JP4818770B2 - Concentration separation apparatus and method - Google Patents

Description

  The present invention relates to a concentration separation apparatus and method. More specifically, the present invention introduces a sample into a concentrating tube, cools the concentrating tube, concentrates the chemical component contained in the sample, and desorbs the concentrated chemical component by heating the concentrating tube. The present invention relates to a concentration and separation apparatus and method for introducing a desorbed chemical component into a separation tube and separating the chemical component by type using an adsorbent filled in the separation tube.

  In a chromatographic method of separating a variety of chemical components contained in a sample by utilizing a slight difference between the chemical components, for example, Patent Document 1 discloses that a specific portion of a sample is irradiated with a laser beam, thereby The chemical component desorbed from the sample is attached to the wall surface of the sample chamber, the entire sample chamber is heated with a heater, the chemical component adhering to the wall surface is gasified and desorbed, and then the chemical component is cooled and concentrated A technique for obtaining a gas chromatograph mass spectrum of a chemical component desorbed from a sample is disclosed by concentrating and trapping by cooling, rapidly heating the cooling concentration tube, desorbing the trapped chemical component and sending it to a detector. . Patent Document 2 discloses a method in which volatile compounds adsorbed on a concentration tube are heated and desorbed, and the desorbed chemical components are cooled and reconcentrated and then introduced into a gas chromatograph.

By the way, when analyzing chemical components by gas chromatographic methods as shown in Patent Documents 1 and 2, the chemical components are generally separated using a concentrating tube and a separating tube. The tube is filled with an adsorbent for adsorbing chemical components. And many types of chemical components are isolate | separated using the difference in adsorption power with adsorption agent. The ease of adsorption of chemical components on the adsorbent depends on the chemical properties of the chemical components. For example, when many kinds of chemical components are introduced into the separation tube, the passage speed in the separation tube varies depending on the difference in adsorption force to the adsorbent due to the respective chemical characteristics. Each chemical component is then sent to the detector. In this way, many kinds of chemical components are separated using the speed difference in the separation tube. However, the ease of adsorption between the chemical component and the adsorbent also depends on the temperature. When the chemical components α to γ are introduced and the desorption temperatures from the adsorbent (hereinafter referred to as “desorption temperatures”) are different, and the desorption temperatures increase in the order of α <β <γ, When the first temperature which is the desorption temperature of the chemical component α is reached by heating, only the chemical component α out of the chemical components α to γ is desorbed from the adsorbent and taken out from the separation tube, and the separation tube is further heated. When the second temperature, which is the desorption temperature of the chemical component β, is reached, only the chemical component β of the remaining chemical components is desorbed from the adsorbent and taken out from the separation tube, and the separation tube is further heated to remove γ. When the third temperature, which is the separation temperature, is reached, the chemical component γ is desorbed from the adsorbent. To become. That is, the separation using the difference in the desorption temperature of each chemical component becomes possible by performing at least multistage temperature control on the separation tube.
JP 7-318552 A JP-A-11-183456

  However, in the conventional method for separating chemical components by gas chromatography as shown in Patent Documents 1 and 2, the concentration tube and the separation tube are simply heated and cooled. Above the temperature, the rate of temperature rise is at most about 0.1 to 0.5 ° C./s. Therefore, the temperature cannot be increased rapidly, and there is a problem that it takes time to separate chemical components. In addition, when the temperature rises monotonically, chemical components gradually desorb from the concentration tube and reach the separation tube. That is, when many kinds of chemical components are separated, the difference in the speed of the chemical components becomes small, so that the chemical components cannot be clearly separated. If it is not possible to clearly separate many kinds of chemical components in this way, for example, the peak shape indicating the magnitude of the concentration of the chemical component displayed on the screen of the display device as the analysis result in the gas chromatograph is low and widens. As a result, the problem arises that it becomes difficult to specify the chemical component. In particular, in the case of a so-called oven-type heating method in which the entire sample chamber is heated with a heater as shown in Patent Document 1, the heat capacity is large, so that the temperature is difficult to be determined at a desired temperature. It is also difficult to quickly return to a predetermined temperature and maintain that temperature, which makes it impossible to perform a highly accurate analysis. When the temperature control is performed according to the desorption temperature of many kinds of chemical components to control the moving speed of each chemical component and they are extracted separately and quickly from the separation tube, In order to give a desorption temperature peculiar to each chemical component, that is, to raise the temperature of the separation tube in a multistage manner and rapidly and to sufficiently desorb each chemical component from the adsorbent, the temperature is set for a certain period of time in each temperature step. Although it is considered necessary to maintain the temperature, such precise temperature control cannot be performed by the existing technology. Therefore, it was not possible to quickly separate many kinds of chemical components and take them out of the separation tube in an independent state.

  Therefore, an object of the present invention is to provide a concentration separation apparatus and method that can improve the separation accuracy of various kinds of chemical components contained in a sample and reduce the time required for the separation.

In order to achieve this object, the concentration separation apparatus according to the first aspect of the present invention introduces a sample into a concentration tube, and cools the concentration tube to concentrate the chemical component contained in the sample, thereby concentrating the sample. After the chemical components are desorbed by heating the concentration tube, the desorbed chemical components are introduced into the separation tube, and the chemical components are separated by type using the adsorbent packed in the separation tube. In the concentrating / separating apparatus, the concentrating tube refrigerant injection means for directly injecting the refrigerant into the concentrating tube from the outside of the concentrating tube, the condensing tube radiant heating means for radiatively heating the concentrating tube cooled by the refrigerant, and the outside of the separating tube a coolant jetting means for separating tube directly inject coolant into the separation tube, a radiant heating means for separation tube for radiating heat of the separated pipe together are multiple circumferentially arranged in the outer periphery of the separation tube, radiation of radiant heating means for concentrating pipe The temperature of the separation tube is stepped by controlling the refrigerant injection by the refrigerant injection means for the separation pipe to the separation pipe into which the chemical component desorbed by heat is introduced and controlling the radiant heating by the radiation heating means for the separation pipe. And a temperature control means for changing the polycyclic aromatic hydrocarbon as a chemical component .

In order to achieve such an object, the concentration separation method according to the seventh aspect of the present invention is to concentrate a chemical component contained in the sample by introducing the sample into the concentration tube and cooling the concentration tube. After the chemical components are desorbed by heating the concentration tube, the desorbed chemical components are introduced into the separation tube, and the chemical components are separated by type using the adsorbent packed in the separation tube. In the concentration and separation method, the step of directly injecting the refrigerant from the outside of the concentration tube to the concentration tube using the concentration tube refrigerant injection means, and the concentration tube cooled by the refrigerant using the concentration tube radiant heating means are radiantly heated. Separating using a step, a step of directly injecting refrigerant from the outside of the separation tube into the separation tube using the refrigerant injection means for the separation tube, and a radiant heating means for separation tubes arranged in the circumferential direction on the outer periphery of the separation tube Radiate tube Controlling the refrigerant injection by the separation pipe refrigerant injection means for the separation pipe into which the chemical component desorbed by the radiation heating of the concentration pipe radiation heating means is introduced and the radiation heating by the separation pipe radiation heating means And controlling the temperature of the separation tube in a stepwise manner to control the polycyclic aromatic hydrocarbon as a chemical component .

