JP2017106903A - Pretreatment device for gas analysis and pretreatment method for gas analysis - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pretreatment device for gas analysis and a pretreatment method for gas analysis capable of separating and extracting an extraction object gas at a high-purity.SOLUTION: A pretreatment device 1 for gas analysis is constituted of a water capture section 3 and an adsorption section 5. The water capture section 3 is constituted of a first cold trap CT1 and a second cold trap CT2. The first cold trap CT1 is cooled by a first temperature, and removes a liquid phase. The second cold trap CT2 cools a semi-extraction object gas containing moisture vapor purified by the first cold trap CT1 by a second temperature and purifies the semi-extraction object gas by removing the moisture vapor. The adsorption section 5 adsorbs a non-extraction object gas in the semi-extraction object gas using a getter. The obtained extraction object gas is introduced into an analysis device 11.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a pretreatment device for gas analysis and a pretreatment method for gas analysis that are used before introducing a gas to be analyzed into a gas analyzer.

  Research and development of hydrothermal deposits are underway, and the establishment of survey methods is urgently needed. As one of the investigation methods, it is considered to measure a rare gas dissolved in seawater in order to trace a hot water plume that advects and diffuses in seawater. For this investigation, it is necessary to separate and extract a rare gas as an extraction target gas from an aqueous solution as a sample.

  For example, Japanese Patent No. 5461144 (Patent Document 1) and Japanese Patent Application Laid-Open No. 7-33417 (Patent Document 2) disclose techniques for removing impurities from a high-pressure noble gas.

  Yuji Sano and Naoto Takahata “Measurement of Noble Gas Solubility in Seawater Using a Quadrupole Mass Spectrometer” Journal of Oceanography, Vol. 61, pp. 465 to 473, 2005 (Non-Patent Document 1) A gas separation / extraction method is disclosed.

Japanese Patent No. 5461144 Japanese Unexamined Patent Publication No. 7-33417

Yuji Sano and Naoto Takahata `` Measurement of Noble Gas Solubility in Seawater Using a Quadrupole Mass Spectrometer '' Journal of Oceanography, Vol.61, pp.465 to 473, 2005

  However, the techniques described in Patent Document 1 and Patent Document 2 are techniques for increasing the purity of a high-pressure noble gas used in a semiconductor manufacturing process, and separating and extracting a trace amount of noble gas contained in a sample. It cannot be applied directly.

  The method described in Non-Patent Document 1 is intended for seawater. Seafloor hot water has elements of both hot spring water and seawater, so it is expected that a large amount of halogen compounds and sulfur compounds are dissolved in the seafloor hot water. In the method of Non-Patent Document 1, a large amount is dissolved. The halogen compounds and sulfur compounds are not completely removed. Therefore, the halogen compound may adversely affect the analysis result, and the sulfur compound may damage the flow path through which the analyzer and the sample pass. Therefore, it is necessary to remove the halogen compound and the sulfur compound with high accuracy. In particular, if the flow path through which the analyzer and the sample pass for purification and measurement of rare gas is made of all metal (metal), it is susceptible to corrosion due to the influence of halogen compounds and sulfur compounds. Therefore, corrosion can be remarkably prevented by accurately removing the halogen compound and the sulfur compound.

Furthermore, the method described in Non-Patent Document 1 is a substance whose isotope ratio called “spike” is different from that of the sample and whose ratio and amount are known (in Non-Patent Document 1, specifically, , ²² Ne, ³⁶ Ar, ⁸⁶ Kr, and ¹²⁴ Xe) is added to the sample, and the sample water is used as a cryogen consisting of ethanol and dry ice in the water capture section. (About -80 ° C) is rapidly cooled to remove water (page 468, left column, lines 2 to 4). Therefore, a part of the test substance that should not be removed is removed together with moisture. Therefore, the method described in Non-Patent Document 1 is not suitable for analysis performed by separating and extracting a trace amount of rare gas without using the spike method.

  The object of the present invention is to obtain a high-purity rare gas (extraction target gas) from sample water in which a halogen compound, a sulfur compound and a rare gas (extraction target gas) as a test substance are dissolved, such as undersea hot water. An object of the present invention is to provide a pretreatment apparatus for gas analysis and a pretreatment method for gas analysis that can be separated and extracted.

  Another object of the present invention is to provide a pretreatment apparatus for gas analysis and a pretreatment method for gas analysis that are provided with a getter capable of accurately removing halogen compounds and sulfur compounds.

  The pretreatment apparatus for gas analysis of the present invention has, as a basic configuration, a water capturing section that captures water from sample water in which the extraction target gas is dissolved and purifies the semi-extraction target gas, and a non-extraction in the semi-extraction target gas. And an adsorption section for adsorbing the extraction target gas.

