JP2010071895A - Sulfuryl fluoride detector tube, sulfuryl fluoride detection apparatus, and sulfuryl fluoride detection method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a technique for safely and surely detecting a sulfuryl fluoride. <P>SOLUTION: An alkaline material, a pH indicator and moisture are disposed within a detector tube body 11. If a sample gas containing the sulfuryl fluoride flows through the detector tube 11, the sulfuryl fluoride is hydrolyzed in the presence of the alkaline material, and a pH within the detector tube body 11 is changed by a generated hydrofluoric acid. If the pH indicator is discolored by the pH change, a concentration of the sulfuryl fluoride in the sample gas is obtained by a length of a discolored portion. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to the technical field of detector tubes, and more particularly to a detector tube for detecting sulfuryl fluoride.

There are cases where animals (insects) from the country of origin (producing country) are attached along with imported goods in the present when there are many imports and exports.
As a concrete example, “American white hitori” invaded the country along with post-war munitions, and domestic breeding was allowed. Other than this, there are numerous weevil such as “weevil” that harms rice, “fruit fly” that blows citrus fruits, “pine wood nematode” that kills pine trees, and “termite” that causes problems in housing. Has entered the country.

In order to prevent such pest damage, the Plant Protection Law has been enacted and pest control is carried out by fumigation.
There are many fumigants currently in use, but due to termite control etc., sulfuryl fluoride (Sulfuryl fluoride: abbreviated as “SF” hereinafter. Distributor: Dow Chemical Co., Ltd., trade name: Baikane) (Which is a registered trademark of Dow AgroScience L.C.)) has been used a lot.

  In fumigation, post-dose concentrations must be measured to confirm the effect. Two measuring instruments are sold by several companies (JMS, etc.), but one detector tube (DRAGER) is an HF generator tube and two HF detector tubes measure the HF generated by decomposition. SF detector tubes are sold.

  In this HF generator tube, a heat source material that reacts with oxygen gas and becomes high temperature is arranged in the tube, and when the sample gas is sucked and introduced into the HF detector tube, the oxygen in the sample gas Reacts with the heat source material, SF is decomposed by the generated heat, and HF (hydrogen fluoride) is generated.

  Quinarizarin (quinalizarin CAS No .: 81-61-8) is placed inside the HF detector tube as a pH indicator, and the generated HF and pH indicator react chemically, and the HF detector tube is in the sample gas The color changes to pink for the length corresponding to the amount of SF.

HF + zircon / quinalizarin → Pink reaction product
The reaction of SF with alkali is described in the following literature.
"RED Sulfuryl Fluoride. September 1993", US Environmental Protection Agency, p17

However, when using the above pyrolysis reaction, the detector tube (HF generator tube) needs to be heated to a high temperature, so there is not only a risk of burns, but also the tube where the detector tube is laminated burns. In addition, there is a risk of becoming an ignition source in an explosion hazard area.
In addition, since the pyrolysis reaction is greatly affected by temperature and humidity (measuring atmosphere), the measurement accuracy is unstable, and there is a restriction that the measurement must be started within 30 to 60 seconds after the detector tube is opened. is there.

  An object of the present invention is to solve the above-mentioned problems of the prior art and provide an SF detector tube that is safe to handle and can perform stable measurement.