Therefore, the chemical component is concentrated in the concentration tube by introducing the sample into the concentration tube and cooling the concentration tube with the refrigerant injected from the concentration tube refrigerant injection means. Next, when radiation is radiated from the concentration tube radiation heating means to the concentration tube, the concentration tube rapidly rises in temperature. Due to this rapid temperature increase, the concentrated chemical components are released all at once. This makes it possible to reach the separation tube in a very short time after introducing the chemical components in the sample into the concentration tube. When a chemical component is introduced from the concentrating tube into the separation tube, the chemical component proceeds toward the outlet in the separation tube while repeating adsorption and desorption with respect to the adsorbent. Here, when the separation pipe is cooled by the refrigerant injected from the refrigerant injection means for the separation pipe, the chemical component is reliably adsorbed on the adsorbent. Further, when radiation is emitted from the radiant heating means for the separation tube to the separation tube, the temperature of the separation tube is rapidly increased, and the chemical components are desorbed from the adsorbent. In this desorption process, the temperature of the separation tube is changed stepwise by controlling the refrigerant injection and radiation heating to the separation tube. That is, a series of operations are repeated in which the temperature of the separation tube is rapidly raised to a predetermined temperature, that is, a desorption temperature of a certain chemical component, and the temperature is maintained for a predetermined time. In other words, the temperature of the separation tube is raised in a multi-stage manner and rapidly between each stage so that the temperature is maintained for a predetermined time in each temperature stage. Then, during this time, separation of the chemical component is selectively performed according to the desorption temperature of the chemical component. Therefore, when there are many kinds of chemical components introduced from the concentrating tube to the separating tube, the chemical components that pass through the separating tube faster by performing temperature control by refrigerant injection and radiation heating to the separating tube, than that It becomes possible to divide each chemical component according to the passing speed, such as a chemical component that passes slowly and a chemical component that passes further slowly. That is, each chemical component can be extracted in a state of being clearly separated by type, that is, by desorption temperature. In addition, since a plurality of radiant heating means for the separation tube are arranged in the circumferential direction on the outer periphery of the separation tube, radiation rays are radiated from various directions on the outer periphery of the separation tube toward the separation tube, and these radiation rays are separated. Converge to a certain range of tubes. Thereby, the temperature increase rate of the separation tube can be increased.

  According to a second aspect of the present invention, in the concentrating / separating apparatus according to the first aspect, a plurality of concentrating tube radiant heating means are arranged in the circumferential direction on the outer periphery of the concentrating tube. The invention according to claim 8 is the concentration separation method according to claim 7, further comprising a step of arranging a plurality of radiant heating means for the concentration tube in the circumferential direction on the outer periphery of the concentration tube. In this case, radiation rays are radiated from various directions on the outer periphery of the concentrating tube toward the concentrating tube, and these radiation rays are converged to a certain range of the concentrating tube. Thereby, the temperature increase rate of the concentration tube can be increased.

  Further, the invention according to claim 3 is the concentrating and separating apparatus according to claim 1 or 2, wherein the reflecting member for the concentrating tube reflects the radiation radiated from the radiant heating means for the concentrating tube toward the concentrating tube. Is trying to arrange. The invention according to claim 9 is the concentration separation method according to claim 7 or 8, wherein the reflecting member for the concentration tube reflects the radiation emitted from the radiation heating means for the concentration tube around the concentration tube toward the concentration tube. The process of arrange | positioning is provided. In this case, the radiation emitted from the concentration tube radiation heating means is reflected by the reflection member for the concentration tube and applied to the concentration tube. In other words, the concentration tube can be directly and indirectly radiantly heated by the concentration tube radiant heating means. Therefore, the temperature increase rate of the concentration tube can be further increased.

The invention according to claim 4 is the concentrating / separating apparatus according to any one of claims 1 to 3 , wherein the radiation emitted from the radiation heating means for the separation tube is directed around the separation tube toward the separation tube. A reflection member for the separation tube to be reflected is arranged. The invention according to claim 10 is directed to the concentration separation method according to any one of claims 7 to 9 , wherein the radiation emitted from the radiation heating means for the separation tube is directed to the separation tube around the separation tube. A step of arranging a reflecting member for the separation tube to be reflected is provided. In this case, the radiation emitted from the radiation heating means for the separation tube is reflected by the reflection member for the separation tube and applied to the concentration tube. That is, the separation tube can be directly and indirectly radiantly heated by the radiant heating means for the separation tube. Therefore, the heating rate of separation can be further increased.

According to a fifth aspect of the present invention, in the concentrating / separating device according to any one of the first to fourth aspects, the separation tube is formed in a coil shape, and the axial direction is formed inside the coil-shaped portion. Separation pipe refrigerant injection means is arranged, and refrigerant is injected radially from the separation pipe refrigerant injection means. An eleventh aspect of the present invention is the concentration separation method according to any one of the seventh to tenth aspects, wherein the separation tube is formed in a coil shape, and the axial direction is formed inside the coil-shaped portion. And a step of arranging the separation pipe refrigerant injection means along with a step of radially injecting the refrigerant from the separation pipe refrigerant injection means. In this case, since the refrigerant is ejected radially from the central portion of the coil-shaped portion toward the inner peripheral portion, the separation tube can be rapidly cooled. The invention according to claim 6 is the concentrating / separating apparatus according to any one of claims 1 to 5, wherein the separation tube is heated by the radiation heating means for the separation tube and the refrigerant is injected by the refrigerant injection means for the separation tube. Held at 100 ° C. for 3 minutes, and then the separation tube is heated by the radiant heating means for separation tube for 10 seconds to raise the temperature by 50 ° C. The temperature control means controls the temperature of the separation tube so that the temperature is kept at 50 ° C. by repeatedly holding for a minute, and finally raised to 400 ° C. The invention according to claim 12 is the concentration separation method according to any one of claims 7 to 11, wherein in the step of changing the temperature of the separation tube in steps, the separation tube is radiated by the radiant heating means for the separation tube. While being heated, the refrigerant is injected by the separation pipe refrigerant injection means and held at 100 ° C. for 3 minutes, and then the separation pipe is heated by the separation pipe radiant heating means for 10 seconds to increase the temperature by 50 ° C. and the refrigerant injection for the separation pipe The temperature of the separation tube is controlled by the temperature control means so that the refrigerant is injected by the means and the temperature after the temperature rise is maintained for 2 minutes, and the temperature is raised by 50 ° C. and finally raised to 400 ° C. To be. In this case, it is possible to separate many kinds of chemical components separately and accurately and quickly as compared with the conventional method.

According to the concentration separation device according to claim 1 and the concentration separation method according to claim 7, since the concentration tube can be heated rapidly, chemical components can be desorbed all at once in the concentration tube. The separation tube can be reached in a short time. Thereby, for example, the peak shape when the magnitude of the concentration of the chemical component detected by the flame ionization detector is displayed on the screen of the display device can be sharpened. In addition, by controlling the refrigerant injection and radiant heating to the separation tube, the temperature can be raised in multiple steps and rapidly, and the temperature can be maintained for a predetermined time in each temperature step. Can be separated at high speed and with high accuracy. In addition, since the temperature of the separation tube can be rapidly increased, the chemical components can be separated quickly. In addition, since the temperature of the separation tube can be increased rapidly, for example, in the case of an organic substance such as a polycyclic aromatic component that may be decomposed when the chemical component is heated to a high temperature, the separation tube is heated in a short time. By doing so, the decomposition can be reduced.

  Further, in the case of the inventions of claim 2 and claim 8, since it is possible to quickly raise the temperature of the concentration tube, the concentrated chemical component can be desorbed in a short time, and the chemical component is concentrated. This can contribute to shortening the time required for introduction from the tube into the separation tube. By allowing the chemical component to reach the separation tube in a short time in this way, the peak shape when the magnitude of the chemical component concentration detected by, for example, a flame ionization detector is displayed on the display device screen is further sharpened. It becomes possible to. Further, it is possible to shorten the time required from the introduction of the sample into the concentrating tube until the separation of the chemical components is completed.

  Further, in the case of the inventions of claim 3 and claim 9, with a simple structure of reflecting radiation rays, for example, infrared rays, emitted from the radiant heating means for the concentration tube using a reflection member for the concentration tube, for example, a mirror, toward the concentration tube. Since infrared rays can be directly and indirectly condensed on the concentrating tube, the temperature raising rate of the concentrating tube can be increased without increasing the number of radiant heating means for the concentrating tube, that is, without increasing costs. And it becomes possible to raise the moving speed of the chemical component from the concentration tube to the separation tube by increasing the temperature rising rate.

