JP6712012B2 - All sulfur and all halogen continuous concentration measurement system - Google Patents

Description

The present invention relates to a total sulfur and total halogen continuous concentration measuring system, and particularly to a total sulfur and total halogen continuous concentration suitable for continuously measuring a trace amount of a sulfur compound component and a total halogen compound component contained in hydrogen gas. Concentration measurement system.

In recent years, hydrogen stations have become widespread along with the practical use of hydrogen society, especially hydrogen fueled vehicles.

Along with this, the maximum impurity concentration according to ISO is shown as a hydrogen quality item. There are 10 or more components regulated therein, of which 4 ppb for all sulfur compounds and 50 ppb for all halogen compounds are regulated values. Examples of the halogen include gaseous chlorine, bromine, fluorine and the like.

Gas chromatographs (FPD, SCD), mass spectrometers (GC-MS), ICP emission spectrometry, etc. have been proposed as methods for measuring all such sulfur components (see, for example, Patent Document 1 and FIG. 1). ..

JP, 2010-286427, A

However, in the conventional method disclosed in Patent Document 1, it is difficult to measure the minute amount of all sulfur compounds at the ppb level with high accuracy.

Further, since halogen cannot be detected by FPD or SCD, it is considered to increase the sensitivity by using a mass spectrometer (MS). However, when a mass spectrometer is used as a detector, it is difficult to quantify all sulfur compounds because it is difficult to separate if the sample gas to be measured has a very close mass-to-charge ratio (for example, sulfur and oxygen). There was also the problem of being.

In order to measure all the sulfur compounds of this trace concentration by MS (in particular, continuous measurement), it is necessary to realize the following two factors.

That is, firstly, how to measure the sulfur compounds existing as individual components collectively, and secondly, how to continuously measure the trace amount of components.

Specifically, it is theoretically possible to measure all sulfur compounds by qualitatively quantifying all of the individual sulfur compounds and then adding them up, but in reality it is not possible to qualitatively analyze all components, There is a problem that you can not do it.

Further, in the case of an existing analyzer such as a gas chromatograph, it was impossible to measure the regulated value concentration of 4 ppb with high accuracy by directly introducing the sample gas containing the sulfur compound. ..

In addition, the measurement of a trace amount of all halogen compound components contained in hydrogen gas has the same problem as in the measurement of all sulfur compounds.

The present invention has been made in view of these points, and it is possible to continuously and accurately measure a trace concentration of a sulfur compound component and a total halogen compound component contained in hydrogen gas. The purpose is to provide a measurement system.

The present inventors have diligently studied to convert all the sulfur compounds into hydrogen sulfide (H ₂ S), measure the converted hydrogen sulfide, and analyze all the organic halogen compounds among the halogen compounds as inorganic substances. All sulfur compounds and all halogen compounds can be measured by converting them to halogen compounds and measuring inorganic halogen compounds. Furthermore, sample gas converted to hydrogen sulfide and inorganic halogen compounds can be cooled by electronic cooling method. Concentration makes it possible to measure all sulfur compounds with a regulated value concentration of 4 ppb or less and all halogen compounds with a regulated value concentration of 50 ppb or less, and unlike human cooling methods such as liquid oxygen, continuous concentration is possible. The present invention has been completed by finding that measurement is possible.

In order to achieve the above-mentioned object, the total sulfur and total halogen continuous concentration measuring system according to the first aspect of the present invention converts a sulfur compound into hydrogen sulfide by heating a sample gas consisting of hydrogen gas containing a sulfur compound. A reaction furnace having a function of converting the organic halogen compound into an inorganic halogen compound by heating a sample gas composed of hydrogen gas containing an organic halogen compound; and storing a sample gas taken out from the reaction furnace. A sampling unit, a concentration unit for concentrating and trapping the sample gas stored in the sampling unit into a concentrated sample gas, a sample gas stored in the sampling unit, and a concentrated sample gas concentrated and trapped in the concentration unit And an analyzer for measuring the concentrations of the sulfur compound and the inorganic halogen compound.

Since it is formed in this manner, according to the first aspect, by converting the sulfur compound component in a trace amount contained in hydrogen gas into hydrogen sulfide and by converting the organic halogen compound component into an inorganic halogen compound. It is possible to measure continuously and accurately.