In order to solve the above-mentioned problems, the present invention provides a sample tube introduced at least partially in a transparent tube, and an alkaline substance and a pH indicator disposed in the tube, and introduced into the tube. The sulfuryl fluoride detector tube is configured such that sulfuryl fluoride contained therein reacts with the alkaline substance, and the pH indicator changes color due to a pH change in the detector tube body.
The present invention is the sulfuryl fluoride detector tube in which the alkaline substance contains at least any one compound of sodium hydroxide, potassium hydroxide, or lithium hydroxide.
The present invention is also a sulfuryl fluoride detector tube having a porous and particulate main carrier on which the alkaline substance and the pH indicator are adsorbed.
Moreover, the present invention is a sulfuryl fluoride detector tube in which the main carrier contains one or more kinds of particles of alumina particles, silica gel particles, and diatomaceous earth particles.
Moreover, it is a sulfuryl fluoride detector tube in which water is contained at a position in the detector tube body where the alkaline substance and the pH indicator are arranged.
The present invention also provides a sulfuryl fluoride detector tube in which a carbon dioxide removing agent is arranged upstream of a region where the alkaline substance and the pH indicator are arranged in a path through which the sample gas flows in the detector tube body. It is.
Further, the present invention provides the sulfur dioxide fluoride detection agent, wherein the carbon dioxide removing agent has a sub-carrier having a smaller surface area per grain than the main carrier, and a reactant adsorbed on the sub-carrier and reacts with carbon dioxide. It is a tube.
Moreover, this invention is a sulfuryl fluoride detector tube in which the said subcarrier contains any 1 or more types of particle | grains among a glass particle and silica sand.
Further, the present invention is a sulfuryl fluoride detector tube in which at least any one compound of sodium hydroxide, potassium hydroxide, or lithium hydroxide is adsorbed on the auxiliary carrier as the reactant.
The present invention also includes a sample gas that has an auxiliary pipe and a carbon dioxide removing agent disposed in the auxiliary pipe, and that contains carbon dioxide contained in the sample gas introduced into the auxiliary pipe. A carbon dioxide removal pipe for removing the carbon dioxide, a connection for connecting the carbon dioxide removal pipe and any one of the sulfuryl fluoride detection pipes, and introducing the sample gas flowing in the carbon dioxide removal pipe into the sulfuryl fluoride detection pipe The sulfuryl fluoride detector has a tube and measures sulfuryl fluoride in the sample gas flowing through the carbon dioxide removing tube with the sulfuryl fluoride detector tube.
Further, the present invention is the sulfuryl fluoride detection device, wherein the carbon dioxide removing agent has a subcarrier having a smaller surface area than the main carrier and a reactant adsorbed on the subcarrier and reacts with carbon dioxide.
Further, the present invention is a sulfuryl fluoride detector tube in which at least any one compound of sodium hydroxide, potassium hydroxide, or lithium hydroxide is adsorbed on the auxiliary carrier as the reactant.
In the present invention, the sample gas is caused to flow between the main carrier on which the alkaline substance and the pH indicator are adsorbed, and either or both of the water contained in the sample gas and the water adsorbed on the main carrier are used. Reaction of moisture with sulfuryl fluoride contained in the sample gas to generate an acidic substance to move the pH of the main carrier surface in the acidic direction, and the pH indicator in an amount corresponding to the amount of the sulfuryl fluoride This is a method for detecting sulfuryl fluoride that changes the color of the water.
In addition, the present invention provides the sulfuryl fluoride which flows between the sub-carriers in which the carbon dioxide removing agent is adsorbed and the surface area per particle is smaller than that of the main carrier before flowing between the main carriers. It is a detection method.

The present invention is configured as described above, and sulfuryl fluoride reacts with moisture contained in the detector tube main body and moisture contained in the sample gas, and moves the pH in the detector tube main body in the acidic direction. This reaction occurs on the main support surface.
If the sample gas contains an acidic gas such as carbon dioxide, the pH of the main carrier surface moves in the acidic direction also by the acidic gas.

  If the concentration of sulfuryl fluoride in the sample gas is small and carbon dioxide gas is contained in the sample gas, the amount by which the pH of the main carrier surface moves in the acidic direction due to the carbon dioxide gas cannot be ignored. The concentration of sulfuryl fluoride and the concentration of carbon dioxide gas is added as the concentration of sulfuryl fluoride.

  Therefore, a carbon dioxide removing agent is adsorbed on a subcarrier whose surface area per grain is smaller than that of the main carrier, and before passing the sample gas between the main carrier on which the alkaline substance and the pH indicator are adsorbed, When carbon dioxide is removed, the concentration of sulfuryl fluoride can be accurately measured by the amount of discoloration of the main carrier.