Further, in the case of the inventions according to claims 4 and 10 , the reflection member for heating the separation tube, such as a mirror, is used to reflect a radiation ray emitted from the radiation heating means for the separation tube toward the separation tube. Infrared light can be condensed directly and indirectly on the separation tube with the structure, so that the temperature raising rate of the separation tube can be increased without increasing the number of radiant heating means for the separation tube, that is, without increasing the cost. . Therefore, when many kinds of chemical components are introduced into the separation tube, it can be separated in a short time.

Further, in the case of the inventions according to claims 5 and 11 , since the separation tube can be rapidly cooled, each stage temperature can be kept constant when the temperature is raised in multiple stages. Moreover, since it can cool rapidly, the temperature rise of a separation tube can be suppressed rapidly. Further, when it is desired to keep the separation tube at a certain temperature for a predetermined time, the control can be easily performed. In the case of the inventions according to claims 6 and 12, it is possible to separate many kinds of chemical components more accurately and more quickly than in the conventional method, and to take them out separately.

  Hereinafter, the configuration of the present invention will be described in detail based on embodiments shown in the drawings.

  FIGS. 1-11 shows an example of embodiment of the concentration separation apparatus of this invention. The concentration / separation apparatus 1 of the present embodiment introduces a sample gas 14 as a sample into the concentration tube 2, cools the concentration tube 2, concentrates a chemical component contained in the sample gas 14, and concentrates the concentrated chemical component. Is removed by heating the concentrating tube 2, and then the desorbed chemical component is introduced into the separation tube 7, and the chemical component is removed using the adsorbents 13 and 21 filled in the separation tube 7. A cooling gas pipe 3 which is a refrigerant injection means for a concentration pipe for directly injecting a cooling gas as a refrigerant from the outside of the concentration pipe 2 to the concentration pipe 2 and a concentration pipe cooled by the cooling gas. An infrared lamp 4 that is a radiant heating means for the concentration tube that radiates and heats 2, a cooling gas pipe 8 that is a refrigerant injection means for the separation tube that directly injects the cooling gas from the outside of the separation tube 7, and the separation tube Separation tube radiation that radiates 7 Control of cooling gas injection by the cooling gas pipe 8 to the infrared lamp 9 which is a heating means and the separation pipe 7 into which the chemical component desorbed by radiation heating of the infrared lamp 4 is introduced, and radiation by the infrared lamp 9 A control device 12 is provided as temperature control means for changing the temperature of the separation tube 7 stepwise by controlling heating.

  In the concentration and separation method of the present embodiment, the sample gas 14 as a sample is introduced into the concentration tube 2, and the concentration component 2 is cooled to concentrate the chemical components contained in the sample gas 14, and the concentrated chemistry. After the components are desorbed by heating the concentration tube 2, the desorbed chemical components are introduced into the separation tube 7, and the chemical components are utilized using the adsorbents 13 and 21 filled in the separation tube 7. The cooling gas pipe 3 which is the refrigerant injection means for the concentration tube is used to directly inject the cooling gas as the refrigerant into the concentration tube 2 from the outside of the concentration tube 2, and the radiation for the concentration tube A process of radiatively heating the concentration tube 2 cooled by the cooling gas using the infrared lamp 4 which is a heating means, and a cooling gas tube 8 which is a refrigerant injection means for the separation tube, from the outside of the separation tube 7 to the separation tube 7. Direct cooling gas cooling A step of spraying, a step of radiatively heating the separation tube 7 using an infrared lamp 9 which is a radiant heating means for the separation tube, and a separation tube 7 introduced with a chemical component desorbed by the radiant heating of the infrared lamp 4 And a step of changing the temperature of the separation tube 7 stepwise by controlling the cooling gas injection by all the cooling gas tubes 8 and controlling the radiant heating by the infrared lamp 9.

  As shown in FIGS. 1 to 9, the concentration / separation apparatus 1 includes a concentration tube 2, cooling gas tubes 3 and 8, infrared lamps 4 and 9, mirrors 5 and 10, a first furnace 6, a separation tube 7, and a second tube. The furnace 11 and the control device 12 are provided. The concentration / separation apparatus 1 of the present embodiment separates many kinds of chemical components contained in the sample gas 14, such as hydrocarbons and polycyclic aromatics. The chemical components separated by the concentration / separation apparatus 1 are sent to, for example, a flame ionization detector (not shown) and analyzed there. The sample gas 14 used in the present embodiment is general air mainly composed of nitrogen, oxygen, etc., and the chemical component of the sample gas 14 is, for example, nitrogen such as 3,4 benzopyrene molecules in the present embodiment. Indicates chemical components other than the main components of air, such as oxygen and oxygen. In the present embodiment, air will be described as an example of the sample gas 14, but the sample gas 14 introduced into the concentration / separation apparatus 1 is not limited to this, and is discharged from, for example, diesel exhaust gas or a factory chimney. Needless to say, the gas to be used may be targeted.

  The concentration tube 2, a part of the cooling gas tube 3, the infrared lamp 4 and the mirror 5 are accommodated in a first furnace 6 formed in a box shape as shown in FIGS. As shown in FIG. 6, the first furnace 6 includes a main body base 40 on which the concentration pipe 2 and the cooling gas pipe 3 are disposed, and a lid body 41 that closes an opening formed on the upper surface of the main body base 40. The lid 41 is attached to one side edge of the main body base 40 through a hinge mechanism 42 assembled with the main body base 40 so as to be freely opened and closed.

  When the opening of the main body base 40 is closed by the lid 41, a space is formed inside the first furnace 6. A plurality of mirrors 5 are provided on the inner peripheral surface of the first furnace 6 forming this space, that is, the back surface of the lid and the inner surface of the main body base 40 as shown in FIG. A plurality of infrared lamps 4 are provided inside the first furnace 6 so as to be surrounded by a plurality of mirrors 5. Semicircular cutouts 40a are formed at both ends of the main body base 40, and both ends of the concentrating tube 2 are placed on the cutouts 40a in a state of being covered with a heat insulating material. Moreover, the front-end | tip part of the cooling gas pipe | tube 3 is arrange | positioned in the center part vicinity of the concentration pipe | tube 2 (refer FIG. 1). The middle of the cooling gas pipe 3 is covered with one end of the concentrating pipe 2 so as not to contact with each other by a heat insulating material. A semicircular cutout 41 a that faces the cutout 40 a of the main body base 40 when the opening of the main body base 40 is closed is formed at both ends of the lid body 41. Therefore, when the opening of the main body base 40 is closed by the lid 41, both ends of the concentration tube 2 and the cooling gas pipe 3 are formed by the notches 40 a of the main body base 40 and the notches 41 a of the lid 41 through the covering material. As shown in FIGS. 5 and 6, the concentrating tube 2 and the cooling gas tube 3 are surrounded by the infrared lamp 4 and the mirror 5. The lid 41 is locked to the main body base 40 by the lock mechanism 43 while maintaining this state. The first furnace 6 is configured such that air in the internal space naturally escapes from both ends of the first furnace 6. Further, a heat insulating material is filled between the wall of the main body base 40 and the mirror 5 attached to the main body base 40 and between the wall of the lid 41 and the mirror 5 attached to the lid 41. Has been.

  The concentrating tube 2 is for concentrating a small amount of chemical components contained in the introduced sample gas 14 and increasing the concentration to a level that can be analyzed by, for example, a flame ionization detector. The concentrating tube 2 is made of a straight stainless steel tube, and an adsorbent 13 is filled in the central portion of the tube. The adsorbent 13 temporarily adsorbs the chemical component in the sample gas 14 and then desorbs the chemical component by heating and heating. In this embodiment, the adsorbent 13 is a diatomaceous earth-based powder. Adopt the body. Since chemical components are easily adsorbed at low temperatures and difficult to adsorb at high temperatures, they can be concentrated by cooling the concentration tube 2 and desorbed by heating. In the present embodiment, diatomaceous earth-based powder is described as an example of the adsorbent 13, but the adsorbent 13 is not necessarily limited to this, and for example, the particle size is 0.2-0. It may be a diatomaceous earth based powder of about 5 mm or a glass bead.