Further, in the total sulfur continuous concentration measuring system according to the second aspect of the present invention, in the first aspect, the reaction furnace comprises heating means for heating the sample gas, and hydrogen sulfide for converting the heated sample gas into hydrogen sulfide. The sampling unit includes a conversion catalyst and an inorganic halogen conversion catalyst that oxidizes a heated sample gas to convert an organic halogen compound of the halogen compounds into an inorganic halogen compound, and the sampling unit stores a large amount of sample gas. A first unit for storing a small amount of sample gas, and a second unit for storing a small amount of sample gas, wherein the concentration unit includes electronic cooling means for concentrating the sample gas, and trap means for storing the concentrated concentrated sample gas. And the mass spectrometer is equipped with a mass spectrometric means.

Since it is formed in this way, according to the second aspect, in addition to the case of the first aspect, the concentration of the sample gas is selected depending on the concentrations of the sulfur compound and the halogen compound in the sample gas. It can be carried out, and more appropriately, continuously and accurately measuring by converting a trace concentration of a sulfur compound component contained in hydrogen gas into hydrogen sulfide and by converting an organic halogen compound component into an inorganic halogen compound. You can

According to the present invention, it is possible to continuously and accurately measure with a mass spectrometer by converting a trace amount of a sulfur compound component contained in hydrogen gas into hydrogen sulfide and converting an organic halogen compound component into an inorganic halogen compound. It is possible to exhibit an excellent effect of being able to do.

Block diagram showing an embodiment of the total sulfur and total halogen continuous concentration measuring system of the present invention System circuit diagram showing an embodiment of the continuous sulfur and total halogen concentration measuring system of the present invention

An embodiment of the present invention will be described below with reference to FIGS. 1 and 2.

FIG. 1 is a block diagram showing an embodiment of a continuous sulfur and total halogen concentration measuring system according to the present invention.

The all-sulfur and all-halogen continuous concentration measuring system 1 of this embodiment is processed with an all-sulfur and all-halogen processing unit 2 that processes a sample gas SG consisting of a sulfur compound and a hydrogen gas containing a halogen compound to a state where it can be analyzed. It has an analyzer 3 for measuring the concentrations of all sulfur compounds and all halogen compounds in the sample gas SG, and a controller 4 including a central controller (CPU) for controlling the operation of the entire system.

In the all-sulfur and all-halogen processing unit 2, a reaction furnace 5, a sampling unit 6, and a concentration unit 7 are provided in the order of progress of the sample gas SG. The reactor 5 has a function of converting a sulfur compound into hydrogen sulfide by heating a sample gas SG composed of hydrogen gas containing a sulfur compound and a halogen compound, and a sample gas SG composed of hydrogen gas containing a halogen compound. It is formed to have a function of converting an organic halogen compound among halogen compounds into an inorganic halogen compound. The sampling unit 6 is formed so as to store the sample gas SG taken out from the reaction furnace 5. The concentration unit 7 is formed so as to trap the sample gas SG stored in the sampling unit 6 into a concentrated sample gas. The analyzer 3 is formed to measure the concentrations of the sulfur compound and the inorganic halogen compound in the sample gas SG stored in the sampling unit 6 and the concentrated sample gas CSG concentrated and trapped in the concentration unit 7.

Further description will be given including FIG.

In FIG. 2, the connecting pipe through which the sample gas SG containing a sulfur compound and a halogen compound flows is shown by a double line, and is formed by a sulfur compound inert tube, a Teflon tube (Teflon is a registered trademark), or the like. Has been done. The connecting pipe through which the gas other than the sample gas SG flows is shown by a solid line.

