WO2020161833A1

WO2020161833A1 - Sulfur chemiluminescence detector

Info

Publication number: WO2020161833A1
Application number: PCT/JP2019/004269
Authority: WO
Inventors: 雅史山根; 茂暢中野
Original assignee: 株式会社島津製作所
Priority date: 2019-02-06
Filing date: 2019-02-06
Publication date: 2020-08-13
Also published as: JPWO2020161833A1; JP7143902B2; CN113056667A

Abstract

This sulfur chemiluminescence detector is characterized by having: a heating furnace 210; a reaction cell 231 that causes a gas passed through the heating furnace to react with ozone; a photomultiplier tube 233 that detects light from the reaction cell; a high-voltage power source 291 that generates a driving voltage to be applied to the photomultiplier tube; a voltage control unit 311 that controls the high-voltage power source and that has, as an activation mode for the high-voltage power source, a normal mode for generating a first driving voltage to be applied to sample analysis and an abnormality detection mode for generating a second driving voltage lower than the first driving voltage; a determination means 313 for determining whether there is a connection failure between the reaction cell and the photomultiplier tube or between the reaction cell and one or more pipes connected to the reaction cell, on the basis of an output signal of the photomultiplier tube when the high-voltage power source is activated in the abnormality detection mode; and a notification means 314 for giving, when the determination means determines that there is a connection failure, a notification to that effect to a user.

Description

Chemiluminescent sulfur detector

The present invention relates to a chemiluminescence sulfur detector (Sulfur Chemiluminescence Detector).

A chemiluminescent sulfur detector (SCD) is a detector that can detect a sulfur compound in a sample with high sensitivity by using chemiluminescence, and is usually used in combination with a gas chromatograph (GC) (for example, patents). Reference 1).

The gas containing the sample components (sample gas) separated by the GC column is introduced into the heating furnace provided in the SCD. The heating furnace includes a combustion tube and a heater that heats the combustion tube. The sample gas is oxidized in the process of passing through the inside of the combustion tube, and sulfur dioxide (SO ₂ ) is converted from a sulfur compound in the sample gas. Is generated. Further, this SO ₂ is reduced in the process of passing through the inside of the combustion tube, and sulfur monoxide (SO) is generated from SO ₂ . This SO is introduced into a reaction cell provided in the latter stage of the heating furnace and mixed with ozone (O ₃ ) in the reaction cell. As a result, the excited species of sulfur dioxide (SO ₂ ^* ) is generated by the reaction between SO and O ₃ . The emission intensity when this SO ₂ ^* returns to the ground state via chemiluminescence is detected by a photodetector, and the sulfur compound contained in the sample gas is quantified from the emission intensity.

JP 2015-59876 JP

The piping of the SCD may be removed during maintenance work, etc. The removed pipes are reassembled after the completion of maintenance work, etc., but at that time, there may be a part where the connection part of the pipe is insufficiently tightened (hereinafter referred to as a “connection failure part”). If the SCD is started without noticing such a defective connection, the expected performance may not be obtained or the parts may be damaged.

For example, the light generated by the chemiluminescence in the reaction cell of the SCD enters the photomultiplier tube through the optical filter, but if there is a connection failure part in the pipe or the like that constitutes the path of this light, it will leak from that part. The extraneous light that enters may enter the photomultiplier tube, and a large current may flow into the photomultiplier tube, resulting in damage.

In addition, the SCD has a gas flow path from the combustion tube of the heating furnace through the reaction cell to the vacuum pump, and the gas in the flow path is sucked by the vacuum pump when the SCD operates. When there is a poor connection in the piping that constitutes the flow path of such gas, the outside air leaks into the flow path from the location and the reaction in the heating furnace or reaction cell is hindered, and the desired performance cannot be achieved. There is.

The present invention has been made in view of the above points, and an object of the present invention is to allow a user to easily know whether or not there is a defective connection portion in a pipe or the like included in an SCD. Especially.

A chemiluminescent sulfur detector (SCD) according to a first aspect of the present invention made to solve the above problems is
Heating furnace,
A reaction cell for reacting the gas passing through the heating furnace with ozone,
A photomultiplier tube for detecting light from the reaction cell,
A power supply for generating a driving voltage applied to the photomultiplier tube,
The power supply is controlled, and a normal mode for generating a first drive voltage applied to sample analysis and a second drive voltage lower than the first drive voltage are used as start-up modes of the power supply. A voltage control means having an abnormality detection mode to be generated,
When the power supply is started in the abnormality detection mode, based on the output signal of the photomultiplier tube, connected between the reaction cell and the photomultiplier tube, or the reaction cell and the reaction cell Determination means for determining whether or not there is a poor connection with any one of the pipes or the plurality of pipes;
When the determination unit determines that there is a poor connection, a notification unit that notifies the user of that fact,
It is characterized by having.