  As the carbon dioxide removing agent, the same substance as the alkaline substance adsorbed on the main carrier can be used, and by using a substance having a smaller area per grain of the subcarrier than the main carrier, sulfuryl fluoride is formed on the subcarrier. It can be prevented from hydrolysis.

  Since the reaction principle of the present invention is a hydrolysis reaction, it is not necessary to generate high heat and is safe. Because it does not require high heat, it does not become an ignition source even in an environment with combustible materials. Since the temperature of the detection tube main body does not become high, even if the detection tube main body is wound with a resin film, no smoke is generated or the film does not melt.

Further, the detection tube may not be divided into the HF generation tube and the HF detection tube.
Moreover, since the reaction principle is not sensitive to humidity and temperature, the measurement stability is high. Therefore, it is possible to lengthen the time from the end of the detection tube to the end of the measurement.

  In addition to the thermal decomposition reaction described above, the following hydrolysis reaction is known as the SF decomposition reaction.

SO ₂ F ₂ (sulphuryl fluoride) + H ₂ O → HSO ₃ F + HF (acidic substance)
This hydrolysis is also described in the MSDS published by the SF vendor, but the hydrolysis rate is very slow.

When water is made alkaline, it is known that the hydrolysis reaction of SF proceeds rapidly. However, an alkaline substance is sealed inside the sulfuryl fluoride detector tube, and SF is contained from the inlet side of the sulfuryl fluoride detector tube. When gas is introduced, sulfuryl fluoride undergoes a hydrolysis reaction with water enclosed together with an alkaline substance or water contained in a sample gas, and both HF and HSO ₃ F are generated as acidic substances. As a result, the alkaline substance is consumed by the neutralization reaction, the pH shifts to the neutral side or the acidic side, the reaction speed of the part becomes slow, and the generated acidic substance is generated at the inlet side of the sulfuryl fluoride detector tube. Move from to the exit.

That is, SF can be detected by neutralizing the acidic substance produced by hydrolysis with an alkaline substance and changing the color of the pH indicator.
In this case, if water is sufficiently placed inside the sulfuryl fluoride detector tube and the content of the alkaline substance is made uniform, if the position where the pH shifts due to the generation of HF moves, the distance moved will be Depends on the concentration of SF gas contained in the gas.

  Therefore, when water, an alkaline substance, and a pH indicator are sealed in the sulfuryl fluoride detector tube and a sample gas is allowed to flow therein, the following equation (1):

SO ₂ F ₂ + H ₂ O + Alkaline substance → HSO ₃ F + HF + Alkaline substance …… (1)
As a result of the chemical reaction, pH changes from the sample gas inlet side of the sulfuryl fluoride detector tube, and the pH indicator changes color by a length corresponding to the amount of SF introduced into the inside.

If the amount of SF is associated with the length of the discolored portion and a certain amount of sample gas is introduced, the SF concentration in the sample gas can be obtained from the length of the discolored portion.
When the porous main carrier made of fine particles such as alumina is immersed in an aqueous solution in which an alkaline substance and a pH indicator are dissolved, the alkaline substance and the pH indicator are supported. In this case, it is not necessary to inject moisture into the sulfuryl fluoride detector tube as long as it carries moisture necessary for measurement.

  In addition, even if moisture is not present in the sulfuryl fluoride detector tube, if moisture is contained in the sample gas, SF is hydrolyzed by the moisture. Therefore, the sulfuryl fluoride detector tube contains moisture. There is no need to be.

FIG. 1A is an external view of the first and second examples of the sulfuryl fluoride detector tubes 10 and 20 of the present invention, and FIG. 1B is a cross-sectional view of the first example.
Referring to FIGS. 1A and 1B, the sulfuryl fluoride detector tube 10 of the first example has a detector tube body 11 made of a glass tube. Inside the detection tube main body 11, the detection agent 12 is filled in a color changing region that is located in the center of the detection tube main body 11 and has a portion having a constant inner diameter.