The reaction furnace 5 heats the sulfur gas reaction furnace 15 having a function of converting the sulfur compound into hydrogen sulfide by heating the sample gas SG, and the organic gas of the halogen compounds by heating the sample gas SG. A halogen reaction furnace 16 having a function of converting into a compound is provided in parallel. One of the sulfur reaction furnaces 15 is equipped with an electric heating furnace 15a as a heating means for heating the sample gas SG, and a hydrogen sulfide conversion catalyst (not shown) for converting the heated sample gas SG into hydrogen sulfide. There is. The hydrogen sulfide conversion catalyst is formed by a quartz reaction tube (inner diameter: 6 mm, length: 30 cm, soaking zone: 10° C.×50 mm, reaction temperature: 800 to 1100° C.) loaded with specially treated quartz beads. In this hydrogen sulfide conversion catalyst, all the sulfur compounds are converted into hydrogen sulfide by ventilating a sample gas GS containing a sulfur compound and reacting in the presence of hydrogen in a heating environment of 1000°C. According to the hydrogen sulfide conversion catalyst provided with the quartz beads, which are subjected to the special treatment of the quartz beads by the phosphoric acid heat treatment, a good conversion rate is exhibited without a time change. On the other hand, in the case of the conventional metal catalyst such as platinum, the conversion rate deteriorates with the passage of time, and finally it does not contribute to the conversion at all. The other halogen reaction furnace 16 is an electric heating furnace 16a as a heating means for heating the sample gas SG and an inorganic furnace for oxidizing the heated sample gas SG to convert an organic halogen compound of the halogen compounds into an inorganic halogen compound. And a halogen conversion catalyst (not shown). This inorganic halogen conversion catalyst is an oxidation catalyst, and is formed of, for example, Pt/Al ₂ O ₃ . In this inorganic halogen conversion catalyst, a sample gas GS containing an organic halogen compound and an added oxidizing gas are aerated and reacted in the presence of an oxidizing gas in a heating environment of 1000° C. to give an organic halogen compound. Are all converted to inorganic halogen compounds.

The sampling unit 6 has three automatic 6-way valves 6a, 6b, 6c, and the automatic 6-way valve 6a on the most upstream side is a sample as a first unit that stores a large amount (about 100 cc) of the sample gas SG. The automatic 6-way valve 6c on the most downstream side includes a loop 6aa, and a sample loop 6cc as a second unit that stores a small amount (about 1 cc) of the sample gas SG.

The concentration unit 7 includes a Peltier cooler 7a as an electronic cooling means for concentrating the sample gas SG, and a U-shaped tube 7b as a trap means for storing the concentrated concentrated sample gas CSG. The Peltier cooler 7a is installed so as to cover the outside of the U-shaped tube 7b. The Peltier cooler 7a is formed so that a U-shaped tube 7b in which a heater is wound around a cooling block made of aluminum utilizing the Peltier effect is brought into close contact during cooling and is heated away from it when heated.

Next, the piping system will be described.

In the reaction furnace 5, inlets and outlets of the sulfur reactor 15 and the halogen reactor 16 are connected in parallel with two partition valves 17a, 17b and 18a, 18b. An inlet SGin of the sample gas SG and an inlet STDin of the standard gas are pipe-connected to the joint between the two partition valves 17a and 17b. Diluting gas is further supplied to one of the inlets STDin. The inlet of the halogen reaction furnace 16 is connected to the joint between the sluice valve 17b and the sluice valve 17c that is arranged to face the sluice valve 17b. The upstream side of the partition valve 17c is connected to the oxidizing gas inlet OSGin by piping. Examples of the oxidizing gas include oxygen, ozone, air, hydrogen peroxide alone or a mixed gas. The junction between the two sluice valves 18a and 18b is laid so as to be selectively connected to the 1-port 6a1 of the automatic 6-way valve 6a on the most upstream side and the bypass out 10 with the electromagnetic switching valve 9.

In the sampling unit 6, each of the automatic 6-way valves 6a, 6b, and 6c is provided with inlets 1 to 6 in a counterclockwise direction from the inlet at the lower left, and pipes that connect to each other are installed. In the most upstream 6-way valve 6a, a sample loop 6aa is connected between the inlets 6a3 and 6a6, the inlet 6a2 is connected to the inlet 6c1 of the most downstream automatic 6-way valve 6c, and the inlet 6a4. Is connected to the inlet 6b2 of the automatic 6-way valve 6b at the intermediate position, and the inlet 6a5 is connected to the inlet Nin of the nitrogen gas for transporting the sample gas SG through the sluice valve 11. In the automatic 6-way valve 6b in the intermediate position, the inlet 6b1 and the outlet 12 are connected, the inlets 6b3 and 6b6 are connected to the respective ends of the U-tube 7b, and the inlet 6b4 forms the analyzer 3. The column 6b5 of the mass spectrometer MS is read so that the inlet 6b5 is connected to the inlet 6c4 of the automatic 6-way valve 6c on the most downstream side. In the automatic 6-way valve 6c on the most downstream side, the inlet 6c2, the sample gas outlet 13 and the buffer filter 14 are connected, and the sample loop 6cc is connected between the inlets 6c3 and 6c6. Is connected to the inlet CGin of the carrier gas CG of the analyzer 3.

