JP2006058318A - Sample gas sampling device and hazardous material detection device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve the problem of a hazardous material detection apparatus of the conventional technology having the disadvantage of being insufficient in detection sensitivity such that, if the vapor pressure of hazardous material is too low or if there is only a trace amount of hazardous material, it cannot detect the material unless an enrichment process is provided. <P>SOLUTION: A hazardous material, typically a nitro compound, is efficiently ionized using a negative corona discharge and the negative ions created are detected with high sensitivity using a mass spectrometer. In this way the vapor of the hazardous material is detected with high sensitivity whereby a determination can be rapidly made as to whether or not the hazardous material is present. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to dangerous goods detection, and more particularly, to a dangerous goods detection apparatus for detecting vapor generated from explosives with high sensitivity and determining the presence or absence of explosives in luggage or cargo.

  As prior art for detecting the presence or absence of dangerous materials by detecting the vapor of dangerous materials such as explosives represented by nitro compounds, it is disclosed in US Pat. No. 4,987,767 and further 5,109,691. There is a way that is. In these methods, vapor is collected from the person or object to be examined, collected, concentrated, and desorbed, and detected by a detector such as a gas chromatograph or ion mobility analyzer equipped with an electron capture detector. The method was taken.

In the above prior art, since the sensitivity of the detector used is not sufficient, the detection is performed through a chemical concentration process. However, if a chemical concentration process is provided, depending on the degree of concentration, the chemical concentration takes a long time (several minutes to several tens of minutes). There was a problem that the specimen could not be processed at high speed.

  There has been a problem that detection of dangerous goods in baggage and cargo at the airport has been required to be processed in a short time but cannot be realized. Another problem is how to collect sample gas from baggage and cargo.

  In order to solve the above prior art, a sample introduction part for introducing a gas sample to be measured, a corona discharge part for negative corona discharge of the introduced gas sample, and ions generated by the corona discharge part are subjected to mass spectrometry It has a mass spectrometer. That is, according to the present invention, utilizing the fact that dangerous substances represented by nitro compounds are likely to become negative ions, negative ions generated by negative corona discharge are generated by a mass spectrometer. Measured. Since the negative ion generation efficiency by negative corona discharge is very high, the detection sensitivity is sufficiently high. Therefore, the complicated chemical concentration process as in the above prior art is not required.

  It becomes possible to detect a dangerous substance contained in a substantially sealed container, for example, a luggage such as a trunk case. In particular, in order to efficiently detect a substance that generates a small amount of evaporative gas, the gas is ionized and detected at high speed using a small ion accumulation type mass separator. As a result, it is possible to determine the presence or absence of dangerous goods without opening a large amount of packages that are carried in individual units. In addition, it is possible to check the presence or absence of dangerous goods in units of blocks, that is, in units of containers storing a plurality of packages, instead of individually inspecting the packages. This improves the detection speed. By using in combination with a metal detection device or an X-ray inspection device, it becomes possible to further increase the detection sensitivity of dangerous materials.

  According to the present invention, it is possible to detect a nitro compound having a plurality of nitro groups with high sensitivity. These nitro compounds are likely to be negative ions, and negative ions are easily generated by negative corona discharge. Therefore, very high sensitivity can be obtained. Moreover, by using an ion trap mass spectrometer that can store ions inside as a mass spectrometer, the sample can be concentrated at high magnification in this mass spectrometer. Even when the vapor pressure of is extremely low, the analysis can be performed reliably. However, it is possible to use a quadrupole mass spectrometer or a magnetic field mass spectrometer.

  FIG. 1 is a diagram showing a configuration of a dangerous goods detection system according to an embodiment of the present invention. As will be described later, in the present invention, after collecting the vapor of a dangerous substance such as an explosive typified by a nitro compound, it is ionized using a negative corona discharge, and it is detected by a mass spectrometer. In this embodiment, the inspector inhales and analyzes the dangerous substance vapor leaking from the package to be measured by the sampling probe, and detects the presence of the dangerous substance from the analysis result. In addition to this method, the location of dangerous goods can be confirmed by simultaneously using an X-ray inspection apparatus that captures the form of dangerous goods in the luggage from the outside without opening the luggage. Detection sensitivity can be further increased by moving the probe closer.

  Details of this embodiment will be described with reference to FIG. In public facilities such as airports and harbors, baggage is inspected when boarding. The inspection body 1a such as a bag is placed on the belt conveyor 2a and is first sent to the X-ray inspection apparatus 3a. Here, the baggage 1b that has been inspected for dangerous materials centered on metal is further inspected by the off-line analyzing dangerous material detection device 4 for the purpose of detecting the vapor of the dangerous materials. In the case of FIG. 1, the inspector uses the offline analysis sampling probe 5 to bring the offline analysis sampling probe 5 close to an opening such as a keyhole of an inspection object 1 a such as a bag or a gap between an upper lid and a lower lid, The internal steam is collected and inspected. At this time, if the tip of the off-line analysis sampling probe 5 is made thin, the internal vapor of the bag or the like can be directly collected using the gap. The inspector confirms the detection result with the display 64 as shown in FIG. The indicator 64 displays an indicator 65 of a substance corresponding to a certain ion to be detected. For example, if A is detected, A is blinked to notify that A is detected. At this time, an amount indicator 66 and an alarm 67 may be provided at the same time for indicating the concentration level (simply, information such as whether the amount is large or small).

