JP2019132814A - Adsorber, concentrator, and detection device - Google Patents

Abstract

To provide: an adsorber which has a granular adsorbent therein and yet is easy to handle; a concentrator equipped with such adsorber; and a detection device equipped with such adsorber.SOLUTION: An adsorber 1 comprises a gas-permeable base material 12, and a granular adsorbent 10 immobilized on the base material 12.SELECTED DRAWING: Figure 1

Description

  The present invention generally relates to an adsorber, a concentrator, and a detection device, and particularly relates to an adsorber including an adsorbent that adsorbs a chemical substance, a concentrator including the adsorber, and a detection device including the adsorber.

  The adsorbent that adsorbs a chemical substance is used for the purpose of collecting the chemical substance in analyzing the chemical substance in the gas, for example.

  As an example of the adsorbent, there is an aggregate in which nanowires are bundled (see Patent Document 1).

International Publication No. 2014/047041

  Advantages of the aggregate of nanowires include high adsorbability due to a large specific surface area and good handleability due to the aggregate.

  On the other hand, the particulate adsorbent can be manufactured more easily than nanowires. However, it is difficult to fix the particulate adsorbent, so that the particulate adsorbent is less handleable than the nanowire aggregate.

  An object of the present invention is to provide an adsorber with good handleability, a concentrator provided with this adsorber, and a detection device provided with this adsorber, despite having a particulate adsorbent.

  An adsorber according to one embodiment of the present invention includes a base material having gas permeability and a particulate adsorbent fixed to the base material.

  The concentrator which concerns on 1 aspect of this invention is equipped with a concentration chamber and the said adsorption device arrange | positioned in the said concentration chamber.

  A detection apparatus according to an aspect of the present invention includes the adsorber and a sensor unit that detects a chemical substance adsorbed by the adsorber and outputs a signal corresponding to the chemical substance.

  According to one aspect of the present invention, it is possible to provide an adsorber with good handleability, a concentrator provided with this adsorber 1, and a detection device provided with this adsorber, despite having a particulate adsorbent.

FIG. 1 is a schematic cross-sectional view showing an adsorber and a concentrator according to an embodiment of the present invention. FIG. 2 is a perspective view showing the concentrator. FIG. 3 is a block diagram showing a configuration for controlling the concentrator. FIG. 4 is a cross-sectional view showing a modification of the above-described concentrator. FIG. 5 is a cross-sectional view showing a modification of the above-described concentrator. FIG. 6 is a cross-sectional view showing a modification of the above-described concentrator. FIG. 7 is a schematic perspective view showing a detection apparatus including the concentrator. FIG. 8 is a scanning electron micrograph of the cross section of Sample 1 obtained in the example. FIG. 9 is a scanning electron micrograph of the cross section of Sample 2 obtained in the example. FIG. 10 is a scanning electron micrograph of the cross section of Sample 3 obtained in the example. FIG. 11 is a graph showing a part of the chromatogram of Sample 1, Sample 2 and Sample 3 obtained in the example. FIG. 12 is a graph showing a part of the chromatogram of Sample 1, Sample 2 and Sample 3 obtained in the example. FIG. 13 is a graph showing a part of the chromatogram of Sample 1, Sample 2 and Sample 3 obtained in the example.

  Hereinafter, an embodiment of the present invention will be described.

  First, the adsorber 1 will be described with reference to FIGS. 1 and 2. The adsorber 1 according to the present embodiment includes a base material 12 having gas permeability and a particulate adsorbent 10 fixed to the base material 12. The adsorbent 10 is fixed to the base material 12 by being embedded in the base material 12, for example. In this case, a part of the adsorbent 10 may be buried in the base material 12 instead of the entire adsorbent 10. The adsorbent 10 may be fixed to the base material 12 by adhering to the base material 12.

  Since the adsorber 1 includes the particulate adsorbent 10, the adsorber 1 is fixed in the base material 12 so that the adsorber 1 does not scatter. For this reason, the handleability of the adsorber 1 is good. Furthermore, when the adsorber 1 is exposed to gas, the base material 12 can pass the gas and reach the adsorbent 10. Therefore, even though the adsorbent 10 is fixed to the base material 12, the adsorption performance of the adsorbent 10 is not easily impaired.

  The configuration of the adsorber 1 will be described more specifically.

  The base material 12 fixes the adsorbent 10 as described above. The base material 12 is solid and may have any shape as long as it has gas permeability.