  A pipe 15 for introducing the sample gas 14 into the concentration tube 2 is connected to one end of the concentration tube 2. A pipe 17 that connects the concentration tube 2 and one end of the separation tube 7 and communicates the concentration tube 2 and the separation tube 7 is connected to the other end of the concentration tube 2 via a connector 18. In the vicinity of the pipes 15 and 17, heaters 24 and 25 are arranged along the shape of the pipes 15 and 17. The heaters 24 and 25 are for preventing chemical components from adhering to the inner wall of the pipe 17 by heating the pipes 15 and 17. The pipe 15 and the heater 24, and the pipe 17 and the heater 25 are covered with a heat insulating material. In the present embodiment, a stainless steel tube is used as the concentrating tube 2, but it may be made of a material having temperature durability in the range of −40 ° C. to 600 ° C. and rich in thermal conductivity. Alternatively, titanium may be used.

  The cooling gas pipe 3 conveys the cooling gas toward the concentration pipe 2 and directly injects it to the concentration pipe 2. The cooling gas pipe 3 is formed in a straight line, and is arranged in parallel with the concentration pipe 2 along the longitudinal direction. A portion of the cooling gas pipe 3 other than the portion entering the space in the first furnace 6 is covered with a heat insulating material. The base end of the cooling gas pipe 3 is connected to the gas cooling device 28 via the electromagnetic valve 22. The gas cooling device 28 supplies air at normal temperature and cools the air by adiabatic expansion. When the electromagnetic valve 22 is opened, the cooling gas is conveyed toward the concentration tube 2 through the cooling gas tube 3. The front end surface of the cooling gas pipe 3 is closed, and an outlet 3 a through which the cooling gas is jetted is provided along the longitudinal direction of the concentrating pipe 2 on the surface facing the concentrating pipe 2 at the front end of the cooling gas pipe 3. A plurality are arranged at regular intervals. Therefore, when the solenoid valve 22 is opened and the cooling gas flows into the cooling gas pipe 3, the cooling gas is injected toward the concentration pipe 2 from the ejection port 3 a. In the gas cooling device 28, a pressure value for sending the cooling gas to the cooling gas pipe 3 is set in advance, and when the cooling gas is sent into the cooling gas pipe 3 in accordance with this pressure value, the cooling gas is ejected vigorously from the ejection port 3a. Is done. Then, the cooling gas is directly injected into the concentration tube 2 in this manner, so that the temperature of the concentration tube 2 can be rapidly lowered. In this embodiment, the ejection speed of the cooling gas ejected from the ejection outlet 3a is 1 liter / min. The ejection speed can be changed as appropriate. The temperature condition of the cooling gas injected into the concentration tube 2 is normal temperature or lower, specifically −5 ° C. or lower, and a temperature range of −20 ° C. to −5 ° C. is preferable.

  As shown in FIG. 5, four infrared lamps 4 are provided on the outer periphery of the concentrating tube 2 along the circumferential direction at a certain distance from the outer peripheral surface of the concentrating tube 2, that is, along the circular arc shown by the two-dot chain line in FIG. These are arranged at regular intervals. These infrared lamps 4 are all formed in a straight line as shown in FIG. 4, and are arranged in parallel along the longitudinal direction of the concentration tube 2 with the axis of the concentration tube 2 as the center. That is, the concentration tube 2 is surrounded on all sides by the infrared lamp 4. Therefore, when the infrared lamp 4 is energized, infrared rays are emitted from the infrared lamp 4 toward the concentration tube 2. Thus, the temperature of the concentration tube 2 can be rapidly raised by radiatively heating the concentration tube 2 from various directions. In the present embodiment, four infrared lamps 4 are used, but the number of infrared lamps 4 can be changed as appropriate. Further, the installation location of the infrared lamp 4 may be changed as appropriate as long as the concentration tube 2 is directly and efficiently irradiated with infrared rays. Further, the size and shape of the infrared lamp 4 may be any as long as the infrared ray is directly and efficiently irradiated onto the concentrating tube 2, and can be changed as appropriate.

  As shown in FIG. 6, a plurality of mirrors 5 are arranged inside the first furnace 6, and when the lid 41 of the first furnace 6 is closed with respect to the main body base 40, the concentration tube 2 is centered. The concentrating tube 2 and the infrared lamp 4 are surrounded by a plurality of mirrors 5. One mirror 5 is provided for each infrared lamp 4. Each mirror 5 is formed along the longitudinal direction of the infrared lamp 4, and its cross section is curved in a semi-elliptical shape. And the inner surface of the curved part is a mirror surface. When the opening of the main body base 40 is closed by the lid 41 of the first furnace 6, the mirror surface of each mirror 5 is arranged to face the infrared lamp 4 corresponding to the mirror 5. Each mirror 5 concentrates the reflected light from the infrared lamp 4 as shown by the broken line in FIG. 6 when the infrared lamp 4 irradiates infrared rays with the lid 41 of the first furnace 6 closed. It arrange | positions so that it may converge on the center part of the pipe | tube 2. As shown in FIG. Accordingly, the concentration tube 2 is heated by direct infrared irradiation from the infrared lamp 4 and indirect infrared irradiation through the mirror 5. That is, by arranging the infrared lamp 4 as described above, a certain range of the central portion of the concentration tube 2 can be heated uniformly. Thus, the mirror 5 functions as a concentrating tube reflecting member that reflects the infrared rays irradiated from the infrared lamp 4 toward the concentrating tube 2. In the present embodiment, an example in which one mirror 5 is provided for each infrared lamp 4 is described. However, the present invention is not limited to this, and the number of mirrors 5 and the installation locations are irradiated from the infrared lamp 4. As long as the infrared rays to be reflected can be efficiently reflected toward the concentrating tube 2, it can be appropriately changed.

  The separation tube 7, the cooling gas tube 8, the infrared lamp 9, and the mirror 10 are accommodated in a second furnace 11 formed in a box shape as shown in FIGS. 8 and 9. The structure of the second furnace 11 is substantially the same as that of the first furnace 6, and is formed on a main body base 44 on which the separation pipe 7 and the cooling gas pipe 8 are disposed, and on the upper surface of the main body base 44. And a lid 45 that closes the opening. The lid 45 is attached to one side edge of the main body base 44 through a hinge mechanism 46 assembled with the main body base 44 so as to be freely opened and closed.

  When the opening of the main body base 44 is closed by the lid 45, a space is formed in the second furnace 11. A plurality of mirrors 10 are provided on the inner peripheral surface of the second furnace 11 forming this space, that is, on the back surface of the lid 45 and the inner surface of the main body base 44 as shown in FIG. A plurality of infrared lamps 9 are provided inside the second furnace 11 so as to be surrounded by the plurality of mirrors 10. Semicircular cutouts 44a are formed at both ends of the main body base 44, and the both ends of the separation tube 7 are placed on the cutouts 44a in a state of being covered with a heat insulating material. The tip of the cooling gas pipe 8 is disposed near the center of the separation pipe 7 (see FIG. 1). The middle of the cooling gas pipe 8 is covered with one end of the separation pipe 7 so as not to contact each other with a heat insulating material. A semicircular cutout 45a is formed at both ends of the lid 45 so as to face the cutout 44a of the main body base 44 when the opening of the main body base 44 is closed. Therefore, when the opening of the main body base 44 is closed by the lid 45, both ends of the separation tube 7 and the cooling gas pipe 8 are connected to each other by the notches 44 a of the main body base 44 and the notches 45 a of the lid 45 through the heat insulating material. As shown in FIGS. 8 and 9, the separation tube 7 and the cooling gas tube 8 are surrounded by the infrared lamp 9 and the mirror 10. The lid 45 is locked to the main body base 44 by the lock mechanism 47 while maintaining this state. The second furnace 11 is configured such that air in the internal space naturally escapes from both ends of the second furnace 11. Further, a heat insulating material is filled between the wall of the main body base 44 and the mirror 10 attached to the main body base 44 and between the wall of the lid 45 and the mirror 10 attached to the lid 45. Has been.

