temperature by integrating this temperature-raising extraction signal as it is.

Then, when performing a temperature-raising analysis in which the graphite crucible is heated to a relatively high temperature and the coexisting gas N is not ignored (this is called 3rd mode analysis), it is the same as the 2nd mode analysis above. Then, a graphite crucible containing the same sample used for the first analysis was heated with electricity in an extraction furnace, and the gas generated from the extraction furnace was
The sample is passed through a high temperature oxidizer, a room temperature oxidizer, a CO□ remover, and a H□ remover, and then introduced into the TCD via a bypass flow path provided in parallel with the separation column for a second analysis. At this time, the waveforms representing the temperature-increased extraction signals in the first and second analyzes are as shown in Figures 7 (A) and (B). By analyzing the signals obtained from the analysis, it is possible to obtain the amount of hydrogen in each form with the influence of coexisting gases removed.

Furthermore, according to the analyzer having the latter configuration, the third
Although mode analysis cannot be performed, desired hydrogen analysis can be performed by appropriately switching the flow path switching device.

〔Example〕

Embodiments of the present invention will be described below with reference to the drawings.

FIG. 1 is a diagram showing the configuration of an analyzer according to a first embodiment of the present invention together with changes in the form of generated gas.
is a direct energization type extraction furnace, in which the graphite crucible 2 containing the sample is heated by electricity, and the gas generated by this heating is heated by Ar.
It is designed so that it can be led out of the furnace using a carrier gas such as.

3 is a high-temperature oxidizer installed on the exit side of the extraction furnace 1;
, O to co! An oxidation catalyst is provided for oxidizing each of the two. Reference numerals 4A and 4B are flow path switching devices provided on the inlet side and the outlet side of the high temperature oxidizer 3, respectively, and are composed of, for example, electromagnetic three-way valves, and are configured to operate in the same direction. A bypass flow path 5 is provided in parallel with the high temperature oxidizer 3 between the flow path switching devices 4A and 4B.

Reference numeral 6 denotes a room temperature oxidizer installed downstream of the flow path switching device 4B, which selectively converts only the CO contained in the generated gas into CO.
It is filled with an oxidation catalyst that oxidizes to 8. 7 is a CO2 remover provided on the downstream side of the room temperature oxidizer 6, and is a CO2 remover that adsorbs COl generated in the room temperature oxidizer 6.
is filled.

Reference numeral 8 denotes an H and O remover provided downstream of the CO□ remover 7, and is filled with a deH and O agent that adsorbs H and O contained in the generated gas.

Reference numeral 9 denotes a separation column installed on the outlet side of the H, O remover 8, and inside it there are H and N! For example, a molecular error sieve is provided to separate the two. IOA,
IOB is a flow switching device provided on each of the inlet side and outlet side of the separation column 9, and is composed of an electromagnetic three-way valve, and is configured to interlock with each other in the same direction. Further, 11 is a bypass flow path provided in parallel with the separation column 9 between the flow path switching device lO^110B.

Reference numeral 12 denotes a flow rate controller installed between the flow path switching device 10B and the TCD 13 located on the outlet side of the separation column 9, and when gas flows through the separation column 9 by the switching operation of the flow path switching device 10A and IOB. and bypass flow path 11
This prevents fluctuations in the flow rate of the gas flowing to the TCD 13 when the gas flows through the TCD 13.

Next, the operation of the analyzer having the above configuration will be explained. Analysis by this analyzer can be performed in the following three analysis modes by switching the flow path switchers 4^, 4B, IOA, and IOB.

First, in the first mode of analysis that does not require morphological analysis, that is, total hydrogen content analysis (non-temperature-raising analysis), the gas generated from the extraction furnace 1 is passed through the bypass flow path 5 to the normal temperature oxidizer. 6. After passing through a Co, remover 7 and a H, O remover 8 in order, and further through a separation column 9, it is introduced into the TCD 13 via a flow rate controller 12. That is, in the first mode analysis, the high temperature oxidizer 3 is not used, and the generated gas is passed in the same way as in the conventional method. Since the extracted waveform at this time is as shown in FIG. 5, the total amount of hydrogen can be obtained by integrating the signals corresponding to H2.

In addition, in the second mode analysis, which heats the graphite crucible 2 at a relatively low temperature and performs analysis in which the coexisting gas N is negligible, the gas generated from the extraction furnace 1 is passed through the bypass flow. Passing through line 5, room temperature oxidizer 6, CO8 remover 7
, HxO remover 8, and further passes through the bypass flow path 11, and then the TCD 13 via the flow rate controller 12.
It will be introduced in That is, in the second mode analysis, N! which is a coexisting gas! Since this can be ignored, the generated gas is introduced into the TCD 13 without passing through the separation column 9. The waveform representing the temperature-raising extraction signal at this time is as shown in Figure 6, so by integrating this temperature-raising extraction signal as it is, it is possible to obtain the amount of hydrogen for each form from the relationship with each temperature. .

In the third mode analysis, which is temperature raising analysis, in which the graphite crucible 2 is heated to a relatively high temperature and the coexisting gas N3 cannot be ignored, the first analysis is performed in the same manner as the second mode analysis. Then, the graphite crucible 2 containing the same sample used for the first analysis was placed in the extraction furnace l.
The gas generated from the extraction furnace 1 is passed through a high temperature oxidizer 3 to a room temperature oxidizer 6, a CO remover 7, H, O
After passing through the remover 8 and further passing through the bypass channel 11, it is introduced into the TCD 13 via the flow rate controller 12.
Perform the first analysis.At this time, the first analysis.