  The water capture section cools the sample water in the first trap channel at a first temperature at which the extraction target gas does not aggregate, removes the liquid phase, purifies the semi-extraction target gas including water vapor, The first cold trap that makes the inside of one trap path a first vacuum environment, and the semi-extraction target gas that is purified by the first cold trap and contains the steam in the second trap path, agglomerates the steam. However, the extraction target gas does not agglomerate, is cooled at a second temperature that is lower than the first temperature, removes water vapor, purifies the semi-extraction target gas that does not contain water vapor, and passes through the second trap path. A second cold trap having a second vacuum environment having a higher degree of vacuum than the first vacuum environment. The adsorption section adsorbs the non-extraction target gas from the semi-extraction target gas in the getter arrangement path, and makes the inside of the getter arrangement path a third vacuum environment having a higher degree of vacuum than the second vacuum environment. Has a getter.

  As used herein, the term “does not include” is a term having a width that includes not only completely (100%) not including but also substantially not including. For example, “a semi-extraction target gas that does not contain water vapor” refers to a semi-extraction target gas from which water vapor has been removed with a second cold trap to such an extent that water vapor is not detected when the extraction target gas is measured by the analyzer.

  In the present invention, as described above, the water capturing section is divided into the first cold trap and the second cold trap, and water and water vapor are captured in stages. By treating the sample water in this way, it is possible to prevent blockage of the flow path due to rapid ice growth and to prevent the extraction target gas as the test substance from being removed together with water and water vapor. In addition, by adsorbing the non-extraction target gas in the adsorption section, it is possible to send out a high-purity extraction target gas to the analyzer. As a result, analysis accuracy (particularly, quantitative accuracy of isotope analysis) in the analyzer is improved.

  One or more getters in the adsorption section can be changed according to the type of the non-extractable gas. For example, when the halogen compound and sulfur compound dissolved in the sample water are the non-extraction target gas, the adsorption section includes the first adsorption having a first getter that adsorbs the halogen compound from the semi-extraction target gas. It is only necessary to include a section and a second adsorption section including a second getter that adsorbs a sulfur compound from the semi-extraction target gas adsorbed in the first adsorption section.

  In the pretreatment apparatus for gas analysis of the present invention, the water capture section is an arbitrary configuration, and the adsorption section includes a first getter that adsorbs a halogen compound from the semi-extraction target gas in the getter arrangement path. Including a first adsorption section and a second adsorption section having a second getter that adsorbs a sulfur compound from the semi-extraction target gas adsorbed in the first adsorption section. A vacuum environment with a higher degree of vacuum than the vacuum environment in the capture section may be provided.

  By reacting the semi-extraction target gas after capturing water in the order of the first adsorption section and the second adsorption section, it is possible to accurately remove the halogen compounds and sulfur compounds that are pollutants. Therefore, it is possible to prevent the flow path and the analysis device from being damaged, and to improve the analysis accuracy of the analysis device.

  The structure of the first getter is arbitrary, but a structure in which an iron (Fe) getter material, a magnesium (Mg) getter material, and a calcium (Ca) getter material are arranged along the inflow path of the semi-extraction target gas. If it has it, a getter effect will be acquired. In particular, iron wire as the iron-based getter material, magnesium ribbon as the magnesium-based getter material, and granular calcium as the calcium-based getter material are suitable as the getter material. Further, according to the study by the inventors, the weight ratio of the calcium-based getter material, the magnesium-based getter material, and the iron-based getter material is 1 ± 10%: 1 ± 10%: 0.03 ± 10% (that is, 0 .9 to 1.1: 0.9 to 1.1: 0.027 to 0.033), a high getter effect was obtained.

  Similarly, although the structure of the second getter is also arbitrary, a copper oxide (CuO) -based getter material, an iron oxide (FeO) -based getter material, a first aluminum (Al ) -Based getter material, vanadium (V) -based getter material, zirconium (Zr) -based getter material, and second aluminum (Al) -based getter material, a getter effect can be obtained. In particular, as the first aluminum-based getter material and the second aluminum-based getter material, aluminum foil, zirconium-based getter material, plate-shaped zirconium, vanadium-based getter material, plate-shaped vanadium, iron oxide-based getter material Copper oxide wires are suitable as getter materials as iron oxide wires and copper oxide based getter materials. Further, according to the study by the inventors, the weight of the first aluminum-based getter material, zirconium-based getter material, vanadium-based getter material, second aluminum-based getter material, iron oxide-based getter material, and copper oxide-based getter material. The ratio is 0.5 ± 10%: 1 ± 10%: 1 ± 10%: 0.5 ± 10%: 1 ± 10%: 2 ± 10% (ie 0.45 to 0.55: 0.9 -1.1: 0.9-1.1: 0.45-0.55: 1.8-2.2), a high getter effect was obtained.