As described above, in the chemiluminescent sulfur detector according to the first aspect of the present invention, the presence or absence of poor connection of the pipe is determined based on the output signal of the photomultiplier tube. The photomultiplier tube may be damaged by a large current flowing inside when excessive light is incident, but the chemiluminescent sulfur detector according to the first aspect of the present invention uses the photomultiplier to prevent this. It has an anomaly detection mode in which the drive voltage applied to the tube is suppressed compared to when the sample is analyzed. In the abnormality detection mode, since the current amplification factor in the photomultiplier tube becomes small, it is possible to prevent a large current from flowing through the photomultiplier tube even when excessive light is incident. Therefore, according to the chemiluminescent sulfur detector according to the first aspect of the present invention, the above determination is performed without damaging the photomultiplier tube even when external light is leaking due to poor connection. be able to.

Note that it is desirable that the first voltage is 500V or more and the second voltage is less than 500V.

Further, the program according to the first aspect of the present invention is
Heating furnace,
A reaction cell for reacting the gas passing through the heating furnace with ozone,
A photomultiplier tube for detecting light from the reaction cell,
A power supply for generating a driving voltage applied to the photomultiplier tube,
A program for controlling a chemiluminescent sulfur detector having:
Computer,
The power supply is controlled, and as a start-up mode of the power supply, a normal mode for generating a first drive voltage applied to sample analysis and a second drive voltage lower than the first drive voltage are generated. A voltage control means having an abnormality detection mode,
When the power supply is started in the abnormality detection mode, based on the output signal of the photomultiplier tube, connected between the reaction cell and the photomultiplier tube, or the reaction cell and the reaction cell In addition, when the determination unit determines whether there is a connection failure with one or a plurality of pipes, and the determination unit determines that there is a connection failure, the user is notified of that fact. Notification means,
It is characterized by functioning as.

Further, a chemiluminescent sulfur detector according to a second aspect of the present invention made to solve the above-mentioned problems,
A heating furnace provided with a first pipe and a heating means for heating the first pipe;
A reaction cell connected to the heating furnace by a second pipe,
A vacuum pump connected to the reaction cell by a third pipe;
A fourth pipe for introducing gas into the first pipe;
Pressure measuring means for measuring the pressure inside at least one of the second pipe, the third pipe, and the fourth pipe;
Pump control means for controlling the vacuum pump,
Based on the measured value of the pressure measuring means in a state where the vacuum pump is operated by the pump control means, the first pipe, the reaction cell, or a plurality of pipes connected to the first pipe or the reaction cell. Any of the piping of, the determination means for determining whether there is a defective connection point,
When the determination unit determines that there is the defective connection portion, a notification unit that notifies the user of that fact,
It is characterized by having.

Here, the “plurality of pipes connected to the first pipe or the reaction cell” means a pipe directly connected to the first pipe or the reaction cell (for example, the second pipe, the third pipe). , And the fourth pipe), and a pipe indirectly connected to the first pipe or the reaction cell via another pipe.

In the chemiluminescent sulfur detector, if it is operated for a long time, a part of the first pipe (an internal combustion pipe described later) may be deformed and blocked, and in that case, a gas flow path from the heating furnace to the vacuum pump In, the pressure difference between the upstream region of the heating furnace and the downstream region of the heating furnace becomes large. Therefore, it is desirable that the chemiluminescent sulfur detector according to the second aspect of the present invention further determine whether or not the first pipe is blocked based on such a pressure difference. ..

That is, the chemiluminescent sulfur detector according to the second aspect of the present invention is
The pressure measuring means further measures a pressure difference between the inside of the second pipe or the third pipe and the inside of the fourth pipe,
It is desirable that the determination means further determine whether or not the first pipe is closed based on the difference.