Next, the operation of this embodiment will be described.

<When measuring the concentration of all sulfur compounds in the sample gas SG>
The measurement of the concentration of all sulfur compounds proceeds in the order of a sample collecting step, a sample cooling/concentrating step, and a sample heating unloading=concentration measuring step. Each step will be described below.

(Sample collection process)
The state setting of each component is as follows.
Electromagnetic switching valve 9: Double line (ON state)
Automatic 6-way valve 6a: solid line connected state Automatic 6-way valve 6b: solid line connected state Automatic 6-way valve 6c: solid line connected state Peltier cooler 7a: cooling state Electromagnetic switching valve 9 is turned off before the sampling process The residual gas in the system is discharged from the bypass out 10 through the pipe of (1), and the switching valve 9 is returned after the discharge is completed.

After that, the sluice valves 17a and 18a in the upstream and downstream of the sulfur reactor 15 are opened, and the sluice valves 17b and 18b in the upstream and downstream of the halogen reactor 16 are closed to operate the sulfur reactor 15. Let the state. In this state, the sample gas SG that has flowed in from the sample gas cylinder connected to the sample gas inlet SGin passes through the sulfur sulfide conversion catalyst in the sulfur reaction furnace 15 which is in a heated state at 1000° C. The compound reacts with the hydrogen gas in the sample gas GS to convert all sulfur compounds into hydrogen sulfide. After that, the sample gas SG is gradually stored in the sample loop 6aa until it reaches 100 cc while passing through the automatic 6-way valve 6a. At the same time, excess gas is discharged out of the system through the inlet 6a2 of the automatic 6-way valve 6a, the inlets 6c1 and 6c2 of the automatic 6-way valve 6c, and the sample gas outlet 13 to sufficiently replace the sample loop 6aa with the sample gas.

(Cooling and concentration process of sample)
The state setting of each component is switched as follows.
Electromagnetic switching valve 9: Solid line (OFF state)
Automatic 6-way valve 6a: Broken line connection state Automatic 6-way valve 6b: Solid line connection state Automatic 6-way valve 6c: Solid line connection state Peltier cooler 7a: Cooling state In this way, the electromagnetic switching valve 9 is turned off and the sulfur reactor 15 is connected to the bypass out 10 to prevent the sample gas SG from flowing into the sampling unit 6. In this state, a large amount of 100 cc of the sample gas SG stored in the sample loop 6aa is introduced into the inlets 6a3 and 6a4 by causing the nitrogen gas to flow into the inlet 6a5 of the most upstream automatic 6-way valve 6a from the carrier gas inlet Nin. , Through the inlets 6b2, 6b3 of the automatic 6-way valve 6b in the intermediate position in order to be introduced into the concentration unit 7 cooled to about 5°C by the Peltier cooler 7a, and all the sulfur components are gradually stored in the U-shaped pipe 7b. Go on. At the same time, excess gas derived from hydrogen is discharged to the outside of the system through the other inlet of the U-shaped pipe 7b, the inlets 6b6 and 6b1 of the automatic 6-way valve 6b, and the outlet 12. As a result, the concentrated sample gas DSG is formed in the U-shaped tube 7b.

Since the molecules derived from oxygen are not stored in the U-shaped tube 7b, and the molecules derived from sulfur are almost completely converted to hydrogen sulfide and stored in the U-shaped tube 7b, the mass spectrometer MS is used as a detector. Even in such a case, the sulfur component and the oxygen-derived molecule can be easily separated to measure the concentration of all sulfur compounds.

(Expulsion of sample heating = concentration measurement process)
The state setting of each component is switched as follows.
Electromagnetic switching valve 9: Solid line (OFF state)
Automatic 6-way valve 6a: solid line connection state Automatic 6-way valve 6b: dashed line connection state Automatic 6-way valve 6c: solid line connection state U-shaped tube 7b: heating state In this state, carrier gas CG for analysis is supplied with carrier gas CG for analysis. By flowing into the inlet 6c5 of the most downstream 6-way valve 6c, the carrier gas CG passes through the inlet 6c4 and the inlets 6b5 and 6b6 of the automatic 6-way valve 6b in the intermediate position in this order, and the U-shaped tube 7b of the concentrating unit 7 is passed. Is supplied to the other entrance. At the same time, the concentrated sample gas DSG in the U-shaped tube 7b is supplied to the inlet of the column (not shown) of the analyzer 3 through one inlet of the U-shaped tube 7b and the inlets 6b3 and 6b4 of the automatic 6-way valve 6b. The hydrogen sulfide in the concentrated sample gas DSG collected in this column is detected by the mass spectrometer MS forming the analyzer 3 and output to the data processing device 4 for measuring total sulfur and total halogen, and then the sample gas SG. The concentration of all sulfur compounds in is displayed.