  The separation tube 7 separates chemical components introduced from the concentration tube 2 through the pipe 17 by type. The separation tube 7 is made of a bent stainless steel tube, and a pipe 17 is connected to one end of the separation tube 7 via a connector 19. A flame ionization detector (not shown) is connected to the other end of the separation tube 7 via a pipe 26. A heater 27 is arranged in the vicinity of the pipe 26 along the shape of the pipe 26. The heater 27 warms the pipe 26 to prevent chemical components from adhering to the inner wall of the pipe 26. The pipe 26 and the heater 27 are covered with a heat insulating material.

  As shown in FIGS. 1 and 2, the central portion of the separation tube 7 is formed in a coil shape, and an adsorbent 21 is filled in the coiled portion 20. The material of the adsorbent 21 is the same material as the adsorbent 13. A black body such as eaves or platinum black is uniformly applied to the outer wall surface of the coil-shaped portion 20, and the coil-shaped portion 20 is uniformly heated by infrared rays. In this embodiment, a stainless steel tube is used as the separation tube 7, but it is made of a material having a temperature durability in the range of −40 ° C. to 600 ° C. and having a high thermal conductivity, such as copper or titanium. Also good.

  The cooling gas pipe 8 conveys the cooling gas toward the separation pipe 7 and injects it directly to the separation pipe 7. As shown in FIGS. 1 and 3, the cooling gas pipe 8 is bent in a step shape, and the base end thereof is connected to the gas cooling device 29 via an electromagnetic valve 23. The gas cooling device 29 supplies normal temperature air and cools the air by adiabatic expansion. When the electromagnetic valve 23 is opened, the cooling gas is conveyed toward the separation pipe 7 through the cooling gas pipe 8. The distal end portion of the cooling gas pipe 8 is formed in a linear shape, and the linear portion 8 a is disposed on the axis inside the coiled portion 20. The distal end surface of the cooling gas pipe 8, that is, the distal end surface of the linear portion 8a is closed. A plurality of ejection ports 8b through which cooling gas is ejected are formed at equal intervals along the circumferential direction on the outer peripheral surface of the linear portion 8a. A plurality of ejection openings 8b arranged in the circumferential direction are formed at equal intervals along the longitudinal direction of the linear portion 8a. Therefore, when the electromagnetic valve 23 is opened and the cooling gas flows into the cooling gas pipe 8, the cooling gas is injected radially from the outlet 8b toward the inner peripheral portion of the coiled portion 20. In the gas cooling device 29, a pressure value for sending the cooling gas to the cooling gas pipe 8 is set in advance, and when the cooling gas is sent into the cooling gas pipe 9 according to this pressure value, the cooling gas is ejected vigorously from the ejection port 8b. Is done. As described above, the cooling gas is sprayed radially and directly from the central portion to the inner peripheral portion of the coil-shaped portion 20, whereby the temperature of the separation tube 7 can be rapidly lowered. The ejection speed of the cooling gas ejected from the ejection outlet 8b in this embodiment is 1 liter / min. The ejection speed can be changed as appropriate. Moreover, the temperature conditions of the cooling gas injected to the coil-shaped part 20 are below normal temperature, specifically 10 degreeC or less, and the temperature range of -20 degreeC-10 degreeC is preferable.

  As shown in FIG. 8, the infrared lamp 9 is provided on the outer periphery of the coil-shaped portion 20 along the circumferential direction at a certain distance from the outer peripheral surface of the coil-shaped portion 20, that is, along the arc shape indicated by a two-dot chain line in FIG. Are arranged at equal intervals. These infrared lamps 9 are all formed in a straight line as shown in FIG. 7, and are arranged in parallel along the axial direction with the axis of the coil-shaped portion 20 as the center. That is, the separation tube 7 is surrounded on all sides by the infrared lamp 9. Therefore, when the infrared lamp 9 is energized, infrared rays are irradiated from the infrared lamp 9 toward the separation tube 7, and a certain range of the separation tube 7 can be heated uniformly. And it becomes possible to raise the temperature of the separation pipe 7 rapidly by radiatively heating the separation pipe 7 from many directions.

  A plurality of mirrors 10 are arranged inside the second furnace 11, and when the lid 45 of the second furnace 11 is closed with respect to the main body base 44, the separation tube 7 and the infrared lamp are centered on the separation tube 7. 9 is surrounded by a plurality of mirrors 10. One mirror 10 is provided for each infrared lamp 9. Each mirror 10 is formed along the longitudinal direction of the infrared lamp 9, and its cross section is curved in an arc shape. And the inner surface of the curved part is a mirror surface. When the opening of the main body base 44 is closed by the lid 45 of the second furnace 11, the mirror surface of each mirror 10 is arranged to face the infrared lamp 9 corresponding to the mirror 10. Further, each mirror 10 is configured such that when the infrared ray 9 is irradiated with infrared rays with the lid 45 of the second furnace 11 closed, the reflected light from the infrared lamps 9 is coiled as shown by the broken line in FIG. It arrange | positions so that it may converge on the center part of the shape part 20. FIG. Therefore, the separation tube 7 is heated by direct infrared irradiation from the infrared lamp 9 and indirect infrared irradiation through the mirror 10. That is, by arranging the infrared lamp 4 as described above, a certain range of the central portion of the separation tube 7, that is, the coiled portion 20 can be uniformly and rapidly heated. In this way, the mirror 10 functions as a separation member for the separation tube that reflects the infrared rays emitted from the infrared lamp 9 toward the separation tube 7. In the present embodiment, an example is described in which one mirror 10 is provided for each infrared lamp 9. However, the present invention is not limited to this, and the number of mirrors 10 can be changed as appropriate. Further, in the present embodiment, a mirror 5 is described as an example of the reflecting member for the concentrating tube for reflecting the infrared ray irradiated from the infrared lamp 4 toward the concentrating tube 2, and the infrared ray irradiated from the infrared lamp 9 is separated. Although the mirror 10 has been described as an example of the reflecting member for the concentrating tube for reflecting toward the tube 7, for example, a light reflecting member made of a transparent resin in which a reflective prism or a thin film metal layer is closely attached instead of the mirrors 5 and 10. It may be a member that can reflect radiation rays such as infrared rays toward the concentrating tube 2 and can be appropriately changed.

  One set of thermocouples 28, 29, 30, 31, 32, 33, 34 is spotted on the outer wall of each of the concentrating pipe 2, pipes 15, 17, 26, the cooling gas pipes 3, 8, and the coiled part 20. It is attached by welding. In this embodiment, a K-type thermocouple having a diameter of 0.3 mm is employed. The type of thermocouple is not limited to this and can be changed as appropriate.