The program according to the second aspect of the present invention is
A heating furnace provided with a first pipe and a heating means for heating the first pipe;
A reaction cell connected to the heating furnace by a second pipe,
A vacuum pump connected to the reaction cell by a third pipe;
A fourth pipe for introducing gas into the first pipe;
Pressure measuring means for measuring the pressure inside at least one of the second pipe, the third pipe, and the fourth pipe;
Pump control means for controlling the vacuum pump,
A program for controlling a chemiluminescent sulfur detector having:
Computer,
Based on the measured value of the pressure measuring means in a state where the vacuum pump is operated by the pump control means, the first pipe, the reaction cell, or a plurality of pipes connected to the first pipe or the reaction cell. Any of the piping of, the determination means for determining whether there is a connection failure location, and the notification means for notifying the user to that effect when it is determined by the determination means that there is a connection failure location,
It is characterized by functioning as.

As described above, according to the chemiluminescent sulfur detector of the present invention, the presence or absence of a connection failure of the pipe or the like is automatically determined based on the output signal from the photomultiplier tube or the measurement value of the pressure measuring means. .. As a result, the user can easily know whether or not there is a connection failure in the piping, etc., so that the chemiluminescent sulfur detector is normally activated without noticing the connection failure, and the component is damaged or desired. It is possible to prevent that the performance of is not obtained.

1 is a front view showing the appearance of a GC system including an SCD according to an embodiment of the present invention. The figure which shows the principal part structure of said SCD. The front view which shows typically the internal structure of the GC system containing the said SCD. The top view which shows the internal structure of the said GC system typically. Sectional drawing which shows the structure of the said SCD heating furnace vicinity. The flowchart which shows the operation|movement at the time of the connection failure check by said SCD. The schematic diagram which shows another structural example of the GC system containing the SCD of this invention. The schematic diagram which shows another structural example of GC system containing SCD of this invention.

A configuration for implementing the present invention will be described below with reference to the drawings. FIG. 1 is a front view showing the external appearance of a gas chromatograph system (GC system) including a chemiluminescent sulfur detector (SCD) according to this embodiment. FIG. 2 is a diagram showing a main part configuration of the SCD according to the present embodiment. 3 and 4 are schematic diagrams showing the internal structure of the GC system, FIG. 3 is a front view, and FIG. 4 is a top view. FIG. 5 is a cross-sectional view showing a structure near the heating furnace of the SCD.

The GC 100 includes a sample introduction unit 110, a column oven 120 that accommodates and heats a column 140, and a control substrate accommodation unit 130 that accommodates a control substrate (not shown) and the like. A front surface of the column oven 120 is a door 121 that can be opened and closed, and a front surface of the control board housing unit 130 is provided with an operation panel 131 including a touch panel 132 and operation buttons 133.

In the GC 100, the sample is introduced into the flow of the carrier gas in the sample introduction unit 110, and the carrier gas containing the sample is introduced into the inlet end of the column 140 housed in the column oven 120. The sample is separated into components as it passes through the column 140, and a gas containing each separated sample component (hereinafter referred to as “sample gas”) is sequentially eluted from the outlet end of the column 140.

As shown in FIG. 2, the SCD 200 is connected to a heating furnace 210 for oxidizing and reducing a sample gas at a high temperature, a reaction cell 231 for reacting the gas passing through the heating furnace 210 with ozone, and a reaction cell 231. , A photomultiplier tube 233 for detecting chemiluminescence due to a reaction in the reaction cell 231, a high-voltage power source 291 for generating a driving voltage applied to the photomultiplier tube 233, and ozone for supplying to the reaction cell 231. An ozone generator 234 for controlling, a vacuum pump 236 for evacuating the reaction cell 231 and the heating furnace 210, an ozone scrubber 235 for removing ozone from the exhaust of the reaction cell 231, a flow controller 237, and a control/processing unit 300. , And a housing 240 (see FIG. 1) for housing these. A vacuum gauge (hereinafter referred to as “first vacuum gauge 238”) is provided in the pipe 281 between the reaction cell 231 and the ozone scrubber 235. Further, a vacuum gauge (hereinafter referred to as “second vacuum gauge 239”) is also provided on the inert gas flow path 264 described later. The first vacuum gauge 238 and the second vacuum gauge 239 correspond to the “pressure measuring means” in the present invention. Further, the SCD 200 is provided at the boundary with the GC 100 and includes an interface 250 for connecting the GC 100 and the SCD 200.