  A plug body 13 made of Teflon (registered trademark) or the like and having air permeability is arranged on both sides of the detection agent 12 inside the detection tube body 11, and the detection agent 12 moves inside the detection tube body 11. Not to be. Reference numeral 14 denotes ceramic powder, which is disposed between the detection agent 12 and the plug body 13 so that the detection agent 12 and the plug body 13 do not come into contact with each other.

  As the detection agent 12, an alkaline substance (here, KOH was used) and a pH indicator (here, titanium yellow was used) were dissolved in water, and a porous powder (here, alumina powder particles) was dissolved in the aqueous solution. And dried so that the water content is 10 wt% or more.

  Both ends of the detection tube main body 11 are cut at positions closer to the end than the plug 13 to form openings at both ends. One opening is the entrance side and the other opening is the exit side. When the sample gas containing SF is introduced, the SF gas in the introduced sample gas, the moisture and the alkaline substance in the detection agent 12 undergo a chemical reaction of the above formula (1), and the detection agent 12 in the discoloration region. However, the color changes from the entrance side to the exit side.

  Since the inner diameter of the discoloration region is a constant value and the alkaline substance is arranged at a uniform concentration, the length of the discolored portion is proportional to the amount of SF introduced into the detector tube body 11. Therefore, the concentration of SF in the sample gas can be obtained by associating the length of the discolored portion in advance with the amount of SF gas, introducing a certain amount of sample gas, and measuring the length of the discolored portion. .

  The sulfuryl fluoride detection tube 10 is provided with a scale 18 on the detection tube main body 11, and the length can be understood by reading the number on the scale 18 at the boundary between the discolored region and the non-discolored region. (The smaller the scale value is on the entrance side).

  The alkaline substance used in the above examples was potassium hydroxide, but any alkaline substance having alkalinity similar to potassium hydroxide can be used. For example, sodium hydroxide, lithium hydroxide, hydrazine, ammonia, and amine can be used.

  In the above embodiment, titanium yellow (the pink color changes to yellow when SF gas is detected) is used as the pH indicator. However, the pH indicator is not limited to this, and the pH shifts to the acidic side due to the generation of an acidic substance. It only has to be detected. For example, when alizanin yellow is contained in the detection agent 12, light purple changes to yellow due to the reaction of SF gas.

  In the case of hydrazine, the reaction product with SF is acidic, and the part that reacts with SF inside the detector tube changes from alkaline to acidic, so the crystal violet changes color when the pH changes from alkaline or neutral to acidic. PH indicators such as can be used.

  In the above embodiment, the powder particles are used as the main carrier to which the alkaline substance, water and the indicator are attached, but a fibrous substance can be used instead of the powder particles. The main carrier is not limited to alumina particles, and inert porous particles (silica gel particles, diatomaceous earth particles, etc.) made of a substance that does not react with SF or HF can be widely used.

  When the sample gas contains an acidic gas, it reacts with an alkaline substance adsorbed on the main carrier, and moves the pH in the detection tube main body 11 in the acidic direction in the same manner as sulfuryl fluoride.

  In the above example, the concentration of the acid gas in the sample gas was significantly smaller than the concentration of sulfuryl fluoride in the sample gas, and the reaction between the acid gas and the alkaline substance was negligible.

  On the other hand, in order to detect low-concentration sulfuryl fluoride, the detection agent is configured so that the pH indicator reacts even with low-concentration sulfuryl fluoride, or the concentration of acidic gas in the sample gas is When the concentration is higher than the concentration of sulfuryl chloride, the reaction between the acid gas and the alkaline substance cannot be ignored.

  Carbon dioxide gas is an acid gas and is contained in air at 350 ppm to 500 ppm. When measuring a sample gas containing sulfuryl fluoride in the air, if 1% or more of sulfuryl fluoride is contained and the detection agent is configured to detect a high concentration of sulfuryl fluoride, carbon dioxide The presence of gas can be ignored.