  The inspection flow in the above inspection is as shown in FIG. If an abnormality cannot be detected by the X-ray inspection apparatus 3a or the off-line analysis dangerous substance detection apparatus 4, the package will be allowed to pass, but if an abnormality is detected, a detailed reexamination will be performed. Become. In FIG. 1, the X-ray inspection apparatus 3 a and the offline analysis dangerous substance detection apparatus 4 are used together, but the offline analysis dangerous substance detection apparatus 4 can also be used alone. Further, the X-ray inspection apparatus 3 may be passed after the dangerous substance detection apparatus 4 for offline analysis. In this case, when there is a dangerous substance, the inspection time in the X-ray inspection apparatus 3 is shortened. Furthermore, there may be a case where the off-line analysis dangerous substance detection device 4 is used alone. In this case, it is effective when an object that is exposed to light or changes color or deforms by X-rays is housed inside.

  Such a dangerous substance detection apparatus 4 for off-line analysis can also be applied to vehicle inspection for inspecting whether there is any dangerous substance in the trunk.

  By adopting such an inspection apparatus configuration, there are the following effects. In other words, in the case of a plastic bomb, if the explosives exist as a thick mass inside the luggage, there is a possibility that they will be observed by an X-ray inspection device. Hard to observe. At this time, when the inspector inspects with the dangerous substance detection device for offline analysis as the next stage, even if the explosive is in the form of a sheet, if the vapor leaks inside or outside the luggage, it will detect the dangerous goods. As a result, the possibility of detecting a dangerous substance becomes higher than the case of the X-ray inspection apparatus alone. Also, in the case of re-inspection, it is possible to immediately check on the spot whether the substance inside the package is explosive or not, and also analyze the type. In this case, it is more useful than the X-ray inspection apparatus.

  Hereinafter, the operation in the actual analysis unit will be described mainly with reference to FIG. The gas sample to be measured is introduced from the gas sample introduction port 17 in the gas sample introduction probe.

  Details of the gas sample introduction probe are shown in FIGS. First, the case of FIG. 9 will be described. In order to introduce the gas sample from the gas sample introduction port 17, a gas sample introduction pump 27 is required. The gas sample introduction pump 27 uses a gas introduction pump having a mechanical mechanism such as a diaphragm pump, and the gas sample introduction flow rate is about several liters to several tens of liters per minute. The capacity of the gas sample introduction pump 27 to be used strongly depends on the length of the gas sample introduction pipe 24. If the gas sample introduction pipe 24 becomes longer, it is necessary to use a gas sample introduction pump 27 having a higher capacity. In order to make it difficult for the gas sample to be adsorbed on the inner wall of the gas sample introduction pipe 24, it is necessary to raise the temperature inside the gas sample introduction pipe 24 when the gas sample is introduced. A flexible pipe is used as the gas sample introduction pipe 24. A hard but bendable pipe 25 such as a bellows pipe is provided around the gas sample introduction pipe 24, and the gas sample introduction pipe 24 inside thereof is structurally reinforced. . A gas sample introduction pipe heater 26 is wound around the gas sample introduction pipe 24 in order to prevent adsorption of the gas sample to the inner wall thereof, and the temperature is controlled. Usually, this temperature is a room temperature (10 to 30 ° C.) or more, and a maximum temperature of about 200 ° C. On the other hand, when a gas sample is introduced using the gas sample introduction pump 27, a handle 19 is provided at the probe tip so as to be easily held in the hand, or a switch 18 of the gas sample introduction pump 27 is provided in the vicinity of the handle 19. Convenient. A probe tip heater 20 is provided at the probe tip to prevent adsorption of the gas sample at the probe tip, and a filter 22 is provided so that large particles and dust are not directly sucked toward the gas sample introduction pipe 24. This is also an important point. At this time, it is preferable to provide a dust outlet 23 for periodically cleaning the inside so that the dust clogged in the filter 22 can be easily taken out. Furthermore, when the target is a solid sample, the solid sample heating means 21 such as an infrared lamp or a halogen lamp may be provided because vapor is generated and detection becomes easier when the solid sample is heated. . When sampling a solid sample, heating the solid sample by the solid sample heating means is also a major point in operating the apparatus.