  The control device 12 is constituted by, for example, a CPU or MPU, and the overall operation of the concentration / separation device 1 such as infrared lamps 4 and 9, electromagnetic valves 22 and 23, heaters 24, 25 and 27, gas cooling devices 28 and 29, and the like. The operation is controlled. The control device 12 is connected to thermocouples 28 to 34. In addition, infrared lamps 4 and 9, electromagnetic valves 22 and 23, and heaters 24, 25, and 27 are connected to the control device 12 via drivers 4a, 9a, 22a, 23a, 24a, 25a, and 27a. A temperature control program is stored in advance in the memory area of the control device 12. This temperature control program raises or lowers the temperature of the concentrating tube 2 or the separating tube 7 at a predetermined speed by jetting cooling gas or irradiating infrared rays, or holds the temperature for a predetermined time at a predetermined temperature. 9, solenoid valves 22 and 23, heaters 24, 25 and 27, gas cooling devices 28 and 29, and the like. It is controlled based on a control program. For example, the control device 12 controls the jetting power of the cooling gas ejected from the ejection ports 3a and 8b, that is, the pressure values of the gas cooling devices 28 and 29 mainly based on the temperature control program. The controller 12 controls the cooling gas ejection time, that is, the opening / closing time of the electromagnetic valves 22 and 23 mainly based on the temperature control program. Further, the control device 12 controls the time of infrared irradiation, that is, on / off of energization of the infrared lamps 4 and 9 mainly based on the temperature control program.

  When the infrared irradiation by the infrared lamps 4 and 9 is performed or the irradiation is stopped, the control device 12 outputs a signal indicating the infrared irradiation or the irradiation stop to the drivers 4a and 9a, and the drivers 4a and 9a are supplied from the control device 12. In response to the input signal, the operation of the infrared lamps 4 and 9 is controlled so as to stop the irradiation of infrared rays or the irradiation. The flow of this process will be described with reference to the flowchart shown in FIG. 10. First, the control device 12 outputs a signal indicating infrared irradiation or a stop of the irradiation to the drivers 4a and 9a (S1). The drivers 4a and 9a irradiate infrared rays from the infrared lamps 4 and 9 (S3) when a signal indicating infrared irradiation is input from the control device 12 (S2). Next, when a signal is not input from the control device 12 to the drivers 4a and 9a (S4; N), the process ends. On the other hand, when the driver 4a, 9a receives a signal indicating that the infrared irradiation or the irradiation is stopped from the control device 12 (S4; Y), the signal indicates that the infrared irradiation is stopped (S5). N), the infrared irradiation by the infrared lamps 4 and 9 is stopped (S6). If the signal indicates the infrared irradiation (S5; Y), the infrared irradiation by the infrared lamps 4 and 9 is continued (S3). .

  Further, when opening and closing the electromagnetic valves 22 and 23, the control device 12 outputs a signal indicating that the electromagnetic valves 22 and 23 are opened or closed to the drivers 22a and 23a. The drivers 22a and 23a open and close the electromagnetic valves 22 and 23 in response to a signal input from the control device 12. The flow of this process will be described with reference to the flowchart shown in FIG. 11. First, the control device 12 outputs a signal indicating that the electromagnetic valves 22 and 23 are opened or closed to the drivers 22a and 23a (S101). The drivers 22a and 23a open the electromagnetic valves 22 and 23 (S103) when a signal indicating that the electromagnetic valves 22 and 23 are opened from the control device 12 is input (S102). Next, when a signal is not input from the control device 12 to the drivers 22a and 23a (S104; N), the process ends. On the other hand, a signal indicating that the electromagnetic valves 22 and 23 are opened or closed is input from the control device 12 of the driver 22a and 23a (S104; Y), and this causes the electromagnetic valves 22 and 23 to be closed. When the signal is a signal indicating (S105; N), the solenoid valves 22 and 23 are closed (S106), and when the signal is indicating opening of the solenoid valves 22 and 23 (S105; Y), the solenoid valve The open state of 22 and 23 is continued (S103).

  Incidentally, when heating by the heaters 24, 25, 27 or stopping of the heating is performed, the control device 12 outputs a signal indicating heating by the drivers 24a, 25a, 27a or stopping of the heating. The drivers 24a, 25a, 27a execute heating by the heaters 24, 25, 27 or stop of the heating in response to a signal input from the control device 12.

  The controller 12 constantly monitors the temperatures of the outer wall portions of the concentrating tube 2, pipes 15, 17, 26, the cooling gas tubes 3, 8 and the coil-shaped portion 20 measured by the thermocouples 28 to 34. The operations of the infrared lamps 4 and 9, the electromagnetic valves 22 and 23, and the heaters 24, 25 and 27 are controlled based on the measurement results of the pairs 28 to 34 and the temperature control program. When the concentration tube 2 is rapidly heated from, for example, an initial set temperature 30 ° C. (hereinafter referred to as normal temperature) in the furnace to 350 ° C. and maintained at a temperature of 350 ° C. for a predetermined time, the control device 12 first sets the infrared lamp 4 To start infrared irradiation. When the controller 12 determines that the temperature of the concentrating tube 2 has reached 350 ° C. based on the measurement result of the thermocouple 28, the infrared irradiation by the infrared lamp 4 is stopped via the driver 4a. Here, when the temperature of the concentration tube 2 exceeds 350 ° C. due to residual heat, the solenoid valve 22 is opened via the driver 22a. As a result, the cooling gas is injected into the concentration tube 2 and the concentration tube 2 is rapidly cooled. When the cooling is excessive, the infrared irradiation by the infrared lamp 4 is performed again. By repeating these operations, the temperature of the concentration tube 2 can be maintained at 350 ° C. for a predetermined time. Thus, the chemical components adsorbed on the adsorbent 13 can be desorbed simultaneously by rapidly raising the temperature to 350 ° C. and maintaining the temperature for a certain period of time.

  When the temperature of the concentrating tube 2 is rapidly lowered from, for example, 350 ° C. to room temperature, first, the infrared irradiation by the infrared lamp 4 is stopped. Then, the electromagnetic valve 22 is opened, the cooling gas is injected into the concentrating tube 2, and the injection is stopped based on the measurement result of the thermocouple 28. In the present embodiment, since organic substances such as polycyclic aromatics are used as separation objects by the concentration / separation apparatus 1, the maximum temperature of the concentration tube 2 is set to 350 ° C. That is, if the temperature of the concentration tube 2 exceeds 350 ° C., organic substances such as polycyclic aromatics may be decomposed.

  On the other hand, when the temperature of the coiled portion 20 in the separation tube 7 is raised from room temperature to 100 ° C., for example, and maintained for a predetermined time, the control device 12 first activates the infrared lamp 9 to start infrared irradiation. Let When the control device 12 determines that the temperature of the coiled portion 20 has reached 100 ° C. based on the measurement result of the thermocouple 34 and the temperature control program, the infrared irradiation by the infrared lamp 9 is stopped via the driver 9a. Here, when the temperature of the coil-shaped part 20 exceeds 100 ° C. due to residual heat, the control device 12 opens the electromagnetic valve 23 via the driver 23a. Thereby, cooling gas is injected radially toward the inner peripheral part from the center part of the coil-shaped part 20, and the coil-shaped part 20 is cooled rapidly. When the cooling is excessive, the infrared irradiation by the infrared lamp 9 is executed again. By repeating these operations, the temperature of the coiled portion 20 can be maintained at 100 ° C. for a predetermined time. Thereafter, the control device 12 performs the same control as described above, that is, the control device 12 controls the operation of the infrared lamp 9 and the electromagnetic valve 23 based on the measurement results of the thermocouples 28 to 34 and the temperature control program. It becomes possible to change the temperature of the shape part 20 in steps. For example, after maintaining the coiled portion 20 at 100 ° C. for a predetermined time as described above, the temperature is rapidly raised by 50 ° C. by infrared irradiation, and then the control device 12 controls the injection of cooling gas and infrared irradiation at that temperature. As a result, it is possible to maintain the temperature at 150 ° C. for a predetermined time. Thereafter, the controller 12 repeatedly performs a similar series of controls to raise the temperature of the coil-shaped portion 20 to a desired temperature stepwise. It is possible to go.