  The adsorption section may further include a third adsorption section that adsorbs the active gas from the semi-extraction target gas that has been subjected to the adsorption treatment in the second adsorption section. The adsorption section may further include a fourth adsorption section that adsorbs hydrogen from the semi-extraction target gas that has been subjected to the adsorption process in the third adsorption section. If the adsorption section is configured in this way, the purity of the extraction target gas can be further increased.

  The pretreatment apparatus for gas analysis of the present invention can be used for any sample water, but is particularly suitable for the case where seawater, seafloor hot water, onshore hot spring water, or the like is used as sample water. ing.

  The pretreatment method for gas analysis of the present invention adsorbs a water capture step of capturing water from sample water in which extraction target gas is dissolved to generate semi-extraction target gas, and non-extraction target gas in the semi-extraction target gas. Adsorption step. In the water capture step, the sample water in the first trap passage is cooled at a first temperature at which the extraction target gas does not aggregate, the liquid phase is removed, the semi-extraction target gas containing water vapor is purified, The first trapping step in which the inside of one trap path is set to a first vacuum environment, and the semi-extraction target gas containing the steam that has been purified in the first trapping step and is contained in the second trap path are condensed with water vapor. The gas to be extracted does not aggregate, is cooled at a second temperature lower than the first temperature, the water vapor is removed to purify the semi-extraction gas without water vapor, and the second trap passage is And a second trapping step in which a second vacuum environment having a higher degree of vacuum than the one vacuum environment is included. In this case, the adsorption step uses one or more getters to adsorb the non-extraction target gas from the semi-extraction target gas that does not contain water vapor in the getter arrangement path, and the getter arrangement path is more than the second vacuum environment. A third vacuum environment with a high degree of vacuum is set.

  The pretreatment method for gas analysis according to the present invention includes a first adsorption step for adsorbing a halogen compound from a semi-extraction target gas in a getter arrangement path, wherein the water capture step is an arbitrary configuration, Including a second adsorption step for adsorbing a sulfur compound from the semi-extraction target gas adsorbed in the first adsorption step, and a vacuum having a higher degree of vacuum than the vacuum environment in the water trapping section in the getter arrangement path You can also make it an environment.

It is the schematic which shows the structure of an example of embodiment of the pretreatment apparatus for gas analysis of this invention. It is a schematic diagram which shows the internal structure of a 1st getter. It is a schematic diagram which shows the internal structure of a 2nd getter. It is a flowchart which shows the flow until it isolate | separates and extracts the noble gas which is extraction object gas using the pretreatment apparatus for gas analysis. (A) And (B) is a figure for showing the getter effect of the 1st getter. (A) And (B) is a figure for showing the getter effect of the 2nd getter. (A) is a figure which shows the result of having analyzed sample water, without performing a getter process, (B) is a figure which shows the analysis result after the getter process by a 1st getter, (C) It is a figure which shows the analysis result after the getter process by 2 getters. (A) is a figure which shows the result of having analyzed sample water, without performing a getter process, (B) is a figure which shows the analysis result after a getter process by a 2nd getter, (C) It is a figure which shows the analysis result after the getter process by 1 getter.

  Hereinafter, embodiments of a pretreatment apparatus for gas analysis and a processing method of the present invention will be described in detail with reference to the drawings.

<Overall configuration>
FIG. 1 is a schematic diagram showing the configuration of the pretreatment apparatus for gas analysis according to the present embodiment, FIG. 2 is a diagram showing the internal structure of the first getter G1, and FIG. 3 is a diagram showing the second getter. It is a schematic diagram which shows the internal structure of G2.

  The gas analysis pretreatment apparatus 1 of the present embodiment is an apparatus that separates and extracts dissolved rare gas as extraction target gas from seabed hot water that is sample water. Undersea hot water is composed of rare gases such as helium (He), neon (Ne), argon (Ar), krypton (Kr), and xenon (Xe), as well as halogen compounds, sulfur compounds, active gases (nitrogen, hydrocarbons, Carbon monoxide, carbon dioxide, oxygen, hydrogen, water vapor, etc.) are dissolved. In the present embodiment, the rare gas is the extraction target gas, and the halogen compound, the sulfur compound, the active gas, and the like are the non-extraction target gas.

  The pretreatment device 1 for gas analysis mainly includes a water capturing section 3 that captures water (liquid phase and water vapor) from sample water in which the extraction target gas is dissolved and purifies the semi-extraction target gas, and the semi-extraction target gas. It is comprised from the adsorption | suction section 5 which adsorb | sucks the non-extraction object gas. The sample water introduced from the sample container connecting portion 9 of the pipe line 7 is processed by the water capturing section 3 and the adsorption section 5 through the pipe line 7 and sent out to the analyzer 11. The pipe line 7 is provided with valves V1 to V7 for switching the flow path and vacuum gauges P1 to P3 for measuring the pressure in the pipe line 7.