On the other hand, with the structure as shown in FIG. 9, when the length of the gas sample introduction pipe 24 exceeds several meters, it is necessary to wind the gas sample introduction pipe heater 26 as much, and the manufacturing cost increases. Therefore, in order to eliminate this drawback, the following structure is also possible. That is, as shown in FIG. 10, a metal wire heater 28a wound in multiples for energizing and heating a passing gas sample at a certain interval (in the case of providing a plurality, in addition to 28a as shown in FIG. 10) 28b may be provided in the middle of the sample introduction pipe 24. If the gas sample introduction pipe 24 is long, this number can be further increased). In actual operation, the gas sample introduction pump 27 starts suction of the gas sample, and then the energization heating of the metal wire heater 28 is started, and measurement is started after a certain time after the metal wire heater 28 is sufficiently heated. Will do. By adopting such a sequence, problems such as a gaseous sample having a low temperature being introduced into the gas sample introduction pipe and adsorbed are alleviated. In addition, by adopting such a structure, even when a long gas sample introduction pipe 24 is used, the metal wire heater 28 may be provided at every certain distance. In addition, since the temperature of the metal wire heater rises to a predetermined temperature in about several seconds in the case of energization heating, there is no need to always heat the metal wire heater, and the operating cost can be reduced in addition to the manufacturing cost. There is a big merit.
Furthermore, a metal wire heater 28a may be provided at the tip of the gas sample introduction pipe 24 from the viewpoint of preventing introduction of large particles containing moisture. If the metal wire heater heated to a high temperature is immediately after the gas sample introduction port 17, there is a high possibility that particles containing moisture are also heated and vaporized. Of course, it is also possible to provide a filter 6 and a dust outlet 7 as shown in FIG.

  As shown in FIG. 8, the gas sample forcibly introduced into the gas sample introduction pipe 24 by the gas sample introduction pump 27 is first introduced into the gas sample heating furnace 29. At this time, when the gas sample introduction pump 27 is continuously moved, a pump cooling fan 63 may be used to cool the drive portion. In the gas sample heating furnace 29, a metal wire heater 31 for heating a gas sample provided in an insulating pipe 30 made of a material that can withstand high temperatures such as quartz provided in a metal block is energized and heated. Then, the gas sample passing through this region is heated to a high temperature. As the metal wire heater 31 for heating the gas sample, a metal wire such as a nichrome wire wound in multiple layers is used. The diameter of the insulating pipe depends on the amount of gas flowing in, but is about 5 mm when a gas of about 2 liters per minute is introduced. The length of the insulating pipe is about 10 cm. The heating temperature of the metal wire heater 31 for gas sample heating is about 30 to 400 ° C., although it depends on the sample to be measured. It is important that the introduced gas sample does not go directly to the corona discharge region described later. This is because, when particles (including moisture) are directly introduced into the corona discharge region, the corona discharge becomes unstable. If there is a gas sample heating region such as the gas sample heating metal wire heater 31 as shown in FIG. 8 before the corona discharge region, even if particles are introduced, the gas sample is heated to a high temperature. It collides with the metal wire heater 31 and is vaporized in this region. The temperature of the metal sample heater 31 for gas sample heating is controlled by a metal wire heater heating power source 32. Usually, the temperature in this region is maintained at about 50 to 400 ° C. Note that the gas sample heating furnace 29 may not be required if it is sufficiently heated at the portion of the gas sample introduction pipe 24 at the preceding stage.

The gas sample that has passed through the sample heating furnace 29 is introduced into the corona discharge unit 33 for ionization. The tip of the narrowed gas sample introduction path 58 is placed in the vicinity of the corona discharge needle electrode 37 so that the introduced gas sample is efficiently sent to the corona discharge region at the tip of the corona discharge needle electrode 37. For example, when the inner diameter of the path to the middle is about 5 mm, if the inner diameter of the tip is set to about 1 mm, the introduced gas sample is surely and efficiently placed in the corona discharge region at the tip of the corona discharge needle electrode 37. Will be introduced. At this time, the length of the gas sample introduction path 58 is about 5 cm.
The gas sample introduction path 58 existing in the vicinity of the corona discharge needle electrode 37 is made of an insulating material such as Teflon (registered trademark), Macor glass, or ceramic in order not to weaken the electric field at the tip of the corona discharge needle electrode 37. . Similar to the gas sample heating furnace 29, this region can be heated by the corona discharge part heater 35. Normally, the temperature in this region is maintained at about 50 to 300 ° C. by the corona discharge heater power supply 36.
The corona discharge portion 33 is provided with a corona discharge needle electrode 37 so that a negative high voltage (about −2 to −5 kV) can be applied by a corona discharge power source 38. At this time, the distance from the surrounding counter electrode 33 is about 1 to 10 mm. Excess gas other than ions and molecules introduced from the first pores 40 is discharged out of the system through an excess gas outlet 39.