In the present embodiment, the second vacuum gauge 239 is made up of an absolute pressure sensor, and the first vacuum gauge 238 is made up of a differential pressure sensor. The first vacuum gauge 238, which is a differential pressure sensor, has a pressure at a position where it is provided (that is, a pressure downstream of the reaction cell 231) and a pressure at a position where the second vacuum gauge 239 is provided (that is, the heating furnace 210). The pressure at the upstream side) is output as a measured value.

As shown in FIGS. 3 and 4, in the SCD 200, the heating furnace 210 is housed in the upper front side of the housing 240 of the SCD 200, and the reaction cell 231 and other components (not shown in FIGS. 3 and 4) are It is housed in the remaining space inside the housing 240 (for example, below or behind the heating furnace 210). The upper surface of the space in which the heating furnace 210 is housed in the housing 240 of the SCD 200 is a removable top plate 241 (see FIG. 1).

As shown in FIG. 5, the heating furnace 210 includes an external combustion pipe 211, an internal combustion pipe 212, an oxidant supply pipe 213, an inert gas introduction pipe 214, and a heater 215 (in the “heating means” of the present invention). Equivalent) and a housing 216 that houses them. The external combustion pipe 211, the internal combustion pipe 212, the oxidant supply pipe 213, and the inert gas introduction pipe 214 correspond to the “first pipe” in the present invention. Hereinafter, the respective conduits shown in FIG. 5, that is, the outer combustion pipe 211, the inner combustion pipe 212, the oxidant supply pipe 213, the inert gas introduction pipe 214, and the pipe 251 (described later) are located on the left side in the drawing. The end that is located is called the “left end” of each conduit, and the end located on the right side in the figure is called the “right end” of each conduit.

The external combustion pipe 211 is arranged inside the oxidant supply pipe 213 coaxially with the oxidant supply pipe 213, and the left end of the inert gas introduction pipe 214 is inserted into the right end of the external combustion pipe 211. .. The right end of the internal combustion pipe 212 is inserted into the left end of the external combustion pipe 211. The external combustion pipe 211, the internal combustion pipe 212, the oxidant supply pipe 213, and the inert gas introduction pipe 214 are all made of ceramic such as alumina.

A connector 217 is attached to the right ends of the oxidant supply pipe 213 and the external combustion pipe 211, and the inert gas introduction pipe 214 is inserted into this connector 217. The right end openings of the oxidant supply pipe 213 and the external combustion pipe 211 are closed by a connector 217, but a groove is cut on the left end surface of the connector 217, and the oxidant supply pipe is inserted through the groove. Gas can flow between 213 and the external combustion pipe 211. The right end of the inert gas introduction pipe 214 projects from the housing 216 of the heating furnace 210, and is connected to the left end of the pipe 251 provided inside the interface 250 arranged at the boundary between the GC 100 and the SCD 200. The interface 250 includes, in addition to the pipe 251, a heater 252 for heating the pipe 251 and a housing 253 that houses the pipe 251 and the heater 252, and is provided on the right side wall 242 of the housing 240 of the SCD 200. The opening 242a and the opening 122a provided in the left side wall 122 of the housing of the GC 100 are inserted. The right end of the pipe 251 projects from the housing 253 of the interface 250, and the first joint 221 is attached to the right end. An inert gas flow path 264 (corresponding to the “fourth pipe” in the present invention) for supplying an inert gas (here, nitrogen) to the inert gas introduction pipe 214 is connected to the first joint 221. ing. Note that the first joint 221 is provided with a hole (not shown) for inserting the column 140 of the GC 100. The end on the outlet side of the column 140 is inserted into the first joint 221 through this hole, and is inserted into the inside of the heating furnace 210, specifically, the inside of the inert gas introducing pipe 214 via the pipe 251 in the interface 250. Be done. At this time, the outlet end of the column 140 is arranged at a position slightly retracted from the front end of the inert gas introduction pipe 214.

On the other hand, the left ends of the oxidant supply pipe 213, the external combustion pipe 211, and the internal combustion pipe 212 project from the housing 216 of the heating furnace 210, and further to the outside through an opening 243a provided in the left side wall 243 of the housing 240 of the SCD 200. It is protruding. A second joint 222 is attached to the left end of the oxidant supply pipe 213 outside the housing 240. The second joint 222 supplies the oxidant (here, oxygen) to the oxidant supply pipe 213. An oxidant flow channel 265 is connected to this. The external combustion pipe 211 is inserted through the second joint 222, and the third joint 223 is attached to the left end thereof. A reducing agent flow passage 266 for supplying a reducing agent (here, hydrogen) to the external combustion pipe 211 is connected to the third joint 223. The internal combustion pipe 212 is inserted through the third joint 223, and the left end thereof is connected to the transfer pipe 270 leading to the reaction cell 231. This transfer pipe 270 is a feature that corresponds to the "second pipe" according to this invention.