[Water capture section]
The water trapping section 3 is composed of a first cold trap CT1 and a second cold trap CT2. The first cold trap CT1 cools the sample water in the first trap path (section of the pipe line 7 divided by the valves V1, V2, and V3) at a first temperature at which the extraction target gas does not aggregate, It is a cold trap which removes a liquid phase and makes the inside of a 1st trap path | route the 1st vacuum environment. In the case of the present embodiment, the first temperature is −10 ° C. to −15 ° C. (more preferably, −12 ° C. to −15 ° C.).

  The second cold trap CT2 is a semi-extraction target gas containing water vapor that has been purified by the first cold trap CT1 and is in the second trap path (section separated by the valves V3 and V4 in the pipe line 7). Water vapor is condensed, but the extraction target gas is not aggregated. Cooling is performed at a second temperature lower than the first temperature, the water vapor is removed, the semi-extraction target gas is purified, and the inside of the second trap path is purified. The cold trap is a second vacuum environment having a higher degree of vacuum than the first vacuum environment. In the case of the present embodiment, the second temperature is −25 ° C. to −40 ° C. (more preferably, −30 ° C. to −35 ° C.).

[Suction section]
The adsorption section 5 adsorbs the non-extraction target gas from the semi-extraction target gas that does not contain water vapor in the getter arrangement path (section of the pipe line 7 that is divided by the valves V4 and V7). One or more getters that provide a third vacuum environment having a higher degree of vacuum than the vacuum environment are provided. Specifically, the adsorption section 5 includes a first adsorption section having a first getter G1, a second adsorption section having a second getter G2, and a third getter having a third getter G3. An adsorption section and a fourth adsorption section having a fourth getter G4 are included.

  The first getter G1 is a getter that adsorbs a halogen compound, and as shown in FIG. 2, an iron (Fe) -based getter material GM11, a magnesium (Mg) -based getter material GM12 along the inflow path of the semi-extraction target gas. And a structure in which calcium (Ca) -based getter materials GM13 are arranged. Specifically, the iron-based getter material is an iron wire, the magnesium-based getter material is a magnesium ribbon, and the calcium-based getter material is granular calcium. According to the experiments by the inventors, when the weight ratio of the calcium-based getter material, the magnesium-based getter material, and the iron-based getter material is 1 ± 10%: 1 ± 10%: 0.03 ± 10%, a high getter is obtained. The effect was able to be acquired.

  Of course, other materials may be used as the getter material of the first getter G1. For example, in place of or in addition to any of the above getter materials, or in addition, any of nickel (Ni), cobalt (Co), copper (Cu), zirconium (Zr), or vanadium (V) or its A combination of getter materials may be used.

  The second getter G2 is a getter that adsorbs a sulfur compound (and an active gas generated by being decomposed when the sulfur compound is adsorbed), and as shown in FIG. 3, along the inflow path of the semi-extraction target gas. Copper oxide (CuO) getter material GM21, iron oxide (FeO) getter material GM22, first aluminum (Al) getter material GM23, vanadium (V) getter material GM24, zirconium (Zr) getter material The GM25 and the second aluminum (Al) -based getter material GM26 are arranged side by side. Specifically, the first aluminum-based getter material and the second aluminum-based getter material are aluminum foils, the zirconium-based getter material is plate-like zirconium, and the vanadium-based getter material is plate-like vanadium. The iron oxide getter material is an iron oxide wire, and the copper oxide getter material is a copper oxide wire. According to the experiments by the inventors, the weight ratio of the first aluminum getter material, the zirconium getter material, the vanadium getter material, the second aluminum getter material, the iron oxide getter material, and the copper oxide getter material is 0.5 ± 10%: 1 ± 10%: 1 ± 10%: 0.5 ± 10%: 1 ± 10%: 2 ± 10%, a high getter effect could be obtained.

  Of course, other materials may be used as the getter material of the second getter G2. For example, silver (Ag), gold (Au), platinum (Pt), molybdenum (in place of, or in addition to, one or all of the iron oxide type getter material and the copper oxide type getter material among the above getter materials. A getter material of any one of Mo) or a combination thereof may be used. Further, any one or combination of chromium (Cr), nickel (Ni), and cobalt (Co) may be used instead of or in addition to any or all of zirconium-based getter materials, vanadium-based getter materials, and aluminum-based getter materials. The getter material may be used.

  The third getter G3 is a getter that adsorbs an active gas from the semi-extraction target gas adsorbed in the second adsorption section, and a titanium (Ti) getter material along the inflow path of the semi-extraction target gas. And a structure in which zirconium (Zr) -based getter materials are arranged.