Various kinds of mass spectrometers can be used for analyzing ions generated by the corona discharge unit 33. In the following, the case of using an ion trap type ion trap mass spectrometer will be described with reference to FIG. . The same applies when other mass spectrometers such as a quadrupole mass spectrometer and a magnetic field type mass spectrometer are used. The ions generated in the corona discharge part 33 are the first pore 40 (about 0.3 mm in diameter and about 20 mm in length) and the second pore 41 (about 0.2 mm in diameter) of the differential exhaust part heated by the heater. In the process of passing through the third pore 42 (diameter: about 0.3 mm, length: about 0.5 mm), the cluster ions are cleaved due to heating, collision with neutral molecules, etc. Molecular ions are generated. In addition, a voltage can be applied between the first pore 40 and the second pore 41, and between the second pore 41 and the third pore 42, thereby improving the ion permeability and at the same time remaining molecules. The cluster is cleaved by collision with. The differential exhaust section is usually exhausted by a roughing pump 56 such as a rotary pump, a scroll pump, or a mechanical booster pump. It is also possible to use a turbo molecular pump for exhausting in this region. The pressure between the second pore 41 and the third pore 42 is between 0.1 and 10 Torr. The generated ions pass through the third pore 42 and are converged by the electrostatic lens 43. As the electrostatic lens 43, an Einzel lens composed of three electrodes is usually used. The ions further pass through the slit 44, are deflected by the deflector 45, pass through the gate electrode 46, and are introduced into an ion trap mass spectrometer including a pair of bowl-shaped end cap electrodes 47 a and 47 b and a ring electrode 48. The slit 44 limits the solid angle of the jet including neutral particles flowing from the skimmer, and prevents unnecessary particles from being introduced into the ion trap mass spectrometer. The reason why the deflector 45 is used is to prevent neutral particles that have passed through the skimmer from being directly introduced into the ion trap mass spectrometer through the pores of the end cap electrode 47a. Here, a double-cylindrical deflector 45 composed of an inner cylinder and an outer cylinder provided with a large number of openings is used, and deflection is performed using the electric field of the outer cylinder that has oozed out from the opening of the inner cylinder. . The gate electrode 46 serves to prevent ions from being introduced from the outside into the mass analyzer when the ions stored in the ion trap mass analyzer are taken out of the system. The ions introduced into the ion trap mass analyzing unit collide with a gas such as helium introduced into the ion trap mass analyzing unit and the trajectory becomes small, and then the high frequency electric field applied to the ring electrode 48 is scanned. As a result, it is discharged out of the system and detected by the ion detector through the extraction lens 49. A gas such as helium is supplied through a regulator 55 from a supply source such as a cylinder 54. One of the merits of an ion trap mass spectrometer is that it has the property of accumulating ions, so that it can be detected by extending the accumulation time even if the sample concentration is low. Therefore, even when the sample concentration is low, high-concentration of ions can be performed at the ion trap mass spectrometer, so that sample pretreatment can be greatly simplified. In detecting the ions taken out from the ion trap mass spectrometer, the conversion dynode 50 converts the ions into electrons, and the scintillation counter 51 detects the electrons. The obtained signal is amplified by the amplifier 52 and then sent to the data processing device 53.
The chamber in which the electrostatic lens 43, the slit 44, the deflector 45, the gate electrode 46, the ion trap mass analyzer, and the ion detector exist is evacuated by the turbo molecular pump 57. The turbo molecular pump 57 requires an auxiliary pump on the back pressure side, but this can also be used as the roughing pump 56 used for the differential exhaust section. In this embodiment, a scroll pump having an exhaust capacity of about 900 liters / minute is used in the differential exhaust part, and a turbo molecular pump of about 200 liters / second is used as an exhaust device for the chamber. As a scroll pump. By using such a system, the exhaust system of the atmospheric pressure ionization mass spectrometer, which tends to be complicated, can be greatly simplified. In this apparatus, the deflector 45 is used. Of course, it is conceivable that ions are not deflected. In this case, an ion trap mass analyzer is arranged immediately after the electrostatic lens 43.
In the example of FIG. 7, two-stage differential exhaust is used, but a three-stage or higher differential exhaust system may be used. In this case, it is possible to reduce the number of pores used for the first stage differential pumping from three to two and increase the number of stages of differential pumping on the high vacuum side after the second stage.

  Normally, the data processing device 53 displays the relationship between the mass number / charge and the ion intensity (mass spectrum), the temporal change in the ion intensity of a certain mass number / charge (mass chromatogram), and the like. Further, in the data processing device 53, as described above, the final display may be further simplified instead of the mass spectrum or the mass chromatogram. That is, in the case of a dangerous substance detection device, it may be only necessary to display whether or not a problematic nitro compound has been detected. In addition, in order to identify the package, the owner can be quickly identified by displaying it on the passenger identification screen from a code read by a barcode reader (not shown). For example, as shown in FIG. 25, noise in a specific ion to be detected (in this case, TNT is shown, and the detected ion is a negative ion having an electron in the TNT molecule and its mass number is 227). Assume that this ion is detected when a certain threshold value is set for the level and a signal is detected above that level. At this time, in order to distinguish from simple spike noise, an algorithm is used that, if observed for a certain period of time or more, for example, if it is accumulated for 1 to 5 seconds, it is regarded as a signal. By adding such an algorithm, malfunctions can be reduced. In addition, when processing a package at high speed, it is required to detect in as short a time as possible, and this method can sufficiently cope. At this time, as a final display, a case as shown in FIG. 24 is considered. An indicator 65 of a substance corresponding to a certain ion to be detected is displayed on the display 64, and if A is detected by the algorithm as described above, for example, A is detected by blinking A. Inform you that At this time, an amount indicator 66 and an alarm 67 may be provided at the same time for indicating the concentration level (simply, information such as whether the amount is large or small).