The transfer tube 270 is made of a flexible tube, and is folded back outside the housing 240 of the SCD 200 and is opened again from another opening 243b (see FIG. 4) provided in the left side wall 243 of the housing 240. It enters the inside of the body 240 and is connected to the reaction cell 231 in the housing 240. Although not shown in FIG. 5, a cover 271 that can be opened and closed is provided on the outer surface of the left side wall 243 of the SCD 200 so as to cover the

openings

243a and 243b.

The inert gas flow channel 264, the oxidant flow channel 265, and the reducing agent flow channel 266 are all connected to the flow controller 237. The flow controller 237 allows the inert gas supply source 261 and the oxidant supply source 262. , And the reducing agent supply source 263 respectively control the flow rates of the gases supplied to the inert gas passage 264, the oxidizing agent passage 265, and the reducing agent passage 266. The inert gas supply source 261, the oxidant supply source 262, and the reducing agent supply source 263 may be, for example, gas cylinders filled with nitrogen, oxygen, and hydrogen, or the like.

Nitrogen supplied from the inert gas supply source 261 to the inert gas flow path 264 via the flow controller 237 flows into the right end of the inert gas introduction pipe 214 via the first joint 221 and the pipe 251 and is supplied with the inert gas. The inside of the introduction pipe 214 advances from the right end to the left end. In this embodiment, nitrogen is used as the inert gas, but other inert gas (for example, helium) can be used.

Oxygen supplied from the oxidant supply source 262 to the oxidant flow path 265 via the flow controller 237 flows into the left end of the oxidant supply pipe 213 via the second joint 222, and the inner wall of the oxidant supply pipe 213 and the outside Proceed to the right in the space between the outer wall of the combustion tube 211. The oxygen reaching the right end of the oxidant supply pipe 213 flows into the inside of the external combustion pipe 211 from the groove (described above) formed in the left end surface of the connector 217, and travels leftward in the external combustion pipe 211. .. In this embodiment, oxygen is used as the oxidizing agent, but air can be used as the oxidizing agent.

Hydrogen supplied from the reducing agent supply source 263 to the reducing agent flow path 266 via the flow controller 237 flows into the left end of the external combustion pipe 211 via the third joint 223, and the inner wall of the external combustion pipe 211 and the internal combustion pipe 212 Proceed to the right in the space between the outer wall of the. The hydrogen that has reached the vicinity of the right end of the internal combustion pipe 212 is drawn into the internal combustion pipe 212 from there, and travels leftward inside the internal combustion pipe 212.

The sample gas introduced into the heating furnace 210 from the outlet end of the column 140 of the GC 100 is mixed with oxygen at the right end of the external combustion tube 211, and travels inside the external combustion tube 211 to the left while reaching a high temperature. It is decomposed by oxidation. At this time, when the sample component is a sulfur compound, sulfur dioxide is produced. The gas containing the oxidatively decomposed sample component is drawn into the internal combustion pipe 212 together with hydrogen introduced from the vicinity of the left end of the external combustion pipe 211. When the oxidatively decomposed sample component contains sulfur dioxide, the sulfur dioxide reacts with hydrogen and is reduced to sulfur monoxide. In order to accelerate the above redox reaction, the inside of the heating furnace 210 is heated to 500° C. or higher (desirably 700° C. to 1200° C.) by the heater 215. The gas that has passed through the internal combustion pipe 212 is introduced into the reaction cell 231 through the transfer pipe 270.

Inside the heating furnace 210, nitrogen is supplied from the inert gas introducing pipe 214 around the outlet end of the column 140. This nitrogen has an effect of preventing detector contamination due to deterioration of the column 140 and an effect of promoting the redox reaction in the heating furnace 210.