  The fourth getter G4 is a getter that adsorbs hydrogen, and in this embodiment, a getter pump sold by SAES under the name SORB-AC (registered trademark) is used.

<Flow until the extraction target gas is introduced into the analyzer>
FIG. 4 is a flowchart until a rare gas that is an extraction target gas is introduced into the analyzer 11.

  As described above, the inside of the pipe line 7 of the gas analysis pretreatment apparatus 1 is normally in a state where the valves V1, V2, V3 and V7 are closed and the valves V4, V5 and V6 are opened. It is evacuated by the pump VP2 (step ST1). Thus, normally, the second cold trap CT2 is maintained in a vacuum environment corresponding to a high vacuum region or an ultrahigh vacuum region. The inside of the first cold trap CT1 is maintained in a vacuum environment corresponding to a low vacuum region by the exhaust operation at the end of the analysis prior to this.

  First, a water capture step is performed. In order to introduce the extraction target gas into the analyzer 11, first, the valve V2 is opened, the first cold trap CT1 is evacuated to a pressure in the middle vacuum region (step ST2), and then the valve V2 is closed (step ST2). ST3). If necessary, close the getter valves GV1 to GV3 and V6 (or V5 in addition) and open the valve V3 to check the degree of vacuum with the vacuum gauge P1, but the vacuum pump VP1 operates normally. As long as this is done, the medium vacuum region is sufficiently reached by exhausting for about 5 minutes. Next, the sample container 13 enclosing the sample water is connected to the sample container connecting portion 9, the valve V1 is opened, the sample water is introduced into the first cold trap CT1 (step ST4), and the valve V1 is quickly closed (step S4). Step ST5). The sample water of the present embodiment is seabed hot water and is enclosed in the sample container 13. When the valve V1 is opened and sample water enters the first cold trap CT1, the pressure in the first cold trap CT1 becomes a low vacuum region. In this state, the first cold trap CT1 is cooled at the first temperature to condense the liquid phase (step ST6). As a result, the pressure in the first cold trap CT1 is in the vacuum region where the pressure is lower than before cooling. Next, the valve V4 is closed, the valve V3 is opened, and the semi-extraction target gas containing water vapor is introduced into the second cold trap CT2 (step ST7). As a result, the pressure in the second cold trap CT2 becomes a pressure near the boundary between the low vacuum region and the medium vacuum region. In this state, the second cold trap CT2 is cooled at the second temperature, the water vapor is condensed, and the valve V3 is closed while continuing the cooling (step ST8). As a result, the inside of the second cold trap CT2 becomes a vacuum environment corresponding to a medium vacuum region.

  Next, an adsorption step is performed. First, the getter valves GV1 to GV4 and the valves V5 and V6 attached to the first to fourth getters are closed (step ST9). As a result, the pressure in the conduit between the valves V4 and V6 is high vacuum, and the pressure between the valves V6 and V7 is maintained in the ultrahigh vacuum. The valve V4 is opened, and the semi-extraction target gas is introduced between the valves V4 and V6 (step ST10). Thereby, this section becomes the pressure in the medium vacuum region (measured by the vacuum gauge P2 when the gas is introduced).

  The getter valve GV1 is opened and the first getter G1 is activated (step ST11). The first getter G1 is activated by being heated to about 400 ± 10 ° C. in advance, and after acting for about 10 minutes, the getter valve GV1 is closed (step ST12).

  Next, the getter valve GV2 is opened, and the second getter G2 is operated (step ST13). The second getter G2 is activated by being heated to about 400 ± 10 ° C. in advance, and after acting for about 10 minutes, the getter valve GV2 is closed (step ST14).

  Next, the getter valve GV3 is opened, and the third getter G3 is operated (step ST15). The third getter G3 is activated by being heated to about 650 ± 10 ° C. in advance. The third getter G3 is allowed to act for about 10 minutes, and then is allowed to act while cooling for about 10 minutes until the temperature reaches room temperature. GV3 is closed (step ST16). Due to the getter effect of the first to third getters G1 to G3, the section from the valves V4 to V6 becomes a pressure in the high vacuum region or a pressure near the boundary between the high vacuum region and the ultrahigh vacuum region.