  The importance of providing the gas sample heating furnace 29 as described above can be understood from the data shown in FIGS. FIG. 14 shows the relationship between the temperature of the gas sample and the ionic strength obtained when heated in the gas sample heating furnace 29. It can be seen that when the gas temperature rises, the ionic strength increases rapidly, and the change particularly when the temperature exceeds 100 ° C. is remarkable. FIG. 15 shows the difference in ionic strength obtained when the temperature of the gas sample is (a) 150 ° C. and (b) 30 ° C. The sample used was mononitrotoluene, which is a peak obtained by sucking vapor from the sample at room temperature with the gas sample suction pump 27. At the same corona discharge voltage (−2.5 kV), it can be seen that the current value increases about 2.5 times when heated without heating. Moreover, the current stability is much better when heated. When the temperature of the gas sample is high, for example, when the temperature is raised to 100 ° C. or higher, the moisture of the introduced gaseous sample is also vaporized, and ionization by corona discharge is performed efficiently and stably. Further, when the temperature of the corona discharge needle electrode 21 is indirectly increased by the gas sample heated to a high temperature, a high corona discharge current can be obtained even at the same discharge voltage, so that the ion generation efficiency is also increased.

  On the other hand, the pressure in the region where ions are generated by corona discharge is also important. Usually, in an atmospheric pressure ion source using corona discharge, a surplus gas outlet 39 is provided for taking out a surplus gas that does not flow from the pores that take in ions into the vacuum to the outside of the ion source. Therefore, since the surplus gas outlet 39 is always open, the corona discharge region is almost atmospheric pressure (about 760 Torr). However, in reality, the higher the molecular density in the corona discharge region, the higher the ionization efficiency, and the optimum value of the pressure in the corona discharge region is higher than the atmospheric pressure of 760 Torr. However, on the other hand, if the pressure in the vicinity of the pores (diameter of about 0.2 to 0.5 mm) for taking ions into the vacuum is too high, the number of molecules flowing into the mass spectrometer under high vacuum through the pores. As a result, it becomes difficult to maintain a high vacuum in the mass spectrometer. Therefore, as shown in FIG. 13, the surplus gas outlet 39 is closed and gas is continuously introduced by the gas sample introduction pump 27 to increase the pressure inside the corona discharge part 33. At this time, the structure is as shown in FIG. That is, FIG. 13A shows a method of controlling the pressure inside the corona discharge part 33 by placing a weight 59 made of a light material for reducing the conductance at the surplus gas outlet. . If the pressure inside the corona discharge part 33 becomes too high, the weight 59 floats and surplus gas exits from the surplus gas outlet. The pressure in the corona discharge region can be controlled near the optimum value based on the relationship between the amount of gas flowing into the corona discharge unit 33 and the weight of the weight. Further, as shown in FIG. 7B, a pressure adjusting unit 60 is provided at the surplus gas outlet, and while the gas sample introduction pump 27 is operating, the pressure adjusting unit 60 controls the pressure in the corona discharge region. It is also possible to control. FIG. 16 shows the relationship between the ion source pressure and the ion intensity. It is clear that the maximum ionic strength is above 760 Torr. FIG. 17 shows a case where measurement is performed by placing a weight on the surplus gas outlet and increasing the pressure in the corona discharge region (about 1.2 atm), and a case where the surplus gas outlet is opened and measurement is performed at almost atmospheric pressure (1 atm). The degree of sensitivity). The sample used was mononitrotoluene, which is a peak obtained by sucking vapor from the sample at room temperature with the gas sample suction pump 27. The sensitivity of the former is about 3 times higher than that of the latter, and it can be seen that it is effective to increase the pressure inside the corona discharge portion 33.

  The case where a gas sample is continuously introduced and detected by the gas sample introduction pump 27 as shown in FIG. 12 has been described. In this case, the result shown in FIG. 21 (sample is mononitrotoluene (MNT)) is obtained. On the other hand, as shown in FIG. 11, it is also possible to collect a gas sample in the syringe 61 and directly introduce it offline through the septum 62. At this time, a sampling method as shown in FIG. 18 can be used. That is, the solid sample 70 is placed in the sample bottle 72, and the vapor of the solid sample 70 is sampled using the syringe 69 from the gas sample introduction port 68. At this time, an air intake 71 is provided so as not to wind up in the case of a powder solid sample. Under such conditions, several tens of cc of air containing the vapor of the solid sample is collected using a syringe and directly introduced into the analyzer as shown in FIG.