The gas sent from the transfer pipe 270 to the reaction cell 231 is mixed with ozone in the reaction cell 231. At this time, chemiluminescence generated by the reaction of sulfur monoxide and ozone is detected by the photomultiplier tube 233 via the optical filter 232. The ozone is generated in the ozone generator 234 using oxygen supplied from the oxidant supply source 262 via the oxygen flow path 267, and is supplied to the reaction cell 231 via the pipe 268. At this time, the flow controller 237 also controls the flow rate of oxygen supplied to the ozone generator 234 via the oxygen flow path 267. An ozone scrubber 235 and a vacuum pump 236 are provided downstream of the reaction cell 231, and the gas in the reaction cell 231 sucked by the vacuum pump 236 has ozone removed by the ozone scrubber 235 and is then exhausted. It is discharged to the outside. The pipe 281 between the reaction cell 231 and the ozone scrubber 235 and the pipe 282 between the ozone scrubber 235 and the vacuum pump 236 correspond to the “third pipe” in the present invention. Further, the transfer pipe 270, the pipe 268, and the pipe 281 in the present embodiment correspond to “one or a plurality of pipes connected to the reaction cell” in the present invention. Further, the inert gas channel 264, the oxidant channel 265, the reducing agent channel 266, the oxygen channel 267, the pipe 268, the transfer pipe 270, the pipe 281, the pipe 282, the pipe 251, and the column 140 in the present embodiment are provided. Corresponds to the “plurality of pipes connected to the first pipe or the reaction cell” in the present invention.

The output signal from the photomultiplier tube 233 is sent to the control/processing unit 300, and the control/processing unit 300 determines the concentration of the sulfur compound in the sample gas based on the output signal.

The substance of the control/processing unit 300 is a microcomputer including a CPU, a ROM, a RAM, an input/output circuit for communicating with external peripheral devices, and the like. For example, the control program and the control parameters stored in the ROM are stored in the microcomputer. By executing the following arithmetic processing mainly by the CPU, processing of the output signal and operation control of each part, specifically, the heater 215 of the heating furnace 210, the heater 252 of the interface 250, the high-voltage power supply 291, the ozone. Control of the generator 234, the vacuum pump 236, the flow controller 237, etc. is performed. Further, the control/processing unit 300 is connected to an input device 320 including a keyboard, a mouse, a touch panel, or an operation button for inputting a user's instruction, and an output device 330 including a monitor or a speaker.

Note that, in FIG. 2, the voltage control unit 311, the pump control unit 312, the determination unit 313, and the notification unit 314 are shown so as to relate to the control/processing unit 300. These are functional means for realizing the characteristic operation of the SCD according to the present embodiment, and both are software-based by the CPU of the control/processing unit executing the program installed in the control/processing unit 300. Will be realized. The voltage control unit 311 controls a high voltage power supply 291 that generates a drive voltage applied to the photomultiplier tube, and generates a first drive voltage (for example, 850V) applied to sample analysis as a control mode. It has a normal mode and an abnormality detection mode for generating a second drive voltage (for example, 460 V) lower than the first drive voltage.

The procedure of the pipe connection check realized by the above functional means will be described below with reference to the flowchart of FIG.

First, the user turns off the power of the SCD and performs maintenance work, and then inputs an instruction to execute a pipe connection check from the input device 320 to the control/processing unit 300. When this instruction is input to the control/processing unit 300 (step 11), first, the high voltage power supply 291 is activated in the abnormality detection mode under the control of the voltage control unit 311 (step 12). As a result, the photomultiplier tube 233 is in a state in which a voltage (second drive voltage) lower than the voltage (first drive voltage) applied during sample analysis is applied. Then, the output signal of the photomultiplier tube 233 at this time is input to the control/processing unit 300, and the determination unit 313 determines whether or not the output signal is equal to or more than a predetermined threshold value (step). 13). Here, when it is determined that the output signal is equal to or more than the threshold value (Yes in step 13), that is, when it is determined that the light amount detected by the photomultiplier tube 233 is equal to or more than a predetermined value. The notification unit 314 controls the output device 330 to cause a poor connection between the photomultiplier tube 233 and the reaction cell 231 or between the reaction cell 231 and the transfer tube 270, the pipe 268, or the pipe 281. This is notified to the user (step 14). As a notification method at this time, for example, a character string for notifying the poor connection may be displayed on a monitor, or a voice for notifying the poor connection may be generated from a speaker.

If it is determined in step 13 that the output signal of the photomultiplier tube 233 is less than the threshold value (that is, No in the same step), it is determined in step 13 that the output signal of the photomultiplier tube 233 is greater than or equal to the threshold value. (That is, Yes at the same step) After the notification to the user (step 14), the vacuum pump 236 is activated by the pump control unit 312 (step 15). As a result, the inside of the reaction cell 231 and various pipes (for example, the internal combustion pipe 212, the external combustion pipe 211, and the inert gas introduction pipe 214) provided in the heating furnace 210 are evacuated. After that, when a predetermined time has elapsed since the vacuum pump 236 was started (Yes in step 16), the output signals of the first vacuum gauge 238 and the second vacuum gauge 239 are captured by the determination unit 313, and the output signals are output. Is determined to be equal to or greater than a predetermined threshold value for each. Specifically, first, it is determined whether or not the absolute pressure measured by the second vacuum gauge 239 is equal to or higher than a predetermined first threshold value (step 17), and then the first vacuum gauge 239 measures the absolute pressure. It is determined whether the determined differential pressure is equal to or more than a second threshold value set in advance (step 19). When it is determined in step 17 that the absolute pressure is equal to or higher than the first threshold value (Yes in step 17 ), it is considered that there is a defective connection point in the gas flow path, and therefore the notification unit 314 causes the output device The user is notified of this via 330 (step 18). Further, when it is determined in step 19 that the differential pressure is equal to or higher than the second threshold value (Yes in step 19 ), it is considered that the internal combustion pipe 212 is blocked, so the notification unit 314 outputs The user is notified via the device 330 (step 20). Note that step 17 and step 19 may be executed in reverse order.

Although the embodiments for carrying out the present invention have been described above with reference to specific examples, the present invention is not limited to the above embodiments, and modifications can be appropriately made within the scope of the gist of the present invention. For example, in the above embodiment, the first vacuum gauge 238 is composed of a differential pressure sensor and the second vacuum gauge 239 is composed of an absolute pressure sensor. However, both the first vacuum gauge 238 and the second vacuum gauge 239 are included. May be an absolute pressure sensor, and the difference between the output signal of the second vacuum gauge 239 and the output signal of the first vacuum gauge 238 may be used for the determination in step 19. Further, in the above-described embodiment, after the output signal of the photomultiplier tube 233 is determined to be the threshold value or more in step 13 and the user is notified in step 14, the process proceeds to step 15. The series of check operations may be terminated at the time when the notification is issued.

Further, in the above-described embodiment, after checking and notifying the poor pipe connection based on the output of the photomultiplier tube 233 (steps 12 to 14), the poor pipe connection and the closed pipes based on the outputs of the

vacuum gauges

238 and 239 are detected. Although the check and the notification (steps 15 to 20) are performed, both may be performed in the reverse order, or only one of the two may be performed in response to a user's instruction.

Further, in the above embodiment, the program for realizing the voltage control unit 311, the pump control unit 312, the determination unit 313, and the notification unit 314 is installed in the microcomputer (control/processing unit 300) built in the SCD. However, the program may be installed in the microcomputer in the GC 100 connected to the SCD 200 (FIG. 7). The PC 400 may be connected to the SCD 200 via the GC 100 as shown in FIG. 7, or may be directly connected to the SCD 200 as shown in FIG. 8.

Further, in the above-described embodiment, when the user gives an instruction to check the pipe connection or the like from the input device 320 provided in the SCD 200 and there is a connection failure in the pipe, the output device 330 provided in the SCD 200 is used. Although the user is notified of that fact, the present invention is not limited to this, and the user can use the touch panel 132 or the operation button 133 provided on the operation panel 131 of the GC 100 or the input device 520 such as a keyboard or a mouse connected to the PC 400. The user is instructed to perform the check, or a display device such as a speaker (not shown) provided in the GC 100 or a liquid crystal panel included in the touch panel 132, or an output device 530 such as a liquid crystal display or a speaker provided in the PC 400 is used to inform the user. The above notification may be performed. Further, the program according to the present invention is not necessarily a single program, and may be, for example, a program for controlling the SCD 200 or a part of a program for controlling the GC 100. ..

Further, in the above-described embodiment, the example in which the present invention is applied to the SCD including the horizontal heating furnace (that is, the heating furnace including the combustion tube extending in the horizontal direction) is shown, but the invention is not limited to this, and Patent Document 2 The present invention can be similarly applied to an SCD including a vertical heating furnace as described in 1 (that is, a heating furnace including a combustion tube extending in the vertical direction).

100... Gas chromatograph 200... Chemiluminescent sulfur detector 210... Heating furnace 211... External combustion pipe 212... Internal combustion pipe 213... Oxidizing agent supply pipe 214... Inert gas introduction pipe 215... Heater 216... Housing 231... Reaction cell 233... Photomultiplier tube 291... High-voltage power supply 234... Ozone generator 235... Ozone scrubber 236... Vacuum pump 238... First vacuum gauge 239...

Second vacuum gauge

268, 281... Piping 270... Transfer tube 300... Control/processing section 311... Voltage control unit 312... Pump control unit 313... Judgment unit 314... Notification unit 400... Personal computer

Claims

Heating furnace,
A reaction cell for reacting the gas passing through the heating furnace with ozone,
A photomultiplier tube for detecting light from the reaction cell,
A power supply for generating a driving voltage applied to the photomultiplier tube,
The power supply is controlled, and a normal mode for generating a first drive voltage applied to sample analysis and a second drive voltage lower than the first drive voltage are used as start-up modes of the power supply. A voltage control means having an abnormality detection mode to be generated,
When the power supply is started in the abnormality detection mode, based on the output signal of the photomultiplier tube, connected between the reaction cell and the photomultiplier tube, or the reaction cell and the reaction cell Determination means for determining whether or not there is a poor connection with any one of the pipes or the plurality of pipes;
When the determination unit determines that there is a poor connection, a notification unit that notifies the user of that fact,
A chemiluminescent sulfur detector comprising:
The chemiluminescent sulfur detector according to claim 1, wherein the second drive voltage is less than 500V.
Heating furnace,
A reaction cell for reacting the gas passing through the heating furnace with ozone,
A photomultiplier tube for detecting light from the reaction cell,
A power supply for generating a driving voltage applied to the photomultiplier tube,
A program for controlling a chemiluminescent sulfur detector having:
Computer,
The power supply is controlled, and as a start-up mode of the power supply, a normal mode for generating a first drive voltage applied to sample analysis and a second drive voltage lower than the first drive voltage are generated. A voltage control means having an abnormality detection mode,
When the power supply is started in the abnormality detection mode, based on the output signal of the photomultiplier tube, connected between the reaction cell and the photomultiplier tube, or the reaction cell and the reaction cell In addition, when the determination unit determines whether there is a connection failure with one or a plurality of pipes, and the determination unit determines that there is a connection failure, the user is notified of that fact. Notification means,
A program characterized by making it function as.
A heating furnace provided with a first pipe and a heating means for heating the first pipe;
A reaction cell connected to the heating furnace by a second pipe,
A vacuum pump connected to the reaction cell by a third pipe;
A fourth pipe for introducing gas into the first pipe;
Pressure measuring means for measuring the pressure inside at least one of the second pipe, the third pipe, and the fourth pipe;
Pump control means for controlling the vacuum pump,
Based on the measured value of the pressure measuring means in a state where the vacuum pump is operated by the pump control means, the first pipe, the reaction cell, or a plurality of pipes connected to the first pipe or the reaction cell. Any of the piping of, the determination means for determining whether there is a defective connection point,
When the determination unit determines that there is the defective connection portion, a notification unit that notifies the user of that fact,
A chemiluminescent sulfur detector comprising:
The pressure measuring means further measures a pressure difference between the inside of the second pipe or the third pipe and the inside of the fourth pipe,
The chemiluminescent sulfur detector according to claim 4, wherein the determination means further determines whether or not the first pipe is closed based on the difference.
A heating furnace provided with a first pipe and a heating means for heating the first pipe;
A reaction cell connected to the heating furnace by a second pipe,
A vacuum pump connected to the reaction cell by a third pipe;
A fourth pipe for introducing gas into the first pipe;
Pressure measuring means for measuring the pressure inside at least one of the second pipe, the third pipe, and the fourth pipe;
Pump control means for controlling the vacuum pump,
A program for controlling a chemiluminescent sulfur detector having:
Computer,
Based on the measured value of the pressure measuring means in a state where the vacuum pump is operated by the pump control means, the first pipe, the reaction cell, or a plurality of pipes connected to the first pipe or the reaction cell. Any of the piping of, the determination means for determining whether there is a connection failure location, and the notification means for notifying the user to that effect when it is determined by the determination means that there is a connection failure location,
A program characterized by making it function as.
The pressure measuring means further measures a pressure difference between the inside of the second pipe or the third pipe and the inside of the fourth pipe,
7. The program according to claim 6, wherein the determination means further determines whether or not the first pipe is closed based on the difference.