  Thereafter, the valve V6 is opened, and getter-treated gas is introduced into the section from the valves V6 to V7 (step ST17). As a result, the section becomes the pressure in the high vacuum region or the pressure in the vicinity of the boundary between the high vacuum region and the ultrahigh vacuum region (measured by the vacuum gauge P3 when introducing the gas). Then, the getter valve GV4 is opened, the fourth getter G4 is operated (step ST18), and the getter valve GV4 is closed (step ST19). The fourth getter G4 acts in a heated state or at room temperature. In the present embodiment, the gas obtained through the getter process by the fourth getter G4 is the extraction target gas (rare gas). Even after the getter process by the fourth getter G4, if the section from the valve V6 to V7 does not reach the pressure in the ultra-high vacuum region, the amount of gas to be extracted is too large, so the valve V6 is closed and the valve V5 is opened. Thus, it is possible to evacuate a part by the vacuum pump VP2 and adjust the gas amount (steps ST20 and ST21). Depending on the analysis contents and the analysis device, the obtained extraction target gas may be introduced into the analysis device 11 as it is, and when it is necessary to further separate the obtained extraction target gas, a separation trap The valve VST is opened and closed, the rare gas is separated using the separation trap ST (steps ST22 and 23), and introduced into the analyzer (step ST24).

The term “vacuum region” used in the present specification is based on the definition defined in JIS Z 8126-1: 1999. Specifically, the low vacuum region is a pressure of 100 Pa or more defined by JIS. The medium vacuum region means a pressure range of less than 100 Pa and less than 0.1 Pa specified by JIS, and the high vacuum region means a pressure range of less than 0.1 Pa and less than 10 ^-5 Pa specified by JIS, The ultra-high vacuum region means a pressure range less than 10 ⁻⁵ Pa specified by JIS.

<Getter effect of first and second getters>
The getter effect of the first and second getters G1 and G2 will be described with reference to FIGS.

  FIG. 5A is a diagram showing the result of analyzing tap water (sample water containing a large amount of chlorine) without getter treatment, and FIG. 5B shows the analysis after acting on the first getter G1. It is a figure which shows a result. The vertical axis is the logarithmic axis of pressure (torr), and the horizontal axis is the mass number (AMU). In FIG. 5A, the analyzer is saturated with a high-pressure (medium vacuum range) gas that exceeds the operating limit of the analyzer, and a mass spectrum is not obtained. On the other hand, in FIG. 5B, the pressure in the apparatus decreases due to the effect of the getter G1, and various gas species separated for each mass number 1 (1 AMU) are detected. Of these, the mass number 35 corresponds to the mass number of chlorine-35, which is the main isotope of chlorine, but this is not detected. Thus, when FIGS. 5A and 5B are compared, it is clear that chlorine is reduced by three orders of magnitude or more in FIG. 5B.

FIG. 6 (A) is a diagram showing the result of analyzing hot spring water (sample water containing a large amount of sulfur compound) without getter treatment, and (B) shows the result after acting on the second getter G2. It is a figure which shows an analysis result. The vertical axis is the logarithmic axis of pressure (torr), and the horizontal axis is the mass number (AMU). In FIG. 6A, there is a mass number at which the analyzer is saturated by a gas close to the operating limit of the analyzer (the pressure at the boundary between the medium vacuum and the high vacuum), and the mass spectrum is disturbed. Among these, the mass number 48 corresponds to the mass number of sulfur monoxide in which sulfur-32 and oxygen-16, which are the main isotopes of sulfur and oxygen, are detected, but this is barely detected and is in the order of 10 ^-9 . It is. On the other hand, in FIG. 6B, the pressure in the apparatus decreases due to the effect of the getter G2, and various gas species separated for each mass number 1 (1 AMU) are detected. The part of the mass number 48 corresponding to the mass number of sulfur monoxide is a trough of the mass spectrum and is in the order of 10 ⁻¹⁰ . Thus, when FIGS. 6A and 6B are compared, it is clear that the sulfur compound in FIG. 6B is reduced by 1 to 2 digits.

  Next, the difference in getter effect due to the difference in processing order between the first and second getters G1 and G2 will be described with reference to FIGS. In the example of FIG. 7, getter processing is performed in the order of the first and second getters. FIG. 7A is a diagram showing the result of analyzing sample water containing a halogen compound and a sulfur compound without getter treatment, and FIG. 7B shows the analysis result after getter treatment by the first getter. (C) is a figure which shows the analysis result after the getter process by the 2nd getter. The vertical axis is the logarithmic axis of pressure (torr), and the horizontal axis is the mass number (AMU). 7A to 7C, it is understood that the getter effect of the first and second getters is sufficiently exhibited when the getter process using the first getter is performed first.

  On the other hand, in the example of FIG. 8, getter processing is performed in the order of the second and first getters. FIG. 8A is a diagram showing the result of analyzing sample water containing a halogen compound and a sulfur compound without getter treatment, and FIG. 8B shows the analysis result after getter treatment by the second getter. (C) is a figure which shows the analysis result after the getter process by the 1st getter. The vertical axis is the logarithmic axis of pressure (torr), and the horizontal axis is the mass number (AMU). From FIGS. 8A to 8C, when the getter processing by the second getter is performed first, no effect is obtained even when the second getter is operated, and the mass spectrum is not obtained. Further, it can be seen that a peak corresponding to sulfur monoxide remains in the mass number 48 even in the second stage by the first getter later, and the sulfur compound cannot be completely adsorbed.