Thus, all sulfur compounds can be measured by converting all the sulfur compounds into hydrogen sulfide (H ₂ S) and measuring the converted hydrogen sulfide, and further, the sample gas converted into hydrogen sulfide can be measured. By cooling and concentrating with an electronic cooling method, it is possible to suitably separate from molecules derived from oxygen, and it is possible to measure a regulated value concentration of 4 ppb or less. Furthermore, unlike the cooling method using liquid oxygen, etc., no human labor is required. It has been found that continuous concentration measurement is possible.

It should be noted that at the time of calibration curve calibration, it is advisable to supply the standard gas into the system through the standard gas inlet STDin.

<When the concentration of total halogen compounds in the sample gas SG is low>
The measurement of the concentration of all halogen compounds proceeds in the order of a sample collecting step, a sample cooling/concentrating step, and a sample heating unloading=concentration measuring step. Each step will be described below.

(Sample collection process)
The state setting of each component is as follows.
Electromagnetic switching valve 9: Double line (ON state)
Automatic 6-way valve 6a: solid line connected state Automatic 6-way valve 6b: solid line connected state Automatic 6-way valve 6c: dashed line connected state Peltier cooler 7a: cooling state Electromagnetic switching valve 9 is turned off before sampling process Unnecessary gas in the system is discharged from the bypass out 10 through the pipe, and the switching valve 9 is returned after the discharge is completed.

Thereafter, the upstream and downstream sluice valves 17b and 18b of one of the halogen reaction furnaces 16 are opened, the upstream and downstream sluice valves 17a and 18a of the other sulfur reaction furnace 15 are closed, and the halogen reaction furnace 16 The upstream/downstream sluice valve 17c is also opened and the oxidizing gas OGS is supplied from the inlet OGSin to activate the halogen reaction furnace 16. In this state, the sample gas SG flowing in from the sample gas cylinder connected to the sample gas inlet SGin is sampled while passing through the inorganic halogen conversion catalyst in the halogen reaction furnace 16 heated at 1000° C. The halogen compound in the gas GS and the oxidizing gas OGS composed of oxygen undergo an oxidation reaction to convert all the organic halogen compounds of the halogen compounds into inorganic halogen compounds.

The reaction is performed according to the following formula.
_{R-Cl + O 2 → CO} 2 + HCl + H 2 O

In this case, the supply amount of oxygen may be 100 to 4000 ppm, preferably 100 to 2000 ppm, more preferably 400 to 2000 ppm, and further preferably 400 to 1000 ppm with respect to the sample gas SG. Regarding ozone and air, the supply amount of oxygen may be the same as that of oxygen alone. In the case of air, it may be 2000 to 10000 ppm (=0.2 to 1.0%). Further, the oxygen supply position may be an upstream position immediately before the inorganic halogen conversion catalyst.

After that, the sample gas SG is gradually stored in the sample loop 6aa until it reaches 100 cc while passing through the automatic 6-way valve 6a. At the same time, unnecessary gas is discharged out of the system through the inlet 6a2 of the automatic 6-way valve 6a, the inlets 6c1 and 6c2 of the automatic 6-way valve 6c, and the sample gas outlet 13.

In consideration of the reactivity of the inorganic halogen compound (for example, hydrogen chloride) generated by the conversion, it is preferable to use resistant members for the pipes and the gas contacting parts after the halogen reaction furnace 16.