If the material of the base material 12 has gas permeability, there will be no restriction | limiting in particular. The base material 12 contains, for example, a resin having gas permeability. Having gas permeability is determined based on common general technical knowledge. In the adsorber 1, even if the adsorbent 10 is covered with the base material 12, if it can be confirmed that the adsorbent 10 adsorbs a chemical substance, it can be determined that the base material 12 has gas permeability. The gas permeability of the resin can be evaluated by the value of the free volume of the resin, for example. The free volume of the resin is measured by the positron annihilation method. The relationship between free volume and gas permeability will be described. The free volume of polydimethylsiloxane is about 0.2 nm ³ . The diameter of a sphere having a volume of 0.2 nm ³ is about 0.74 nm and is approximately equal to the size of the benzene ring. For this reason, polydimethylsiloxane is a porous body that can permeate molecules having a benzene ring, and therefore can be evaluated as having particularly good gas permeability. That is, if the free volume is equal to or greater than 0.2 nm ³ , it can be evaluated that the gas has particularly good gas permeability. The free volume of the resin contained in the base material 12 is preferably 0.1 nm ³ or more.

  The base material 12 contains, for example, at least one of a hydrophobic resin and a hydrophilic resin as a resin having gas permeability.

  When the base material 12 contains a hydrophobic resin, that is, when the base material 12 has a portion containing a hydrophobic resin (hereinafter referred to as a hydrophobic portion), the adsorption performance of the adsorbent 10 in the hydrophobic portion is Less susceptible to moisture. This is considered to be because the hydrophobic resin particularly impedes the permeation of moisture in the base material 12. Hydrophobic chemicals include, for example, compounds with LogP (octanol-water partition coefficient) values greater than 0, such as isopropyl alcohol (LogP = 0.05), phenol (LogP = 1.46), benzaldehyde (LogP). = 1.48), indole (LogP = 2.14), and the like. The hydrophobic portion may be a part of the base material 12 or the entire base material 12.

In addition, it is prescribed | regulated based on technical common sense that hydrophobic resin has hydrophobicity. In particular, the contact angle with water in the hydrophobic resin is preferably 80 ° or more. The contact angle is more preferably 100 ° or more, and even more preferably 100 ° or more and 170 ° or less. In addition, the contact angle of water is measured according to JIS R3257: 1999. Examples of hydrophobic resins are polydimethylsiloxane (water contact angle 130-170 °, free volume about 0.2 nm ³ ), polyisobutylene (water contact angle 100-120 °), paraffin (water contact angle 100-110 °). , Hexatriacontane (water contact angle 100-110 °), nylon (water contact angle 80-100 °), and polycarbonate (water contact angle 80-90 °).

  Even when the base material 12 contains a hydrophilic resin, that is, when the base material 12 has a portion containing a hydrophilic resin (hereinafter referred to as a hydrophilic portion), the adsorption performance of the adsorbent 10 in the hydrophilic portion is gas. It can be expected to be less affected by moisture in the inside. Examples of hydrophilic chemicals include compounds having an octanol-water partition coefficient (LogP) value less than 0, such as formic acid (LogP = −0.54), acetic acid (LogP = −0.17), and the like. . The hydrophilic portion may be a part of the base material 12 or the entire base material 12.

  In addition, it is prescribed | regulated based on technical common sense that hydrophilic resin has hydrophilicity. In particular, the contact angle with water in the hydrophilic resin is preferably 100 ° or less. The contact angle is more preferably 80 ° or less, and even more preferably 70 ° or less. Examples of hydrophilic resins are polyethylene glycol (water contact angle 5 to 20 °), polyvinyl alcohol (water contact angle 40 to 60 °), polyamide resin (water contact angle 40 to 80 °), acrylic resin (water contact angle 60). ~ 80 °) and epoxy resin (water contact angle 70-80 °).

  The base material 12 may have both a hydrophobic part and a hydrophilic part. In this case, among the adsorbents 10 in the adsorber 1, the adsorbent 10 in the hydrophobic portion adsorbs the hydrophobic chemical substance efficiently, and the influence of moisture on the adsorption performance is particularly reduced, so that the hydrophilic portion has A certain adsorbent 10 adsorbs hydrophilic chemical substances efficiently. Thereby, various chemical substances can be adsorbed by one adsorber 1.

  The adsorbent 10 has a property of adsorbing a chemical substance when in contact with the chemical substance and desorbing the chemical substance when heated. The adsorbent 10 is particulate as described above.

As long as the adsorbent 10 has a property of adsorbing at least one kind of chemical substance, the material is not limited. The adsorbent 10 is made of, for example, a metal such as SnO ₂ , ZnO, In ₂ O ₃ , In _2−x Sn _x O ₃ (for example, 0.1 ≦ x ≦ 0.2), NiO, CuO, TiO ₂ , and SiO _2. It contains oxides, metals such as Al, Ag, Au, Pd, and Pt, carbon, or silicon. When the adsorbent 10 contains carbon, the adsorbent 10 is, for example, a carbon nanotube.

  The adsorbent 10 may include a core and a shell that is a film covering the core. In this case, it is preferable that the shell has a property of adsorbing at least one kind of chemical substance. The core may contain a metal oxide, metal, carbon, or silicon as described above, or may contain a resin. The shell contains, for example, the metal oxide as described above.

  The adsorption characteristics of the adsorbent 10 depend on the material of the adsorbent 10, specifically, the material of the entire adsorbent 10 or the material of the shell. That is, the type of chemical substance adsorbed on the adsorbent 10 can be changed by changing the material of the entire adsorbent 10 or the material of the shell.

  The adsorbent 10 is preferably nano-sized. The average particle diameter of the adsorbent 10 is, for example, not less than 10 nm and not more than 5000 nm. The average particle size is preferably 10 nm or more, and preferably 1000 nm or less. In addition, the average particle diameter in this invention means the number average value of the particle size calculated | required from the electron micrograph. Specifically, the average particle diameter is obtained by calculating the diameter of each particle in terms of a perfect circle from the particle area obtained by image processing of an electron micrograph, and obtaining the average value. When the adsorbent 10 has such dimensions, the adsorbent 10 can have high adsorption performance by having a high specific surface area.

  As described above, the adsorbent 10 is fixed to the base material 12 by being buried in the base material 12 and being carried on the base material 12 or attached to the base material 12, for example.

  When the adsorbent 10 is embedded in the base material 12, the adsorbent 10 is dispersed in at least a part of the base material 12, for example. When the adsorbent 10 is dispersed, the adsorbent 10 can exhibit good adsorbability. In this case, the adsorbent 10 may be dispersed throughout the base material 12 or may be dispersed only partially in the base material 12. In the portion of the base material 12 where the adsorbent 10 is present, the concentration of the adsorbent 10 may be uniform or non-uniform.

  At least some of the adsorbents 10 may be connected by contacting each other. When at least some of the adsorbents 10 are connected to each other by being in contact with each other, the heat transfer between the particles of the adsorbent 10 is efficient when heating to desorb the chemical substance from the adsorbent 10. Well done. In addition, when the adsorbent 10 is heated by causing Joule heat to flow through the adsorbent 10, the particles of the adsorbent 10 can form a current path. For this reason, the heating efficiency of the adsorbent 10 is good.

  The adsorbent 10 can include particles of an appropriate shape such as spherical particles, needle-like particles, scale-like particles, irregularly shaped particles, and crushed particles. The acicular particles may also include particles called fibrous particles, whiskers, whiskers, rods, rods, and the like.

  In particular, when the adsorbent 10 includes acicular particles, the adsorbent 10 can have high adsorption performance. Furthermore, the acicular particles are likely to come into contact with each other. For this reason, the acicular particles are likely to be connected by contacting each other. Therefore, it is easy to increase the heating efficiency of the adsorbent 10. When the adsorbent 10 includes acicular particles, the dimensions of the acicular particles are preferably, for example, an average diameter of 10 nm or more and 1000 nm or less, an average length of 1 μm or more and 100 μm or less, and an average aspect ratio of 5 or more and 1000 or less. This dimension can be obtained by measuring the distance between the outer edge of the particle by two parallel lines by image processing of an electron micrograph.

  The amount of the adsorbent 10 in the adsorber 1 can be appropriately designed so that the adsorber 1 has appropriate adsorption performance. The amount of the adsorbent 10 is, for example, 1 w / w% or more and 80 w / w% or less with respect to the weight of the entire gas-permeable resin in the gas permeable layer 12.