  By using an analyzer as described above, even a nitro compound having a low vapor pressure can be measured with high sensitivity. This is because the negative ion generation efficiency of the nitro compound by negative corona discharge is high. In the nitro compound, the negative ion generation efficiency tends to increase as the number of nitro groups increases. Such as trinitrotoluene (TNT) as shown in FIG. 19 and RDX (RDX) as shown in FIG. 20 can sufficiently detect even a substance having a low vapor pressure such as three or more nitro groups. it can. In this measurement, the syringe introduction mode shown in FIG. 11 was used. Of course, if the method of the present invention is used, it is needless to say that even one nitro group (a substance such as mononitrobenzene shown in FIG. 13) or two nitro compounds (a nitro compound such as dinitrotoluene) can be measured with high sensitivity. Yes.

  On the other hand, the importance of increasing the temperature of the measurement sample can be seen from the results of FIGS. FIG. 22 shows the relationship between the sample temperature (in the case of TNT) and ionic strength, and FIG. 23 shows the case where the vapor is diluted when the sample temperature is different (in the case of 40 ° C. and 140 ° C.). This shows the change in ionic strength obtained. When the temperature of the sample itself rises, the ionic strength rises rapidly, and the ionic strength differs by two orders of magnitude or more at room temperature and 140 ° C. Therefore, as shown in FIG. 23, detection with a higher sample temperature is possible even when the sample itself has been diluted at a high magnification. The meaning of the solid sample heating means 21 in FIGS.

  FIG. 2 is a diagram showing the configuration of the dangerous goods detection system according to the embodiment of the present invention. Unlike the case of FIG. 1, the present embodiment is a case where gas is automatically sucked continuously from a load or the like flowing by a belt conveyor and analyzed, and the presence or absence of a dangerous substance is inspected from the analysis result. At this time, it is also possible to use the X-ray inspection apparatus at the same time.

  Details will be described with reference to FIG. In public facilities such as airports and harbors, baggage is inspected when boarding. The inspection body 1c such as a bag is placed on the belt conveyor 2b and first sent to the X-ray inspection apparatus 3b. Here, the baggage that has been inspected for dangerous materials, mainly metal, is further inspected by the on-line analytical dangerous material detection device 6 for the purpose of detecting vapor of dangerous materials. As shown in FIG. 3, the online analysis dangerous substance detection device 6 leaks from the inspection body 1e such as a bag by the online analysis sampling probe 7a having a plurality of openings or gaps in the vicinity of the inspection body 1e such as a bag. Inhaling the vapor of dangerous materials coming in and sending it to the analysis unit. At this time, as shown in FIG. 4, in order to increase the amount of steam leaking from the inspection body 1e such as a bag, an inspection body compression device 8 that compresses the inspection body between the belt conveyor 2d and the belt conveyor 2e. It is also possible to provide a mechanism that pushes the test object and prompts the discharge of the vapor when sampling the hazardous material vapor. In addition to the case where the test object is pressed from the bottom as shown in the figure, it is also effective to perform it from both the left and right directions. The inspector confirms the detection result with the display 64 as shown in FIG. The display 64 displays an indicator 65 of a substance corresponding to a certain ion to be detected. If, for example, A is detected by the above algorithm, A is detected by blinking A. Inform you that At this time, an amount indicator 66 and an alarm 67 may be provided at the same time for indicating the concentration level (simply, information such as whether the amount is large or small).

  The inspection flow in the above inspection is as shown in FIG. If an abnormality cannot be detected by the X-ray inspection apparatus 3b or the dangerous substance detection apparatus 6 for on-line analysis, the package will be allowed to pass. However, if an abnormality is detected, a detailed reexamination will be performed. Become.

  In addition, as a method of collecting sample gas from luggage such as a trunk case, when the trunk case is transported by a belt conveyor, the container of the conveyor is concave, the trunk case is stored at the bottom, and the upper lid is a belt conveyor. The sample gas in the case is exhausted to the outside by covering it almost in synchronism and setting the negative pressure with the pump within 1 second. This is achieved by detecting the discharged gas. Before the conveyor reaches the destination, the top cover is removed and the trunk case at the bottom of the recess is removed.

  This is not limited to moving, but a room for storing the trunk case is provided when it is received, and after it is stored there, the sample gas from the trunk case is sampled by the sampling device with a slight negative pressure. Detect. By detecting the sample gas with a negative pressure in this way, it is possible to quickly detect without damaging the load.

  By adopting such an inspection apparatus configuration, the same effects as in (Example 1) can be obtained. Furthermore, in this case, since both the X-ray inspection device and the dangerous material detection device are 100% inspection, the result of the X-ray inspection device and the result of the dangerous material detection device can be inspected together, and the probability of the dangerous material detection is improved. Since the inspector's hands are not bothered, the inspection can be performed efficiently.