  However, when detecting sulfuryl fluoride in a sample gas containing about 10 ppm to 100 ppm of sulfuryl fluoride in the air, the detection agent is configured to detect low concentration sulfuryl fluoride. The pH indicator is also discolored by carbon dioxide at a concentration similar to that of sulfuryl.

  FIG. 4 shows the discoloration length of the sulfuryl fluoride concentration tube on the horizontal axis and the sulfuryl fluoride detector tube for the low concentration on the vertical axis, and the symbol P indicates that the sample gas containing 500 ppm of carbon dioxide gas is present in the carbon dioxide removal agent. The color change length was 13 mm when it was introduced into a low-concentration sulfuryl fluoride detector tube without passing through.

  The broken line of the symbol Q is the relationship between the sulfuryl fluoride concentration and the color change length when the carbon dioxide concentration is zero. The relationship between the sulfuryl fluoride concentration and the color change length when the carbon dioxide concentration is 500 ppm is a value obtained by adding 13 mm to the color change length of the broken line Q.

  Thus, since the low concentration sulfuryl fluoride detector tube is affected by carbon dioxide, it is desirable to detect sulfuryl fluoride in the sample gas from which the carbon dioxide gas has been removed, as in the following examples.

  The sulfuryl fluoride detection tube 20 of the second example shown in FIG. 1C is between the detection agent 12 and the sample gas inlet side of the detection tube main body 11 (here, the detection agent 12 and the ceramic powder 14 The carbon dioxide removing agent 15 is disposed in the middle). Other portions have the same structure as the sulfuryl fluoride detector tube 10 of the first example, and the same portions are denoted by the same reference numerals and description thereof is omitted.

  The carbon dioxide removing agent 15 is composed of a subcarrier having a surface area smaller than that of the main carrier and a reactant that is adsorbed on the subcarrier and reacts with carbon dioxide. As the reactive substance, the same chemical substance as the alkaline substance adsorbed on the main carrier in order to detect sulfuryl fluoride can be used.

  The main carrier uses particles with a large surface area such as alumina particles, silica gel particles, diatomaceous earth particles, etc., but the secondary carrier is made of glass particles or silica sand obtained by grinding glass to prevent sulfuryl fluoride from reacting with the reactants. Particles with a small surface area such as particles are used.

In the sulfuryl fluoride detector tube 20, when the end portion on the inlet side and the end portion on the outlet side of the detector tube body 11 are cut and the sample gas is introduced from the inlet side, the sample gas passes between the carbon dioxide removing agents. Since the detection agent 12 is reached after the carbon dioxide is removed, the measurement of sulfuryl fluoride has no effect on carbon dioxide.
The carbon dioxide removing agent may be arranged in a tube different from the detector tube main body of the sulfuryl fluoride detector tube to constitute the carbon dioxide removing tube.

FIG. 2 (a) is an appearance of such a carbon dioxide removal pipe 30, and FIG. 2 (b) is a cross-sectional view.
A carbon dioxide removing agent 35 having the same configuration as described above is disposed inside the auxiliary pipe 31 made of glass, and is made of Teflon (registered trademark) fibers at both ends inside the auxiliary pipe 31 and has a breathable plug 33. The carbon dioxide removing agent 35 is configured to be maintained inside the auxiliary pipe 31.

  When the sample gas passes through the inside of the carbon dioxide removal pipe 30, carbon dioxide is removed and sulfuryl fluoride is not removed. Therefore, the sample gas that has passed through the carbon dioxide removal pipe 30 is used as the sulfuryl fluoride of the first example. It can introduce | transduce in the detection tube 10 and can measure a sulfuryl fluoride.

Reference numeral 40 in FIG. 3 is a sulfuryl fluoride detector according to the third embodiment of the present invention.
The sulfuryl fluoride detection device 40 includes a sulfuryl fluoride detection tube 10, a carbon dioxide removal tube 30, and a connection tube 41 of the first example.

  Here, both ends of the sulfuryl fluoride detection tube 10 and both ends of the carbon dioxide removal tube 30 are cut, and an end on the outlet side of the carbon dioxide removal tube 30 and an end on the inlet side of the sulfuryl fluoride detection tube 10. The parts are connected by a connecting pipe 41.