The waveforms representing the temperature increase extraction signal in the second analysis are as shown in FIGS. 7(A) and (B), respectively, so the signal obtained in the second analysis can be changed from the signal obtained in the first analysis. By subtracting, the influence of coexisting gas can be removed. In addition, by visually comparing the analysis signal obtained from the first analysis and the analysis signal obtained from the second analysis, it is possible to know the generation status of gases other than H (coexisting gas), and When there is almost no generation of hydrogen, the amount of hydrogen for each form can be immediately obtained from the relationship with each temperature.

In addition, in the analyzer having the above configuration, when the second mode analysis or the third mode analysis is selected, the flow path switching devices 4A, 4B and 104. The IOB is designed to be automatically switched and controlled.

In the above embodiment, a conventional analyzer includes a high-temperature oxidizer 3, a bypass channel 5 provided in parallel to the high-temperature oxidizer 3, and a channel switch for switching between the high-temperature oxidizer 3 and the bypass channel 5. In addition to providing vessels 4A and 4B, a separation column 9
Flow path switching device 10A.

Although the bypass flow path 11 was provided through 10B, the second
As shown in the figure, from the configuration of the above-described embodiment, a high temperature oxidizer 3, flow path switching devices 4A and 4B, and a bypass flow path 5 are included.
may be removed. If configured in this way, the third
Although mode analysis cannot be performed, first mode analysis and second mode analysis can be performed, and not only the total amount of hydrogen but also the amount of hydrogen in each form can be measured.

The above embodiments were all performed using one TCD, but as shown in FIGS. 3 and 4, two TCDs were used.
A CD may also be used.

That is, in FIG. 3, two analysis lines 20 and 30 are provided in parallel to each other on the exit side of the extraction furnace 1, and one analysis line 20 includes a high temperature oxidizer 3, a normal temperature oxidizer 6, and a CO remover. 7, H, O remover 8, flow path switch 10^, 10B
A separation column 9 and a bypass channel 11 are connected in parallel via a flow rate controller 12, and a TCD 13^ are installed in this order, and the other analysis line 3o is equipped with a room temperature oxidizer 6, CO,
Remover 7, H, O remover 8, flow rate controller 12, TCD1
3B are provided in this order. With this configuration, the third mode can be performed in one analysis.

In addition, in FIG. 4, a room temperature oxidizer 6, a C
O, remover 7, HzO remover 8, flow path switch 10A,
Separation column 9 and bypass flow path 11 are connected in parallel via IOB, flow rate controller 12, TCD 13A,
A high temperature oxidizer 3, an H and O remover 8, and a TCD 13B are provided in this order. When configured in this way, the configuration is simpler than that shown in FIG. In this embodiment, the flow rate controller 12 may be provided at any other position as long as it adjusts the flow rate that varies when switching between the column separation line and the bypass line.

〔Effect of the invention〕

As explained above, according to the present invention, the amount of N2 generated in the extraction furnace in real time can be continuously detected. By appropriately controlling the electric power supplied to the extraction furnace, it is possible to detect the distribution of the amount of hydrogen generated from moment to moment, and thereby accurately and quickly determine the distribution of hydrogen contained in the sample by form. can be grasped.

The gas generated in the extraction furnace is mostly H2 in the low temperature range (for example, 1000°C or less), and N3 etc. coexist in the high temperature range (for example, 1500'C). In the analyzer according to 1), the influence of Nt can be removed by performing the third mode analysis, and H! You can know the true amount of

Further, the analyzer according to the present invention has a simple configuration, is easy to operate, and operates stably over a long period of time, so it has the advantage of being able to perform measurements over a wide range.

[Brief explanation of drawings]

FIG. 1 is a diagram showing the configuration of an analyzer according to an embodiment of the present invention, together with changes in the form of generated gas. FIG. 2 is a diagram showing the configuration of an analyzer according to another embodiment of the present invention, together with changes in the form of generated gas. FIG. 3 and FIG. 4 are block diagrams each showing the configuration of an analyzer according to still another embodiment of the present invention. Figures 5 to 7 are waveform diagrams representing extracted signals when analyzed using the analyzer shown in Figure 1, respectively. When the mode analysis was performed, FIGS. 7(A) and 7(B) respectively show the results when the third mode analysis was performed. FIG. 8 is a block diagram showing the configuration of a conventional analyzer along with changes in the form of generated gas. FIG. 9 is a waveform diagram showing an extracted signal when analysis is performed using a conventional analyzer. ■...Extraction furnace, 3...High temperature oxidizer, 4A, 4B.
...Flow path switching device, 5...Bypass flow path, 9...Separation column, 10A, IOB...Flow path switching device, 12
...Flow rate controller, 13°13A, 13B...Analyzer.

Claims (2)

[Claims] (1) In an apparatus in which a sample is heated in an extraction furnace and the gas generated at that time is guided to an analyzer via a separation column to analyze hydrogen contained in the sample, high-temperature oxidation is performed on the exit side of the extraction furnace. A flow path switch is provided on each of the inlet side and outlet side of the high temperature oxidizer, a bypass flow path is connected between the flow path switchers, and a flow path switch is provided on each of the inlet side and outlet side of the separation column. A flow path switching device is provided in the flow path switching device, a bypass flow path is connected between the flow path switching devices, and a flow rate controller is further provided between the flow path switching device located on the outlet side of the separation column and the analyzer. An apparatus for analyzing hydrogen in a sample, which is characterized by: (2) In an apparatus in which a sample is heated in an extraction furnace and the gas generated at that time is guided to an analyzer via a separation column to analyze hydrogen contained in the sample, the inlet side and outlet side of the separation column A flow path switching device is provided in each of the flow path switching devices, a bypass flow path is connected between the flow path switching devices, and a flow rate controller is provided between the flow path switching device located on the outlet side of the separation column and the analyzer. An apparatus for analyzing hydrogen in a sample, characterized in that: