JP7143902B2 - Chemiluminescence sulfur detector - Google Patents

Description

The present invention relates to a Sulfur Chemiluminescence Detector.

A sulfur chemiluminescence detector (SCD) is a detector that can detect sulfur compounds in a sample with high sensitivity using chemiluminescence, and is usually used in combination with a gas chromatograph (GC) (for example, patent See reference 1).

A gas (sample gas) containing sample components separated by the GC column is introduced into a heating furnace provided in the SCD. The heating furnace includes a combustion tube and a heater for heating the combustion tube. The sample gas is oxidized while passing through the combustion tube, and sulfur dioxide (SO ₂ ) is produced from sulfur compounds in the sample gas. is generated. Further, the SO2 is reduced while passing through the combustion tube to generate sulfur monoxide ₍ SO) from the _SO2 . This SO is introduced into a reaction cell provided after the heating furnace and mixed with ozone (O ₃ ) in the reaction cell. As a result _, the reaction of SO and O3 produces an excited species of sulfur dioxide (SO2 _* ) ^. The emission intensity when this SO ₂ ^* returns to the ground state through chemiluminescence is detected by a photodetector, and the sulfur compounds contained in the sample gas are quantified from the emission intensity.

Japanese Patent Application Laid-Open No. 2015-59876

The piping of the SCD may be removed during maintenance work or the like. After the maintenance work, etc., the removed pipes are reassembled as they were, but at that time, there may be places where the joints of the pipes are not sufficiently tightened (hereinafter referred to as "poor connection places"). If the SCD is started without noticing such a poor connection, the expected performance may not be obtained, or the parts may be damaged.

For example, the light generated by chemiluminescence in the reaction cell of the SCD passes through an optical filter and enters the photomultiplier tube. A large amount of current flows in the photomultiplier tube, which may damage it.

The SCD also has a gas flow path from the combustion tube of the heating furnace to the reaction cell and to the vacuum pump. During operation of the SCD, the gas in the flow path is sucked by the vacuum pump. If there is a poor connection in the pipes that make up these gas flow paths, outside air leaks into the flow path from these points, hindering the reaction in the heating furnace or reaction cell, and the desired performance may not be achieved. There is

SUMMARY OF THE INVENTION The present invention has been made in view of the above points, and an object of the present invention is to enable a user to easily know whether or not there is a poor connection in a pipe or the like included in an SCD. That's what it is.

A sulfur chemiluminescence detector (SCD) according to a first aspect of the present invention, which has been made to solve the above problems,
a heating furnace;
a reaction cell for reacting the gas that has passed through the heating furnace with ozone;
a photomultiplier tube for detecting light from the reaction cell;
a power supply that generates a drive voltage to be applied to the photomultiplier tube;
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 as activation modes of the power supply. a voltage control means having an anomaly detection mode to generate
connected between the reaction cell and the photomultiplier tube or between the reaction cells based on the output signal of the photomultiplier tube when the power supply is activated in the abnormality detection mode; Determination means for determining whether there is a connection failure between one or more pipes;
a notification means for notifying a user of the fact that the connection failure is determined by the determination means;
It is characterized by having

As described above, in the sulfur chemiluminescence detector according to the first aspect of the present invention, the presence or absence of poor connection of piping is determined based on the output signal of the photomultiplier tube. When an excessive amount of light is incident on the photomultiplier tube, a large current may flow inside the tube, causing damage. It has an anomaly detection mode in which the driving voltage applied to the tube is lower than that during sample analysis. In the abnormality detection mode, the current amplification factor of the photomultiplier tube is reduced, so even when excessive light is incident, a large current can be prevented from flowing through the photomultiplier tube. Therefore, according to the sulfur chemiluminescence detector according to the first aspect of the present invention, the determination can be performed without damaging the photomultiplier tube even when external light leaks due to poor connection. be able to.

It is preferable 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,
a heating furnace;
a reaction cell for reacting the gas that has passed through the heating furnace with ozone;
a photomultiplier tube for detecting light from the reaction cell;
a power supply that generates a drive voltage to be applied to the photomultiplier tube;
A program for controlling a sulfur chemiluminescence detector having
the computer,
It controls the power supply, and has a normal mode for generating a first driving voltage applied to sample analysis and a second driving voltage lower than the first driving voltage as activation modes of the power supply. Voltage control means having an anomaly detection mode that allows
connected between the reaction cell and the photomultiplier tube or between the reaction cells based on the output signal of the photomultiplier tube when the power supply is activated in the abnormality detection mode; determining means for determining whether or not there is a connection failure between one or more pipes, and notifying the user when the determination means determines that there is a connection failure notification means,
It is characterized by functioning as

In addition, a chemiluminescence sulfur detector according to a second aspect of the present invention, which has been made to solve the above problems,
a heating furnace comprising a first pipe and 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 in at least one of the second pipe, the third pipe, or the fourth pipe;
pump control means for controlling the vacuum pump;
the first pipe, the reaction cell, or a plurality of pressure sensors connected to the first pipe or the reaction cell based on the measured value of the pressure measurement means while the vacuum pump is operated by the pump control means; a determination means for determining whether or not there is a defective connection in any of the pipes;
notification means for notifying a user of the fact that the determination means determines that there is the poor connection location;
It is characterized by having

Here, "the first piping or a plurality of piping connected to the reaction cell" includes the first piping or piping directly connected to the reaction cell (for example, the second piping, the third piping , and fourth piping), but also piping indirectly connected to the first piping or the reaction cell via other piping.

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

Further, the program according to the second aspect of the present invention,
a heating furnace comprising a first pipe and 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 in at least one of the second pipe, the third pipe, or the fourth pipe;
pump control means for controlling the vacuum pump;
A program for controlling a sulfur chemiluminescence detector having
the computer,
the first pipe, the reaction cell, or a plurality of pressure sensors connected to the first pipe or the reaction cell based on the measured value of the pressure measurement means while the vacuum pump is operated by the pump control means; determination means for determining whether or not there is a poor connection in any of the pipes, and notification means for notifying the user when the determination means determines that there is a poor connection,
It is characterized by functioning as

As described above, according to the chemiluminescence sulfur detector according to the present invention, the presence or absence of poor connection of piping or the like is automatically determined based on the output signal from the photomultiplier tube or the measured value of the pressure measuring means. . As a result, the user can easily know whether or not there is a poor connection in the piping or the like, so the sulfur chemiluminescence detector may be normally activated without noticing the poor connection, which may damage the parts or cause the desired damage. It is possible to prevent the performance from not being obtained.

1 is a front view showing the appearance of a GC system with an SCD according to one embodiment of the invention; FIG. The figure which shows the principal part structure of said SCD. FIG. 2 is a front view schematically showing the internal configuration of a GC system including the SCD; FIG. 2 is a top view schematically showing the internal configuration of the GC system; Sectional drawing which shows the structure of the heating furnace vicinity of said SCD. 4 is a flow chart showing the operation of checking for poor connection by the SCD; FIG. 4 is a schematic diagram showing another configuration example of the GC system including the SCD of the present invention; FIG. 3 is a schematic diagram showing still another configuration example of the GC system including the SCD of the present invention;

Hereinafter, a configuration for carrying out the present invention will be described with reference to the drawings. FIG. 1 is a front view showing the appearance of a gas chromatograph system (GC system) equipped with a sulfur chemiluminescence detector (SCD) according to this embodiment. FIG. 2 is a diagram showing the main configuration of the SCD according to this embodiment. 3 and 4 are schematic diagrams showing the internal structure of the GC system, wherein FIG. 3 is a front view and FIG. 4 is a top view. FIG. 5 is a cross-sectional view showing the configuration around the heating furnace of the SCD.

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

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

As shown in FIG. 2, the SCD 200 is connected to a heating furnace 210 for causing an oxidation-reduction reaction of a sample gas at a high temperature, a reaction cell 231 for reacting the gas that has passed through the heating furnace 210 with ozone, and the reaction cell 231. , a photomultiplier tube 233 for detecting chemiluminescence due to a reaction in the reaction cell 231, a high-voltage power supply 291 for generating a driving voltage to be applied to the photomultiplier tube 233, and ozone to be supplied to the reaction cell 231. an ozone generator 234, a vacuum pump 236 that evacuates the reaction cell 231 and the heating furnace 210, an ozone scrubber 235 that removes ozone from the exhaust gas of the reaction cell 231, a flow controller 237, and a control/processing unit 300. , and a housing 240 (see FIG. 1) that accommodates them. 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 . A vacuum gauge (hereinafter referred to as a "second vacuum gauge 239") is also provided above the inert gas flow path 264, which will be described later. The first vacuum gauge 238 and the second vacuum gauge 239 correspond to "pressure measuring means" in the present invention. Furthermore, the SCD 200 has an interface 250 arranged at the boundary with the GC 100 to connect the GC 100 and the SCD 200 .

In this embodiment, the second vacuum gauge 239 is assumed to be an absolute pressure sensor, and the first vacuum gauge 238 is assumed to be a differential pressure sensor. The pressure at the position where the first vacuum gauge 238, which is a differential pressure sensor, is provided (that is, the pressure downstream of the reaction cell 231) and the pressure at the position where the second vacuum gauge 239 is provided (that is, the heating furnace 210 pressure) 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). In addition, the upper surface of the space in which the heating furnace 210 is accommodated in the housing 240 of the SCD 200 is a removable top plate 241 (see FIG. 1).

The heating furnace 210 includes, as shown in FIG. equivalent) and a housing 216 that accommodates them. The external combustion pipe 211, internal combustion pipe 212, oxidant supply pipe 213, and inert gas introduction pipe 214 correspond to the "first pipe" in the present invention. 5, i.e., the external combustion pipe 211, the internal 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 of the figure. The end located on the right side in the figure is called the "right end" of each pipeline.

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 tube 212 is inserted into the left end of the external combustion tube 211 . The outer combustion tube 211, the inner combustion tube 212, the oxidant supply tube 213, and the inert gas introduction tube 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 through 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 in the left end surface of the connector 217, through which the oxidant supply pipe is connected. Gas can flow between 213 and external combustion tube 211 . The right end of inert gas introduction pipe 214 protrudes from housing 216 of heating furnace 210 and is connected to the left end of pipe 251 provided inside interface 250 arranged at the boundary between GC 100 and SCD 200 . In addition to the piping 251, the interface 250 includes a heater 252 for heating the piping 251 and a housing 253 for accommodating the piping 251 and the heater 252. It is inserted through the opening 242a and the opening 122a provided in the left side wall 122 of the housing of the GC100. The right end of the pipe 251 protrudes from the housing 253 of the interface 250, and the first joint 221 is attached to the right end. Connected to the first joint 221 is an inert gas flow path 264 (corresponding to a “fourth pipe” in the present invention) for supplying inert gas (here, nitrogen) to the inert gas introduction pipe 214 . ing. The first joint 221 is provided with a hole (not shown) through which the column 140 of the GC 100 is inserted. The outlet side end of the column 140 is inserted through this hole into the first joint 221 and inserted into the interior of the heating furnace 210, specifically, the interior of the inert gas introduction pipe 214 via the pipe 251 in the interface 250. be At this time, the outlet end of the column 140 is arranged at a position slightly retracted from the left 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 protrude from the housing 216 of the heating furnace 210, and further exit from an opening 243a provided in the left side wall 243 of the housing 240 of the SCD 200. Protruding. Outside the housing 240, a second joint 222 is attached to the left end of the oxidant supply pipe 213, and the second joint 222 supplies an oxidant (here, oxygen) to the oxidant supply pipe 213. An oxidant channel 265 is connected. The external combustion pipe 211 is passed through this second joint 222, and a third joint 223 is attached to its left end. A reducing agent flow path 266 for supplying a reducing agent (here, hydrogen) to the external combustion pipe 211 is connected to the third joint 223 . The internal combustion tube 212 is inserted through this third joint 223 and its left end is connected to a transfer tube 270 leading to the reaction cell 231 . This transfer pipe 270 corresponds to the "second pipe" in the present invention.

The transfer tube 270 is made of a flexible tube, and is folded back outside the housing 240 of the SCD 200 to return to the housing through another opening 243b (see FIG. 4) provided in the left side wall 243 of the housing 240. It enters inside the body 240 and is connected to the reaction cell 231 inside 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 at a position that covers the openings 243a and 243b.

The inert gas flow path 264, the oxidizing agent flow path 265, and the reducing agent flow path 266 are all connected to a flow controller 237, and the inert gas supply source 261 and the oxidizing agent supply source 262 are controlled by the flow controller 237. , and the flow rate of the gas supplied from the reducing agent supply source 263 to the inert gas flow path 264, the oxidizing agent flow path 265, and the reducing agent flow path 266, respectively. The inert gas supply source 261, the oxidizing agent supply source 262, and the reducing agent supply source 263 can be composed of, for example, gas cylinders filled with nitrogen, oxygen, and hydrogen, respectively.

Nitrogen supplied from the inert gas supply source 261 to the inert gas flow path 264 through the flow controller 237 flows through the first joint 221 and the pipe 251 into the right end of the inert gas introduction pipe 214, The inside of the introduction pipe 214 is advanced from the right end to the left end. Although nitrogen is used as the inert gas in this embodiment, it is also possible to use other inert gases (for example, helium).

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

Hydrogen supplied from the reducing agent supply source 263 to the reducing agent flow path 266 through the flow controller 237 flows through the third joint 223 into the left end of the external combustion tube 211, and flows into the inner wall of the external combustion tube 211 and the internal combustion tube 212. Towards the right in the space between the outer wall of the Hydrogen reaching near the right end of the internal combustion tube 212 is drawn into the internal combustion tube 212 from there and travels leftward inside the internal combustion tube 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, travels leftward inside the external combustion tube 211, and reaches a high temperature. is oxidatively decomposed. At this time, if the sample component is a sulfur compound, sulfur dioxide is produced. Gas containing oxidatively decomposed sample components is drawn into the internal combustion tube 212 together with hydrogen introduced near the left end of the external combustion tube 211 . If sulfur dioxide is contained in the oxidatively decomposed sample components, the sulfur dioxide reacts with hydrogen and is reduced to sulfur monoxide. In order to promote the oxidation-reduction reaction described above, the inside of the heating furnace 210 is heated to 500° C. or higher (preferably 700° C. to 1200° C.) by the heater 215 . Gas that has passed through the internal combustion tube 212 is introduced into the reaction cell 231 through the transfer tube 270 .

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

The gas sent from the transfer pipe 270 to the reaction cell 231 is mixed with ozone inside the reaction cell 231 . At this time, chemiluminescence generated by the reaction between sulfur monoxide and ozone is detected by the photomultiplier tube 233 through the optical filter 232 . The ozone is generated by an ozone generator 234 using oxygen supplied from an oxidizing agent supply source 262 through an oxygen flow path 267 and supplied to the reaction cell 231 through a pipe 268 . At this time, the flow controller 237 also controls the flow rate of oxygen supplied to the ozone generator 234 through 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 discharged as an exhaust gas. It is discharged 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. Furthermore, the transfer pipe 270, the pipe 268, and the pipe 281 in this embodiment correspond to "one or more pipes connected to the reaction cell" in the present invention. In addition, 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 this embodiment are , corresponds to “a 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 section 300, and the concentration of the sulfur compounds in the sample gas is obtained in the control/processing section 300 based on the output signal.

The substance of the control/processing unit 300 is a microcomputer having a CPU, a ROM, a RAM, and an input/output circuit for communicating with external peripheral devices. The processing of the output signal and the 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 Controls such as generator 234, vacuum pump 236 and flow controller 237 are provided. Also connected to the control/processing unit 300 are an input device 320 such as a keyboard, mouse, touch panel, or operation buttons for inputting user instructions, and an output device 330 such as a monitor or speaker.

Note that FIG. 2 shows a voltage control unit 311 , a pump control unit 312 , a determination unit 313 , and a notification unit 314 so as to relate to the control/processing unit 300 . These are functional means for realizing characteristic operations of the SCD according to the present embodiment, and all of them are executed by the CPU of the control/processing unit 300 by executing the programs installed in the control/processing unit 300 in terms of software. is realized in The voltage control unit 311 controls the high-voltage power supply 291 that generates the drive voltage applied to the photomultiplier tube, and as a control mode, generates the first drive voltage (e.g., 850 V) applied to sample analysis. It has a normal mode and an abnormality detection mode in which a second drive voltage (for example, 460 V) lower than the first drive voltage is generated.

The procedure for checking the pipe connection realized by the above functional means will be described below with reference to the flow chart of FIG.

First, the user turns off the power of the SCD and performs maintenance work, etc., 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 applied with a voltage (second drive voltage) lower than the voltage (first drive voltage) applied during sample analysis. Subsequently, 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 greater than a predetermined threshold value (step 13). Here, if it is determined that the output signal is greater than or equal to the threshold value (Yes in step 13), that is, if it is determined that the amount of light detected by the photomultiplier tube 233 is greater than or equal to a predetermined value, , the notification unit 314 controls the output device 330 to detect that there is a connection failure between the photomultiplier tube 233 and the reaction cell 231, or between the reaction cell 231 and the transfer pipe 270, the pipe 268, or the pipe 281. The user is notified to that effect (step 14). As a notification method at this time, for example, it is conceivable to display a character string informing of the poor connection on a monitor, or to generate a sound informing the poor connection 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 step 13), and if it is determined in step 13 above 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), and after the user is notified (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 started to be evacuated. After that, when a predetermined time has passed since the activation of the vacuum pump 236 (Yes in step 16), the output signals of the first vacuum gauge 238 and the second vacuum gauge 239 are taken into the determination unit 313, and each output signal is equal to or greater than a predetermined threshold value. Specifically, first, it is determined whether or not the absolute pressure measured by the second vacuum gauge 239 is equal to or greater than a predetermined first threshold value (step 17). It is determined whether or not the obtained differential pressure is equal to or greater than a predetermined second threshold (step 19). If it is determined in step 17 that the absolute pressure is equal to or greater than the first threshold value (Yes in step 17), it is considered that there is a poor connection in the gas flow path. 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 greater 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 of this via device 330 (step 20). Note that steps 17 and 19 may be executed in the reverse order.

As mentioned above, although the form for implementing this invention was demonstrated with the specific example, this invention is not limited to the said embodiment, A change is permitted suitably within the scope of the meaning of this invention. For example, in the above embodiment, the first vacuum gauge 238 is a differential pressure sensor and the second vacuum gauge 239 is an absolute pressure sensor. may be composed of 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 determination in step 19. In the above embodiment, the output signal of the photomultiplier tube 233 is determined to be equal to or higher than the threshold value in step 13, and after notifying the user in step 14, the process proceeds to step 15. However, step 14 A series of check operations may be terminated at the time when the notification is made.

Further, in the above-described embodiment, after performing check and notification (steps 12 to 14) of a pipe connection failure based on the output of the photomultiplier tube 233, a pipe connection failure and pipe clogging based on the output of the vacuum gauges 238 and 239 are detected. Although the check and the notification (steps 15 to 20) are performed, the two may be performed in the reverse order, or only one of the two may be performed according to the 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 above program may be installed in a microcomputer within 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.

Further, in the above-described embodiment, the user instructs to check the piping connection or the like from the input device 320 provided in the SCD 200, and if there is a connection failure or the like in the piping, the output device 330 provided in the SCD 200 is used. The user is notified of this fact, but 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 mouse connected to the PC 400. 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 to the user. It is good also as what performs the said notification of this. Also, the program according to the present invention does not necessarily have to be a standalone program, and may be incorporated into a program for controlling the SCD 200 or a part of a program for controlling the GC 100, for example. .

Further, in the above embodiment, an example in which the present invention is applied to an SCD equipped with a horizontal heating furnace (i.e., a heating furnace with a built-in combustion tube extending in the horizontal direction) was shown, but the invention is not limited to this. The present invention can be similarly applied to an SCD having a vertical heating furnace (that is, a heating furnace containing a combustion tube extending vertically) as described in 1 above.

DESCRIPTION OF SYMBOLS 100... Gas chromatograph 200... Chemiluminescence sulfur detector 210... Heating furnace 211... External combustion tube 212... Internal combustion tube 213... Oxidant 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 pipe 300 Control/processing unit 311 Voltage control unit 312 Pump control unit 313 Determination unit 314 Notification unit 400 Personal computer

Claims (5)

a heating furnace;
a reaction cell for reacting the gas that has passed through the heating furnace with ozone;
a photomultiplier tube for detecting light from the reaction cell;
a power supply that generates a drive voltage to be applied to the photomultiplier tube;
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 as activation modes of the power supply. a voltage control means having an anomaly detection mode to generate
connected between the reaction cell and the photomultiplier tube or between the reaction cells based on the output signal of the photomultiplier tube when the power supply is activated in the abnormality detection mode; Determination means for determining whether there is a connection failure between one or more pipes;
a notification means for notifying a user of the fact that the connection failure is determined by the determination means;
A sulfur chemiluminescence detector comprising: 2. The sulfur chemiluminescent detector of claim 1, wherein said second drive voltage is less than 500V. a heating furnace;
a reaction cell for reacting the gas that has passed through the heating furnace with ozone;
a photomultiplier tube for detecting light from the reaction cell;
a power supply that generates a drive voltage to be applied to the photomultiplier tube;
A program for controlling a sulfur chemiluminescence detector having
the computer,
It controls the power supply, and has a normal mode for generating a first driving voltage applied to sample analysis and a second driving voltage lower than the first driving voltage as activation modes of the power supply. Voltage control means having an anomaly detection mode that allows
connected between the reaction cell and the photomultiplier tube or between the reaction cells based on the output signal of the photomultiplier tube when the power supply is activated in the abnormality detection mode; determining means for determining whether or not there is a connection failure between one or more pipes, and notifying the user when the determination means determines that there is a connection failure notification means,
A program characterized by functioning as a heating furnace comprising a first pipe and 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 in at least one of the second pipe, the third pipe, or the fourth pipe;
pump control means for controlling the vacuum pump;
the first pipe, the reaction cell, or a plurality of pressure sensors connected to the first pipe or the reaction cell based on the measured value of the pressure measurement means while the vacuum pump is operated by the pump control means; a determination means for determining whether or not there is a defective connection in any of the pipes;
notification means for notifying a user of the fact that the determination means determines that there is the poor connection location;
and
The pressure measuring means further measures the difference in pressure between the inside of the second pipe or the third pipe and the inside of the fourth pipe,
The sulfur chemiluminescence detector , wherein the determining means further determines whether or not the first pipe is clogged based on the difference . a heating furnace comprising a first pipe and 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 in at least one of the second pipe, the third pipe, or the fourth pipe;
pump control means for controlling the vacuum pump;
A program for controlling a sulfur chemiluminescence detector having
the computer,
the first pipe, the reaction cell, or a plurality of pressure sensors connected to the first pipe or the reaction cell based on the measured value of the pressure measurement means while the vacuum pump is operated by the pump control means; determination means for determining whether or not there is a poor connection in any of the pipes, and notification means for notifying the user when the determination means determines that there is a poor connection,
function as
The pressure measuring means further measures the difference in pressure between the inside of the second pipe or the third pipe and the inside of the fourth pipe,
The program , wherein the determination means further determines whether or not the first pipe is blocked based on the difference .

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