The sample gas that has passed through the inside of the carbon dioxide removal pipe 30 passes through the inside of the connection pipe 41 and is introduced into the inside from the inlet side of the sulfuryl fluoride detection pipe 10. When passing through the inside of the sulfuryl fluoride detector tube 10 from the inlet side to the outlet side, there is no influence of carbon dioxide, and the detecting agent changes color according to the concentration of sulfuryl fluoride, and the scale 18 shows the concentration of sulfuryl fluoride in the sample gas. Has been.
The sulfuryl fluoride detector tube 20 of the second example may be connected to the carbon dioxide removal tube 30 instead of the sulfuryl fluoride detector tube 10 of the first example.

Next, particles that can be used as a main carrier and particles that can be used as a subcarrier will be described.
The reaction of sulfuryl fluoride and carbon dioxide of alumina particles adsorbed with KOH and silica sand particles adsorbed with KOH is shown in Table 1 below.

Thus, it can be seen that the silica sand particles do not remove sulfuryl fluoride and can therefore be used as a secondary carrier for the carbon dioxide removing agent, and alumina can be used as the main carrier because it reacts with sulfuryl fluoride. The diameter of the silica sand is 250Myuemu～350myuemu, specific surface area of 0.05m ² /g~0.15m ² / g.

  Below, the Example of the preparation method of the sulfuryl fluoride detector tube for high concentration, the sulfuryl fluoride detector tube for low concentration, and a carbon dioxide removal tube is described.

<Sulfuryl fluoride detector tube for high concentration>
In 300 ml of methanol solvent, 0.8 g of titanium yellow was added and dissolved. Further, 200 g of potassium hydroxide was added to 400 ml of water and dissolved. These solutions were added to 2000 g of alumina having a particle size of 60 to 100 mesh, and the solvent was completely removed in a 80 ° C. hot water bath to produce a detector for sulfuryl fluoride. This detection agent was sealed in a detection tube main body made of a glass tube having an inner diameter of 3.5 to 3.6 mm to prepare a sulfuryl fluoride detection tube capable of detecting a high concentration of sulfuryl fluoride.

<Sulfuryl fluoride detector tube for low concentration>
0.4 g of Alizarin yellow R and 7 g of potassium hydroxide were dissolved in 900 ml of water. This was added to 2000 g of alumina having a particle size of 60 to 10 mesh, and the solvent was completely removed in a 80 ° C. hot water bath to produce a detector for sulfuryl fluoride. This detection agent was sealed in a detection tube main body made of a glass tube having an inner diameter of 2.5 to 2.6 mm to produce a sulfuryl fluoride detection tube capable of detecting a low concentration of sulfuryl fluoride.

<CO2 removal pipe>
In 150 ml of water, 300 g of potassium hydroxide was added and dissolved. This was added to 1700 g of silica sand having a particle size of 40 to 60 mesh, and water was completely evaporated in a mantle heater at 250 ° C. to produce a carbon dioxide remover. This detection agent was sealed in an auxiliary tube made of a glass tube having an inner diameter of 2.9 to 3.0 mm to prepare a carbon dioxide removal tube.

<Detection tube body and auxiliary tube>
The detection tube main body 11 is not limited to glass, and does not react with SF or HF. At least a part of the detection tube main body 11 is transparent, and the discoloration of the pH indicator disposed therein can be confirmed. Anything that can cut both ends may be used. The auxiliary tube 31 is not limited to glass, but may be any tube that does not react with SF, is elongated, and can be cut at both ends.