  Therefore, it can be seen from FIGS. 7 and 8 that the order of the first and second getters is also an important factor in the present invention.

  As mentioned above, although an example of embodiment of this invention was demonstrated concretely, this invention is not limited to these embodiment, It can change within the range of the technical idea of this invention. Of course. For example, the sample water is not limited to seafloor hot water, and the pretreatment device for gas analysis of the present invention can target any sample water, particularly seawater or onshore hot spring water. It is suitable when environmental water such as is used as sample water.

  According to the present invention, high-purity rare gas (extraction target gas) is extracted from sample water in which a halogen compound, a sulfur compound, and a rare gas (extraction target gas) as a test substance are dissolved, such as undersea hot water. A pretreatment apparatus for gas analysis and a pretreatment method for gas analysis that can be separated and extracted can be obtained.

DESCRIPTION OF SYMBOLS 1 Gas analysis pretreatment apparatus 3 Water capture section 5 Adsorption section 7 Pipe line 9 Sample container connection part 11 Analysis apparatus 13 Sample container V1-V7 Valve CT1 1st cold trap CT2 2nd cold trap G1 1st getter GM11 Iron (Fe) -based getter material GM12 Magnesium (Mg) -based getter material GM13 Calcium (Ca) -based getter material G2 Second getter GM21 Copper oxide (CuO) -based getter material GM22 Iron oxide (FeO) -based getter material GM23 First Aluminum (Al) -based getter material GM24 Vanadium (V) -based getter material GM25 Zirconium (Zr) -based getter material GM26 Second aluminum (Al) -based getter material G3 Third getter G4 Fourth getter GV1 to GV4 Getter valve VP1, VP2 Vacuum port Pump ST Separation Trap VST Separation Trap Valve

Claims (13)