  FIG. 3 is a diagram showing the configuration of the dangerous goods detection system according to the embodiment of the present invention. In this example, for a large cargo such as a container, the inspection tube sets a sampling probe in the opening at the corner of the container, and analyzes by sucking the gas inside the cargo for a certain period of time. In this case, the presence or absence of dangerous goods is inspected. At this time, it is also possible to use the X-ray inspection apparatus at the same time.

  Details will be described with reference to FIG. Large cargoes such as containers are inspected at public facilities such as airports and ports. In a large cargo such as a container, the internal gas is continuously sucked using the sampling probe 10 for container analysis using the opening in the corner and sent to the dangerous substance detection device 11 for container analysis. At this time, other than one opening may be sealed, or sampling may be performed simultaneously from all the openings. The inspector confirms the detection result with the display 64 as shown in FIG. The display 64 displays an indicator 65 of a substance corresponding to a certain ion to be detected. If, for example, A is detected by the above algorithm, A is detected by blinking A. Inform you that At this time, an amount indicator 66 and an alarm 67 may be provided at the same time for indicating the concentration level (simply, information such as whether the amount is large or small).

The inspection flow in the above inspection is as shown in FIG. If no abnormality is detected by the dangerous substance detection device 11 for container analysis, the package is allowed to pass through. However, if an abnormality is detected, a detailed reexamination is performed.
By adopting such a device configuration, if there is explosives inside the container and its vapor is leaking, it can be easily detected by the dangerous substance detection device, and the safety of the container can be analyzed.

FIG. 4 is a diagram showing the configuration of the dangerous goods detection system according to the embodiment of the present invention. This embodiment is a case where a room entrance management gate or the like in an engine such as nuclear power inhales and analyzes gas for a certain period of time, and checks the presence or absence of dangerous goods in the room occupant from the analysis result. At this time, it is also possible to use a metal detection device and an X-ray inspection device at the same time.
Details will be described with reference to FIG. In the public facilities such as nuclear facilities, the gate management of the resident is performed. In the occupant management gate 12, gas is collected from the subject for a certain time (several seconds to several tens of seconds) in the vapor sampling chamber 13, and is sent to the dangerous substance detection device 15 for occupant management gate through the vapor guide 14 for analysis. The inspector confirms the detection result on the monitor 16 of the dangerous substance detection device for the entrance management gate. The monitor 16 displays an indicator 65 of a substance corresponding to a certain ion to be detected. If, for example, A is detected by the algorithm as described above, A is detected by blinking A. Inform you that At this time, an amount indicator 66 and an alarm 67 may be provided at the same time for indicating the concentration level (simply, information such as whether the amount is large or small).

  The inspection flow in the above inspection is as shown in FIG. If no abnormality is detected by the dangerous person detecting device 15 for the occupant management gate, the passage is allowed to pass, but if an abnormality is detected, a detailed reexamination is performed.

  By adopting such an apparatus configuration, it is possible to detect even when an explosive is brought into the facility, and to prevent it.

  When transporting cargo from an airport to an airplane, a temperature controller that can adjust the temperature, a pressure controller that makes negative pressure, a collector that collects sample gas, and ion accumulation mass spectrometry that ionizes and analyzes the collected gas It is transported by a transport vehicle equipped with a meter and a display for notifying the analysis result. If dangerous gas is detected during the transportation, the inspection is performed on a vehicle-by-vehicle basis, thereby speeding up the detection.

The block diagram of the dangerous goods detection system by this invention. The block diagram of the dangerous goods detection system by this invention. The block diagram of a vapor | steam suction part. The block diagram of a vapor | steam suction part. The block diagram of the dangerous goods detection system by this invention. The block diagram of the dangerous goods detection system by this invention. The apparatus block diagram by this invention. The apparatus block diagram by this invention. The apparatus block diagram by this invention. The apparatus block diagram by this invention. The apparatus block diagram in syringe introduction mode. The apparatus block diagram in continuous introduction mode. The block diagram of the apparatus provided with the pressure adjustment mechanism. The figure which shows the relationship between gas temperature and ionic strength. The figure which shows the ionic strength difference when not heating when the gas is heated. The figure which shows the relationship between the pressure inside an ion source, and ion intensity | strength. The figure which shows the ion intensity difference in the case where the inside of an ion source is sealed, and an open state. The figure which shows the sampling method of the sample vapor | steam in syringe introduction mode. The figure which shows the chemical symbol of TNT by the syringe introduction mode, and the example of detection of TNT vapor | steam. The figure which shows the chemical symbol of RDX by the syringe introduction mode, and the example of a detection of RDX vapor | steam. The figure which shows the example of a detection of the MNT chemical symbol and MNT vapor | steam by a continuous introduction mode. The figure which shows the relationship between the temperature of a TNT sample, and ionic strength. The figure which shows the relationship between the dilution rate of TNT vapor | steam, and ionic strength. The figure which shows an example of the indicator in a dangerous material detection apparatus. The figure which shows the detection method in a dangerous material detection apparatus. The flowchart figure which shows the operation method of the offline type | mold dangerous material detection system at the time of combining with an X-ray inspection apparatus. The flowchart figure which shows the operation method of an online type | mold dangerous material detection system at the time of combining with an X-ray inspection apparatus. The flowchart figure which shows the operation method of a walk-through type dangerous material detection system. The flowchart figure which shows the operation method of the dangerous goods detection system for containers.