(a): Appearance of the first and second examples of the sulfuryl fluoride detector tube of the present invention (b): Cross-sectional view for explaining the inside of the first example of the sulfuryl fluoride detector tube (c): First Sectional drawing for demonstrating the inside of two examples of sulfuryl fluoride detector tubes (a): External view of carbon dioxide removal pipe (b): Cross section External view of sulfuryl fluoride detector Graph showing the relationship between sulfuryl fluoride concentration and carbon dioxide concentration and color change length of detection agent

Explanation of symbols

10, 20... Sulfuryl fluoride detection tube 11... Detection tube body 12... Detection agent 15, 35... Carbon dioxide removal agent 30. 41 …… Connection pipe

Claims (14)

A detector tube body that is at least partially transparent;
An alkaline substance and a pH indicator are disposed inside the detector tube body, and sulfuryl fluoride contained in the sample gas introduced into the detector tube body reacts with the alkaline substance, A sulfuryl fluoride detector tube configured such that the pH indicator changes color due to pH change.   2. The sulfuryl fluoride detector tube according to claim 1, wherein the alkaline substance contains at least one of a compound of sodium hydroxide, potassium hydroxide, or lithium hydroxide.   The sulfuryl fluoride detector tube according to any one of claims 1 and 2, further comprising a porous and particulate main carrier on which the alkaline substance and the pH indicator are adsorbed.   The sulfuryl fluoride detector tube according to claim 3, wherein the main carrier contains one or more kinds of particles of alumina particles, silica gel particles, and diatomaceous earth particles.   The sulfuryl fluoride detector tube according to any one of claims 1 to 4, wherein water is contained at a position in the detector tube main body where the alkaline substance and the pH indicator are arranged.   6. The carbon dioxide removing agent is disposed in the detection tube main body upstream of a region where the alkaline substance and the pH indicator are disposed in a path through which the sample gas flows. The sulfuryl fluoride detector tube according to the item.   The sulfuryl fluoride detector tube according to claim 6, wherein the carbon dioxide removing agent has a subcarrier having a smaller surface area per grain than the main carrier, and a reactant adsorbed on the subcarrier and reacts with carbon dioxide. .   The sulfuryl fluoride detector tube according to claim 7, wherein the sub-carrier contains one or more particles of glass particles and silica sand.   The fluorination according to any one of claims 7 to 9, wherein at least any one compound of sodium hydroxide, potassium hydroxide, or lithium hydroxide is adsorbed on the auxiliary carrier as the reactant. Sulfuryl detector tube. An auxiliary tube,
A carbon dioxide removing pipe disposed in the auxiliary pipe and removing carbon dioxide contained in the sample gas introduced into the auxiliary pipe from the sample gas flowing in the auxiliary pipe;
The carbon dioxide removal pipe and the sulfuryl fluoride detection pipe according to any one of claims 1 to 5 are connected, and the sample gas flowing in the carbon dioxide removal pipe is introduced into the sulfuryl fluoride detection pipe. Having a connecting pipe,
A sulfuryl fluoride detector that measures sulfuryl fluoride in a sample gas flowing through the carbon dioxide removal tube with the sulfuryl fluoride detector tube.   The sulfuryl fluoride detection device according to claim 10, wherein the carbon dioxide removing agent has a subcarrier having a smaller surface area than the main carrier, and a reactant adsorbed on the subcarrier and reacts with carbon dioxide.   The sulfuryl fluoride detector tube according to claim 11, wherein at least any one compound of sodium hydroxide, potassium hydroxide, or lithium hydroxide is adsorbed on the auxiliary carrier as the reactant.   A sample gas is allowed to flow between the alkaline carrier and the main carrier on which the pH indicator is adsorbed, and either or both of the moisture contained in the sample gas or the moisture adsorbed on the main carrier and the sample gas are contained in the sample gas. And sulfuryl fluoride which reacts with sulfuryl fluoride contained in the catalyst to generate an acidic substance, shifts the pH of the main carrier surface in the acidic direction, and discolors the pH indicator in an amount corresponding to the amount of sulfuryl fluoride. Detection method.   The sulfuryl fluoride detection according to claim 13, wherein the sample gas is allowed to flow between subcarriers having a carbon dioxide removing agent adsorbed and having a surface area per grain smaller than that of the main carrier before flowing between the main carriers. Method.

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