A water capture section for capturing water from the sample water in which the extraction target gas is dissolved and purifying the semi-extraction target gas;
A pretreatment device for gas analysis comprising an adsorption section for adsorbing a non-extraction target gas in the semi-extraction target gas,
The water capture section is
The sample water in the first trap passage is cooled at a first temperature at which the extraction target gas does not aggregate, the liquid phase is removed, the semi-extraction target gas containing water vapor is purified, and the first extraction target gas is purified. A first cold trap that places the trap path in a first vacuum environment;
The semi-extraction target gas containing the water vapor that has been purified by the first cold trap and is in the second trap path causes the water vapor to aggregate, but the extraction target gas does not aggregate, than the first temperature. Cooling at a second temperature, which is a low temperature, removing the water vapor to purify the semi-extraction target gas that does not contain water vapor, and the second trap path has a higher degree of vacuum than the first vacuum environment. A second cold trap that creates a vacuum environment of 2;
The adsorption section is
A first adsorption section having a first getter that adsorbs a halogen compound out of the semi-extraction target gas in the getter arrangement path, and the semi-extraction target gas adsorbed in the first adsorption section. And a second adsorption section having a second getter that adsorbs sulfur compounds from the first and second getter arrangement paths into a third vacuum environment having a higher degree of vacuum than the second vacuum environment. A pretreatment device for gas analysis characterized by the above. A water capture section for capturing water from the sample water in which the extraction target gas is dissolved and purifying the semi-extraction target gas;
A pretreatment device for gas analysis comprising an adsorption section for adsorbing a non-extraction target gas in the semi-extraction target gas,
The water capture section is
The sample water in the first trap passage is cooled at a first temperature at which the extraction target gas does not aggregate, the liquid phase is removed, the semi-extraction target gas containing water vapor is purified, and the first extraction target gas is purified. A first cold trap that places the trap path in a first vacuum environment;
The semi-extraction target gas containing the water vapor that has been purified by the first cold trap and is in the second trap path causes the water vapor to aggregate, but the extraction target gas does not aggregate, than the first temperature. Cooling at a second temperature, which is a low temperature, removing the water vapor to purify the semi-extraction target gas that does not contain water vapor, and the second trap path has a higher degree of vacuum than the first vacuum environment. A second cold trap that creates a vacuum environment of 2;
The adsorption section is
The non-extraction target gas is adsorbed from the semi-extraction target gas not containing water vapor in the getter arrangement path, and the inside of the getter arrangement path is changed to a third vacuum environment having a higher degree of vacuum than the second vacuum environment 1 A pretreatment apparatus for gas analysis comprising the above getter. A water capture section for capturing water from the sample water in which the extraction target gas is dissolved and purifying the semi-extraction target gas;
A pretreatment device for gas analysis comprising an adsorption section for adsorbing a non-extraction target gas in the semi-extraction target gas,
The adsorption section is
A first adsorption section having a first getter that adsorbs a halogen compound out of the semi-extraction target gas in the getter arrangement path, and the semi-extraction target gas adsorbed in the first adsorption section. And a second adsorption section having a second getter that adsorbs sulfur compounds from the water, and the inside of the getter arrangement path is made a vacuum environment having a higher degree of vacuum than the vacuum environment in the water capturing section. Characteristic pretreatment device for gas analysis.   The first getter has a structure in which an iron (Fe) getter material, a magnesium (Mg) getter material, and a calcium (Ca) getter material are arranged along the inflow path of the semi-extraction target gas. The pretreatment device for gas analysis according to claim 1 or 3. The iron-based getter material is an iron wire,
The magnesium-based getter material is a magnesium ribbon,
The pretreatment device for gas analysis according to claim 4, wherein the calcium-based getter material is granular calcium.   The gas analysis according to claim 4 or 5, wherein a weight ratio of the calcium-based getter material, the magnesium-based getter material, and the iron-based getter material is 1 ± 10%: 1 ± 10%: 0.03 ± 10%. Pre-treatment device.   The second getter includes a copper oxide (CuO) -based getter material, an iron oxide (FeO) -based getter material, a first aluminum (Al) -based getter material, vanadium ( The pretreatment apparatus for gas analysis according to claim 1 or 3, wherein V) a getter material, a zirconium (Zr) getter material, and a second aluminum (Al) getter material are arranged side by side. The first aluminum-based getter material and the second aluminum-based getter material are aluminum foils,
The zirconium-based getter material is plate-like zirconium,
The vanadium-based getter material is plate-like vanadium,
The iron oxide-based getter material is an iron oxide wire,
The pretreatment device for gas analysis according to claim 7, wherein the copper oxide-based getter material is a copper oxide wire.   The weight ratio of the first aluminum getter material, the zirconium getter material, the vanadium getter material, the second aluminum getter material, the iron oxide getter material, and the copper oxide getter material is 0. The pretreatment device for gas analysis according to claim 7 or 8, wherein 5 ± 10%: 1 ± 10%: 1 ± 10%: 0.5 ± 10%: 1 ± 10%: 2 ± 10%.   The pre-gas analysis unit according to claim 1, wherein the adsorption section further includes a third adsorption section that adsorbs an active gas from the semi-extraction target gas that has been subjected to the adsorption treatment in the second adsorption section. Processing equipment.   The pretreatment device for gas analysis according to claim 10, wherein the adsorption section further includes a fourth adsorption section that adsorbs hydrogen from the semi-extraction target gas that has been subjected to the adsorption treatment in the third adsorption section. A water capture step for purifying the semi-extraction target gas by capturing water from the sample water in which the extraction target gas is dissolved;
A pretreatment method for gas analysis comprising an adsorption step for adsorbing a non-extraction target gas in the semi-extraction target gas,
The water capture step comprises
The sample water in the first trap passage is cooled at a first temperature at which the extraction target gas does not aggregate, the liquid phase is removed, the semi-extraction target gas containing water vapor is purified, and the first extraction target gas is purified. A first capture step that places the trap path in a first vacuum environment;
The quasi-extraction target gas containing the water vapor purified in the first trapping step and in the second trap passage causes the water vapor to aggregate, but the extraction target gas does not aggregate, and is lower than the first temperature. Is cooled at a second temperature, the water vapor is removed to purify the semi-extraction target gas not containing water vapor, and the second trap path has a second degree of vacuum higher than that of the first vacuum environment. And a second capture step for creating a vacuum environment of
The adsorption step comprises:
Using one or more getters, the non-extraction target gas is adsorbed from the semi-extraction target gas not containing water vapor in the getter arrangement path, and the degree of vacuum in the getter arrangement path is higher than that in the second vacuum environment. A pretreatment method for gas analysis, characterized in that a third vacuum environment is provided. A water capture step for purifying the semi-extraction target gas by capturing water from the sample water in which the extraction target gas is dissolved;
A pretreatment method for gas analysis comprising an adsorption step of adsorbing a non-extraction target gas in the semi-extraction target gas using a getter,
The adsorption step comprises:
A first adsorption step for adsorbing a halogen compound from the semi-extraction target gas in the getter arrangement path, and a second adsorption for adsorbing a sulfur compound from the semi-extraction target gas adsorbed in the first adsorption step. A pretreatment method for gas analysis, wherein the getter arrangement path is made a vacuum environment having a higher degree of vacuum than the vacuum environment in the water trapping section.

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