Explanation of symbols

1a, 1b, 1c, 1d, 1e --- inspector such as a bag, 2a, 2b, 2c, 2d, 2e --- belt conveyor, 3a, 3b --- X-ray inspection device, 4 --- offline analysis Dangerous Goods Detection Device, 5 --- Offline Analysis Sampling Probe, 6--Online Analysis Dangerous Goods Detection Device, 7a, 7b --- Online Analysis Sampling Probe, 8 --- Inspector Compressor, 9a 9b --- Container, 10--Sampling probe for container analysis, 11 --- Dangerous substance detection device for container analysis, 12 --- Entry control gate, 13 --- Vapor sampling chamber, 14 --- Vapor Guide, 15 --- Dangerous goods detection device for entrance management gate, 16 --- Monitor of dangerous goods detection device for entrance management gate, 17 --- Gas sample inlet, 18 --- Switch, 19 -Handle, 20 --- Probe tip heater, 21 --- Solid sample heating means, 22 --- Filter, 23 --- Garbage outlet, 24 --- Gas sample introduction pipe, 25 --- Bending Possible pipe, 26 --- gas sample introduction pipe heater, 27 --- gas sample introduction pump, 28a, 28b--metal wire heater, 29 --- gas sample heating furnace, 30 --- insulated pipe, 31 --- Metal wire heater for gas sample heating, 32 --- Metal wire heater heating power supply, 33 --- Corona discharge part, 34 --- Gas sample introduction path, 35 --- Corona discharge part heater, 36 --- Corona discharge heater power supply, 37 --- Corona discharge needle electrode, 38 --- Corona discharge power supply, 39 --- Excess gas outlet, 40 --- First pore, 41 --- Second pore, 42 --- third fine 43 --- electrostatic lens, 44 --- slit, 45 --- deflector, 46 --- gate electrode, 47a, 47b --- end cap electrode, 48 --- ring electrode, 49 --- Drawer lens, 50 --- Conversion dynode, 51 --- Scintillation counter, 52 --- Amplifier, 53 --- Data processor, 54 --- Bomb, 55 --- Regulator, 56 --- Roughing pump 57 --- turbo molecular pump, 58 --- throttle gas sample introduction path, 59 --- weight, 60 --- pressure adjusting unit, 61 --- syringe, 62 --- septum, 63 --- Pump cooling fan, 64 --- display, 65 --- substance indicator, 66 --- volume indicator, 67 --- alarm, 68 --- gas sample introduction port, 69 --- gas support Pulling syringe, 70 --- solid sample, 71 --- air inlet, 72 --- sample bottle.

Claims (7)

  Dangerous goods characterized by determining the presence or absence of dangerous goods by collecting the vapor of dangerous goods leaked from the cargo with a sampling probe, ionizing it using negative corona discharge, and detecting it using a mass spectrometer Detecting device.   The presence or absence of dangerous goods is determined by collecting the vapor of dangerous materials leaked from the transmission or reflection with a sampling probe, ionizing it with a sampling probe, and detecting it using an ion storage mass spectrometer. Dangerous goods detection device.   X-ray inspection device by transmission or reflection, sample gas collector for collecting vapor of dangerous materials leaked from luggage online, and mass analysis by ionizing the gas from the sample gas collector using negative discharge A dangerous substance detection device for determining the presence or absence of a dangerous substance by detecting using a meter.   Dangerous substance vapors leaked from large cargoes such as containers are sampled from the gaps of the container with a sampling probe, ionized using discharge, and analyzed with a mass spectrometer to determine the presence of dangerous goods. Dangerous object detection device characterized by performing.   The presence or absence of dangerous goods is detected by sampling the gas of dangerous goods leaked from humans and luggage for a certain period of time in a sealed space, ionizing it using negative discharge, and detecting it using a mass spectrometer. Dangerous object detection device characterized by determining.   A sampling apparatus comprising: a pipe for introducing a sample gas from a specimen; a pump connected to one end of the pipe; and a heating furnace located on the opposite side of the pipe of the pump. A temperature controller that can adjust the temperature, a pressure controller that makes negative pressure, a sampler that collects the sample gas, an ion storage mass spectrometer that ionizes and analyzes the collected gas, and a display that informs the analysis result A transport vehicle characterized by comprising.

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