  When the temperature inside the coiled portion 20 is rapidly lowered from, for example, 150 ° C. to room temperature, the infrared irradiation by the infrared lamp 9 is stopped. Then, the electromagnetic valve 23 is opened, and the cooling gas is injected radially from the central part of the coiled part 20 toward the inner peripheral part, and the injection is stopped based on the measurement result of the thermocouple 34. Incidentally, for the temperature control of the pipes 15, 17, 26, the operation of the heaters 24, 25, 27 is controlled by the control device 12 in the same manner as the temperature control for the concentration pipe 2 and the separation pipe 7 described above. It ’s fine.

  In this way, the control device 12 controls the operation of the infrared lamps 4 and 9, the electromagnetic valves 22 and 23, and the heaters 24, 25 and 27 based on the measurement results of the thermocouples 28 to 34 and the temperature control program, thereby concentrating the tubes. 2. It becomes possible to control the temperature of each of the pipes 15, 17, 26 and the coil-shaped part 20 quickly and easily.

  In the concentration / separation apparatus 1 configured as described above, first, the sample gas 14 is introduced into the concentration tube 2. The concentration tube 2 is cooled by the cooling gas, adsorbed on the adsorbent 13 and concentrated. The temperature inside the concentration tube 2 is rapidly raised to 350 ° C. by the infrared lamp 4 and maintained at 350 ° C. for a predetermined time by injection of cooling gas. During this time, the chemical components concentrated are desorbed from the adsorbent 13 all at once and fed into the separation tube 7. This makes it possible to reach the separation tube in a very short time after the chemical components in the sample are introduced into the concentration tube.

  Next, in the separation tube 7 into which the chemical component has been introduced from the concentration tube 2, infrared irradiation and cooling gas injection are repeatedly performed on the coiled portion 20, for example, to set the temperature of the coiled portion 20 to 100 ° C. to 400 ° C. The temperature is raised in multiple steps by 50 ° C., and the temperature is maintained for a predetermined time in each temperature step. That is, the temperature of the coil-shaped part 20 is changed in steps. As a result, when there are many kinds of chemical components introduced from the concentration tube 2 to the separation tube 7, the chemical components that are desorbed earliest from the adsorbent 21 and pass through the separation tube 7, and then pass through the separation tube 7 at the next speed. It is possible to divide each chemical component according to the passing speed in the separation tube 7 such as a chemical component that passes through the separation tube 7 later than the chemical component. It can be taken out in a separated state.

  As described above, according to the concentration / separation apparatus 1, the cooling gas injection and the infrared irradiation to the separation tube 7 into which various kinds of chemical components are introduced are controlled, and the temperature of the separation tube 7 is adjusted in multiple stages. Since the temperature can be maintained at each temperature stage, that is, the temperature rise rate in the coiled portion 20 of the separation tube 7 can be changed stepwise. It becomes possible to clearly separate chemical components, and when the magnitude of the concentration of chemical components detected by the flame ionization detector is displayed on the screen of the display device, a sharp peak shape is obtained for each chemical component Is possible. Further, since infrared rays are condensed directly and indirectly on the concentration tube 2 and the separation tube 7 by the infrared lamps 4 and 9 and the mirrors 5 and 10, the chemical component concentration tube 2 to the separation tube 7. Therefore, the time required for separating the chemical components can be greatly shortened. Furthermore, since the cooling gas pipe 8 is disposed inside the coiled portion 20 and the cooling gas is jetted radially therefrom, the coiled portion 20 can be rapidly cooled and the temperature can be adjusted quickly. You can do it. Thereby, while the temperature is in a constant state, a chemical component whose temperature is the desorption temperature can be selectively desorbed from the adsorbent and taken out from the separation tube 7. Therefore, when performing separation of many kinds of chemical components using the concentration separation device 1, the temperature is increased rapidly and stepwise so as to correspond to the desorption temperature peculiar to each chemical component. By keeping the temperature at a constant value for a predetermined time, it is possible to clearly separate many kinds of chemical components in a short time, and it is possible to obtain accurate analysis results in a shorter time than in the conventional gas chromatograph analysis. become able to.

  The above-described embodiment is an example of a preferred embodiment of the present invention, but is not limited thereto, and various modifications can be made without departing from the scope of the present invention. For example, in the above-described embodiment, an example in which air at normal temperature is cooled by the gas cooling devices 28 and 29 and the cooling gas is injected from the cooling gas pipes 3 and 8 has been described. However, for example, gas that is vaporized from liquefied carbon dioxide gas May be used as the cooling gas, or a gas that is vaporized from liquid nitrogen may be used as the cooling gas, and can be changed as appropriate.

  Moreover, in this embodiment, although cooling gas was used as a refrigerant | coolant, you may use liquids, such as alcohol liquid, for example as a cooling fluid. In this case, as the cooling liquid, the temperature of the concentrating tube 2 and the coiled portion 20 is set to normal temperature or lower by vaporization heat, specifically, −5 ° C. or lower for the concentrating tube 2 and 10 ° C. or lower for the coiled portion 20. Liquids that can be used are preferred. Further, even when a cooling liquid is employed as the refrigerant, it is preferable that the liquid is ejected vigorously toward the concentration pipe 2 and the coiled portion 20 using the cooling gas pipes 3 and 8.

  In the present embodiment, the operations of the infrared lamps 4 and 9, the electromagnetic valves 22 and 23, and the heaters 24, 25 and 27 are controlled according to instructions from the control device 12. And the operation of the infrared lamps 4 and 9, the electromagnetic valves 22 and 23 and the heaters 24, 25 and 27 may be controlled manually based on the measurement result. Even in this case, it is possible to realize a rapid temperature increase in the concentration tube 2 and maintenance of the temperature, and a stepwise change in the temperature increase rate in the separation tube 7.

  In the present embodiment, the sample gas 14 is used as a sample introduced into the concentration / separation apparatus 1. However, a particulate substance composed of molecules larger than gas molecules or an assembly of molecules may be used as a sample. That is, when it is assumed that many kinds of chemical components are contained in the particulate matter, it is necessary to separate these chemical components after gasifying them. Therefore, the chemical component contained in such particulate matter can also be separated using the concentration separation device 1.

  A temperature increase experiment was performed using the concentration / separation apparatus 1 with the concentration tube 2 and the separation tube 7 filled with air. The material of the concentration tube 2 used in this experiment is stainless steel, the outer diameter is 6 mm, and the total length is 240 mm. The material of the separation tube 7 is stainless steel, the outer diameter is 4 mm, and the total length is 1200 mm. Thermocouples 28 to 34 were K-type having a diameter of 0.3 mm. The thermocouples 28 and 34 were spot welded to the concentration tube 2 and the coiled portion 20.

  First, the concentration tube 2 was set to 5 ° C. with a cooling gas, and the temperature was maintained for 3 minutes. At the same time, the separation tube 7 was heated with infrared rays and kept at 100 ° C. for 3 minutes by spraying a cooling gas. Next, the concentration tube 2 was heated with infrared rays for 70 seconds to 350 ° C., and the temperature was maintained for 2 minutes. At the same time, the separation tube 7 is heated for 10 seconds by irradiating with infrared rays, heated to 50 ° C., and the temperature after the temperature increase is maintained for 2 minutes by injecting a cooling gas to the separation tube 7. . And this was repeated and it heated up 50 degreeC at a time, and finally heated up to 400 degreeC. Further, the temperature was maintained for 2 minutes at each temperature step of 50 ° C. The temperature displacement of the concentration tube 2 and the separation tube 7 in this experiment is shown in FIG.

  From FIG. 12, it is possible to set the temperature rise rate of the concentrating tube 2 to 5 ° C./s in the concentration / separation apparatus 1, and in the conventional oven-type heating method, the temperature rise rate is at most 0.1-0. Considering that it is about 5 ° C./s, it has been found that the rate of temperature increase is dramatically improved. Therefore, it became clear that the chemical component in the concentration tube 2 can be quickly moved from the concentration tube 2 to the separation tube 2.