(Cooling and concentration process of sample)
The state setting of each component is switched as follows.
Electromagnetic switching valve 9: Solid line (OFF state)
Automatic 6-way valve 6a: broken line connected state Automatic 6-way valve 6b: solid line connected state Automatic 6-way valve 6c: solid line connected state Peltier cooler 7a: cooling state In this way, the electromagnetic switching valve 9 is turned off and the halogen reactor 16 is connected to the bypass out 10 to prevent the sample gas SG from flowing into the sampling unit 6. In this state, a large amount of 100 cc of the sample gas SG stored in the sample loop 6aa is introduced into the inlets 6a3 and 6a4 by causing the nitrogen gas to flow into the inlet 6a5 of the most upstream automatic 6-way valve 6a from the carrier gas inlet Nin. , Through the inlets 6b2, 6b3 of the automatic 6-way valve 6b in the middle position in order to be introduced into the concentration unit 7 cooled to about 5° C. by the Peltier cooler, and all the halogen components are gradually stored in the U-shaped tube 7b. go. At the same time, excess gas derived from hydrogen is discharged to the outside of the system through the other inlet of the U-shaped pipe 7b, the inlets 6b6 and 6b1 of the automatic 6-way valve 6b, and the outlet 12. As a result, the concentrated sample gas DSG is formed in the U-shaped tube 7b.

(Expulsion of sample heating = concentration measurement process)
The state setting of each component is switched as follows.
Electromagnetic switching valve 9: Solid line (OFF state)
Automatic 6-way valve 6a: solid line connected state Automatic 6-way valve 6b: dashed line connected state Automatic 6-way valve 6c: solid line connected state U-shaped tube 7b: heating state In this state, carrier gas CG for analysis is supplied from carrier gas CGin for analysis. By flowing into the inlet 6c5 of the most downstream 6-way valve 6c, the carrier gas CG passes through the inlet 6c4 and the inlets 6b5 and 6b6 of the automatic 6-way valve 6b in the intermediate position in this order, and the U-shaped tube 7b of the concentrating unit 7 is passed. Is supplied to the other entrance. At the same time, the concentrated sample gas DSG in the U-shaped tube 7b is supplied to the inlet of the column (not shown) of the analyzer 3 through one inlet of the U-shaped tube 7b and the inlets 6b3 and 6b4 of the automatic 6-way valve 6b. The inorganic halogen compound in the concentrated sample gas DSG collected in this column is detected by the mass spectrometer MS forming the analyzer 3 and output to the data processing device 4 for measuring total sulfur and total halogen, and then the sample gas. The total halogen compound concentration in SG is displayed.

In this way, among halogen compounds, all individual halogen compounds can be converted to inorganic halogen compounds, and all halogen compounds can be measured by measuring inorganic halogen compounds. Furthermore, sample gas converted to inorganic halogen compounds can be measured. It was found that the concentration of 50 ppb or less of the regulated value can be measured by cooling and concentrating with an electronic cooling method, and further, unlike the cooling method using liquid oxygen or the like, no manual labor is required, and thus continuous concentration measurement can be performed. It was

It should be noted that at the time of calibration curve calibration, it is advisable to supply the standard gas into the system through the standard gas inlet STDin.

<When the concentration of all halogen compounds in the sample gas SG is high>
The measurement of the concentration of all halogen compounds proceeds in the order of the sample collecting step and the heating of the sample=concentration measuring step. Since the concentration is high, the cooling concentration step will be omitted. Each step will be described below.

(Sample collection process)
The state setting of each component is as follows.
Electromagnetic switching valve 9: Double line (ON state)
Automatic 6-way valve 6a: Broken line connection Automatic 6-way valve 6b: Solid line connection Automatic 6-way valve 6c: Solid line connection Peltier cooler 7a: Unused Before the sampling process, the electromagnetic switching valve 9 is turned off to the solid line The residual gas in the system is discharged from the bypass out 10 through the pipe of (1), and the switching valve 9 is returned after the discharge is completed.

Then, the sample gas SG flowing from the inside of the sample gas cylinder connected to the sample gas inlet SGin is passed through the inorganic halogen conversion catalyst in the halogen reaction furnace 16 heated at 1000° C. The organic halogen compound therein and the oxidizing gas OGS composed of oxygen undergo an oxidation reaction, whereby all the organic halogen compounds of the halogen compounds are converted into inorganic halogen compounds. Then, the sample gas SG is supplied to the inlets 6a1 and 6a2 of the automatic 6-way valve 6a and the inlet 6c1 of the most downstream automatic 6-way valve 6c, and then 1cc in the sample loop 6cc while passing through the automatic 6-way valve 6c. It will be gradually stored until it becomes. At the same time, excess gas is discharged out of the system through the inlet 6c2 of the automatic 6-way valve 6c and the sample gas outlet 13.

(Expulsion of sample heating = concentration measurement process)
The state setting of each component is switched as follows.
Electromagnetic switching valve 9: Solid line (OFF state)
Automatic 6-way valve 6a: Solid line connected state Automatic 6-way valve 6b: Solid line connected state Automatic 6-way valve 6c: Broken line connected state Peltier cooler 7a: Not used In this way, the electromagnetic switching valve 9 is turned off and the halogen reactor 16 is connected to the bypass out 10 to prevent the sample gas SG from flowing into the sampling unit 6. In this state, the carrier gas CGin is supplied to the inlets 6c5, 6c6 and the sample loop 6cc by causing the carrier gas for analysis to flow into the inlet 6c5 of the most downstream 6-way automatic valve 6c. Subsequently, a small amount of 1 cc of the sample gas SG stored in the sample loop 6cc is supplied to the column inlet of the analyzer 3 through the inlets 6c3 and 6c4 and the inlets 6b5 and 6b4 of the automatic 6-way valve 6b at the intermediate position in this order. To be done. The inorganic halogen in the sample gas SG collected in this column is detected by the mass spectrometer MS forming the analyzer 3,

It is output to the data processor 4 for measuring all sulfur and all halogen, and then the concentration of all halogen compounds in the sample gas SG is displayed.

In this way, all the halogen compounds can be measured by converting all of the halogen compounds to inorganic halogen compounds and measuring the inorganic halogen compounds. Furthermore, it is possible to measure the regulated value concentration of 50 ppb or less. It was also found that continuous concentration measurement is possible because no human labor is required unlike the cooling method using liquid oxygen.

The present invention is not limited to the above-described embodiments and examples, but can be modified as necessary.

For example, in the present embodiment, the concentration amount is about 100 cc in order to enable detection of 1 ppb, but by increasing the concentration amount, it is possible to measure a concentration of 0.1 ppb or less or a further trace amount. Further, since the large-capacity sample loop 6aa physically enlarges the device, a method of setting the concentration amount by a mass flow meter is also possible.

Further, sulfur compounds regulated by the Odor Control Law are subjected to concentration analysis using liquid oxygen, but continuous measurement is impossible because it takes time to supplement liquid oxygen. By utilizing the concentration operation by the electronic cooling method according to the present invention, unattended continuous concentration operation becomes possible.

The present invention is also applicable to the measurement of total sulfur in general gases other than hydrogen gas, such as nitrogen gas, argon gas, carbon dioxide gas.

1 Total Sulfur and Total Halogen Concentration Measuring System 3 Analyzer 5 Reactor 6 Sampling Unit 6aa, 6cc Sample Loop 7 Concentration Unit 7a Peltier Cooler 7b U-tube 15 Sulfur Reactor 16 Halogen Reactor

Claims (2)

Organohalogen compound of the halogen compounds by heating the sample gas composed of hydrogen gas containing a sulfur compound and heating the sample gas composed of hydrogen gas containing a halogen compound by heating the sample gas composed of hydrogen gas containing a sulfur compound And a reaction furnace having a function of converting into an inorganic halogen compound,
A sampling unit for storing the sample gas taken out from the reaction furnace,
A concentrating unit for concentrating and trapping the sample gas stored in the sampling unit as a concentrated sample gas,
An analyzer for measuring the concentrations of the sulfur compound in the sample gas stored in the sampling unit and the concentrated sample gas concentrated and trapped in the concentration unit and the inorganic halogen compound in the concentrated sample gas. Sulfur and halogen continuous concentrating measurement system. The reaction furnace comprises a heating means for heating the sample gas, a hydrogen sulfide conversion catalyst for converting the heated sample gas into hydrogen sulfide, and an organic halogen compound of the halogen compounds as an inorganic substance by oxidizing the heated sample gas. Equipped with an inorganic halogen conversion catalyst for converting to a halogen compound,
The sampling unit includes a first unit that stores a large amount of sample gas and a second unit that stores a small amount of sample gas,
The concentrating unit comprises an electronic cooling means for concentrating the sample gas, and a trap means for storing the concentrated concentrated sample gas,
The total sulfur and total halogen continuous concentration measurement system according to claim 1, wherein the analyzer is provided with a mass spectrometric unit.

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