  In addition, it was confirmed from FIG. 12 that the temperature of the separation tube 7 can be increased stepwise by using the concentration separation device 1 and that the temperature can be maintained for a predetermined time at each temperature stage. . Thus, it has become clear that many types of chemical components can be clearly separated and removed separately. Further, when chemical components are separated by a conventional separation method and the separated chemical components are detected by a detector, for example, it took about 30 minutes to detect 3,4 pyrene. However, the detection time could be shortened by using the concentration / separation apparatus 1. The results are shown in Table 1 and FIG. Table 1 and FIG. 13 show the results of detection of chemical components separated by the concentrating / separating apparatus 1 using a flame ionization detector. By using the concentrating / separating apparatus 1, 3,4 benzopyrene could be detected in about 6.5 minutes as shown in Table 1 and FIG. Moreover, it has confirmed that several peaks were isolate | separated clearly from FIG. As a result, it has been clarified that various kinds of chemical components can be clearly separated by the concentration separation device 1. From the above, it has been found that when the chemical components separated by the separation tube 7 are introduced into the flame ionization detector for detection, the detection result can be obtained more accurately and quickly than the conventional method.

It is a schematic block diagram which shows the structure of the concentration separation apparatus of this invention. FIG. 3 is a layout diagram showing a positional relationship between a separation pipe and a cooling gas pipe. It is a schematic block diagram which shows the structure of the cooling gas pipe | tube used with respect to a separation pipe. It is a schematic plan view which shows the arrangement | positioning relationship between a concentration tube and an infrared lamp. It is a schematic cross-sectional view which shows the arrangement | positioning relationship between a concentrating tube, a cooling gas tube, and an infrared lamp. It is a schematic cross-sectional view which shows the arrangement | positioning relationship between the mirror arrange | positioned around the concentration tube, and an infrared lamp. It is a schematic plan view which shows the arrangement | positioning relationship between a separation tube and an infrared lamp. It is a schematic cross-sectional view which shows the arrangement | positioning relationship between a separation tube, a cooling gas tube, and an infrared lamp. It is a schematic cross-sectional view which shows the arrangement | positioning relationship between the mirror arrange | positioned around the isolation | separation tube, and an infrared lamp. It is a flowchart which shows the flow of a process when operating an infrared lamp. It is a flowchart which shows the flow of a process when operating a solenoid valve. It is a temperature graph which shows each temperature displacement of a concentration tube and a separation tube. It is a graph which shows the result of having analyzed the chemical component isolate | separated with the concentration separator by the gas chromatograph, and is a graph which shows the magnitude | size of the density | concentration in each chemical component.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Concentrator / separator 2 Concentrator tube 3, 8 Cooling gas tube 3a, 8b Outlet 4, 9 Infrared lamp 5, 10 Mirror 7 Separator tube 12 Controller 13, 21 Adsorbent

Claims (12)

The sample is introduced into the concentrating tube, and the chemical component contained in the sample is concentrated by cooling the concentrating tube, and the concentrated chemical component is desorbed by heating the concentrating tube, and then the desorption is performed. In the concentrating / separating apparatus for introducing the separated chemical component into the separation tube and separating the chemical component by type using an adsorbent filled in the separation tube, a refrigerant is supplied from the outside of the concentration tube to the concentration tube. The refrigerant injection means for the concentration tube that directly injects the refrigerant, the radiation heating means for the concentration tube that radiatively heats the concentration tube cooled by the refrigerant, and the refrigerant is directly injected into the separation tube from the outside of the separation tube de a coolant jetting means for separation tube, and a separation tube for radiant heating means for radiant heating of the separation tube while being more disposed in the circumferential direction outer periphery of the separation tube, the radiation heating of the radiant heating means for said concentrate tube The temperature of the separation pipe is controlled by controlling the refrigerant injection by the separation pipe refrigerant injection means for the separation pipe into which the chemical component is introduced and controlling the radiant heating by the radiant heating means for the separation pipe And a temperature control unit that changes the shape of the polycyclic aromatic hydrocarbon as the chemical component .   2. The concentration / separation apparatus according to claim 1, wherein a plurality of the concentration tube radiant heating means are arranged in a circumferential direction on an outer periphery of the concentration tube.   The concentrating / separating apparatus according to claim 1, wherein a concentrating tube reflecting member that reflects radiation emitted from the concentrating tube radiant heating means toward the concentrating tube is disposed around the concentrating tube. To any one of claims 1-3, characterized in that a reflecting member for separation tube for reflecting the radiation emitted from said radiant heating means for separation tube around the separation tube into the separation tube The concentration separator described. The separation pipe is formed in a coil shape, and the refrigerant injection means for the separation pipe is disposed along the axial direction inside the coil-shaped portion, and the refrigerant is injected radially from the refrigerant injection means for the separation pipe. The concentration separator according to any one of claims 1 to 4 . The separation pipe is heated by the separation pipe radiant heating means, and the refrigerant is injected by the separation pipe refrigerant injection means and held at 100 ° C. for 3 minutes, and then the separation pipe is heated by the separation pipe radiant heating means. The mixture is heated for 50 seconds to raise the temperature by 50 ° C., and the refrigerant is injected by the refrigerant injection means for the separation tube, and the temperature after the temperature increase is maintained for 2 minutes. The concentration / separation apparatus according to any one of claims 1 to 5, wherein the temperature control means controls the temperature of the separation tube so that the temperature of the separation pipe is increased. The sample is introduced into the concentrating tube, and the chemical component contained in the sample is concentrated by cooling the concentrating tube, and the concentrated chemical component is desorbed by heating the concentrating tube, and then the desorption is performed. In the concentration / separation method of introducing the separated chemical component into a separation tube and separating the chemical component by type using an adsorbent filled in the separation tube, the concentration tube is used with a refrigerant injection means for the concentration tube. Directly injecting the refrigerant from the outside to the concentrating tube, radiating and heating the concentrating tube cooled by the refrigerant using the concentrating tube radiant heating means, and using the separation pipe refrigerant injecting means. A step of directly injecting a refrigerant from the outside of the separation tube to the separation tube; a step of radiatively heating the separation tube using a plurality of separation tube radiant heating means arranged in the circumferential direction on the outer periphery of the separation tube; in front Controlling the refrigerant injection by the refrigerant injection means for the separation pipe with respect to the separation pipe into which the chemical component desorbed by the radiation heating of the concentration pipe radiation heating means is introduced, and radiant heating by the radiation heating means for the separation pipe And a step of changing the temperature of the separation tube in a step-like manner by controlling to separate polycyclic aromatic hydrocarbons as the chemical component .   8. The concentration and separation method according to claim 7, further comprising a step of arranging a plurality of the concentration tube radiant heating means in a circumferential direction on an outer periphery of the concentration tube.   9. The concentration tube reflecting member for reflecting the radiation emitted from the concentration tube radiation heating means toward the concentration tube is disposed around the concentration tube. Concentrated separation method. Any of claims 7-9, characterized in that it comprises a step of arranging a reflecting member for separation tube for reflecting the radiation emitted from said radiant heating means for separation tube around the separation tube into the separation tube The concentration separation method according to any one of the above. The step of forming the separation tube in a coil shape, the step of disposing the separation tube refrigerant injection means along the axial direction inside the coiled portion, and the refrigerant injection from the separation tube refrigerant injection means radially the method of concentration and separation according to any one of claims 7-10, characterized in that a step. In the step of changing the temperature of the separation tube stepwise, the separation tube is heated by the separation tube radiant heating means and the refrigerant is injected by the separation tube refrigerant injection means and held at 100 ° C. for 3 minutes, Next, the separation tube is heated by the separation tube radiant heating means for 10 seconds to increase the temperature by 50 ° C., and the refrigerant is injected by the separation tube refrigerant injection means, and the temperature after the temperature increase is maintained for 2 minutes. The temperature of the separation tube is controlled by the temperature control means so as to increase the temperature by 50 ° C. and finally increase the temperature to 400 ° C. 12. The concentration separation method described in 1.

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