  In manufacturing the adsorber 1 according to the present embodiment, for example, first, an appropriate base 13 and a raw material liquid containing the raw material of the base material 12 and the adsorbent 10 are prepared. The shape and material of the base 13 are not limited as long as the base 13 can fix the adsorber 1. The raw material of the base material 12 in the raw material liquid includes, for example, a resin raw material having gas permeability. The raw material for the gas permeable resin may be the gas permeable resin itself or a compound that reacts to become a gas permeable resin. The raw material liquid may further contain a solvent. When the raw material liquid contains a solvent, the viscosity of the raw material liquid can be adjusted with the solvent, and when the resin raw material having gas permeability is solid, the resin raw material having gas permeability is dissolved in the solvent. Can be made liquid. The solvent is not particularly limited as long as it has high volatility and does not easily react with the raw material of the base material 12. The solvent is, for example, toluene.

  The raw material liquid is deposited on the substrate 13 by an appropriate method such as a spin coating method. Then, the solvent in the raw material liquid is volatilized by heating the raw material liquid as necessary. Furthermore, if necessary, the raw material for the gas-permeable resin is reacted by an appropriate method according to the type of the raw material for the gas-permeable resin. Thereby, the adsorber 1 can be manufactured.

  The adsorber 1 may be manufactured by an appropriate method other than the above. For example, the adsorber 1 may be manufactured by mold-molding a raw material composition containing a resin raw material having gas permeability and the adsorbent 10.

  Next, the concentrator 2 including the adsorber 1 will be described with reference to FIGS. 1 and 2. The concentrator 2 includes a concentrating chamber 21 and an adsorber 1 disposed in the concentrating chamber 21. When using the concentrator 2, for example, the chemical substance in the sample gas is adsorbed to the adsorber 1 while supplying a gas containing a chemical substance (hereinafter also referred to as a sample gas) into the concentrating chamber 21. Subsequently, the chemical substance is desorbed from the adsorber 1 and discharged into the concentration chamber 21. As a result, a gas whose chemical concentration is higher than that of the sample gas (hereinafter, also referred to as adjustment gas) can be generated in the concentration chamber 21. Examples of sample gases are human and animal exhalation, and car and factory exhaust. Examples of chemical substances are ketones, amines, alcohols, aromatic hydrocarbons, aldehydes, esters, organic acids, volatile organic compounds such as methyl mercaptan, disulfide, and hydrogen sulfide, sulfur dioxide, carbon disulfide. Inorganic compounds such as

  The adsorber 1 preferably includes a heater for heating the adsorbent 10. The adsorber 1 may further include a cooler 25 that cools the adsorbent 10. When the adsorber 1 includes a heater, the chemical substance can be easily desorbed from the adsorbent 10 by heating the adsorbent 10 that has adsorbed the chemical substance with the heater. Furthermore, when the adsorber 1 includes the cooler 25, the adsorbent 10 can be quickly returned to a state in which the chemical substance can be adsorbed by cooling the heated adsorbent 10 with the cooler 25.

  When the adsorbent 10 has conductivity, the concentrator 2 may include a first electrode 221 and a second electrode 222 that are electrically connected to the adsorbent 10 instead of including a heater. In this case, when a voltage is applied between the first electrode 221 and the second electrode 222, the adsorbent 10 is heated by generating Joule heat.

  Hereinafter, an example of a specific configuration of the adsorber 1 when the adsorber 1 includes the first electrode 221, the second electrode 222, and the cooler 25 will be described.

  The concentrator 2 has a housing 23 and a concentrating chamber 21 in the housing 23. The housing 23 includes an arrangement surface 24 that is one surface facing the concentration chamber 21. The adsorber 1 is arranged on the arrangement surface 24 in the concentration chamber 21. The housing 23 is provided with a first electrode 221 and a second electrode 222 that are separated from each other. Each of the first electrode 221 and the second electrode 222 is electrically connected to the adsorbent 10 by being in contact with the adsorbent 10. A cooler 25 is provided in the vicinity of the arrangement surface 24 of the housing 23.

  More specifically, the housing 23 is made of, for example, resin. The housing 23 includes a first substrate 231 and a second substrate 232. The second substrate 232 has a groove. Since the first substrate 231 is overlapped on the surface of the second substrate 232 where the groove is provided, the space in the groove constitutes the concentration chamber 21. The housing 23 includes an inlet 26 that passes through the inside of the concentrating chamber 21 and the outside of the concentrating chamber 21, and an outlet 27 that passes through the inside of the concentrating chamber 21 and the outside of the concentrating chamber 21 and is different from the inlet 26. The inlet 26 and the outlet 27 are opposed to each other with the concentration chamber 21 in between.

  The concentration chamber 21 is configured to be supplied with gas. The concentration chamber 21 is a flow path through which gas can pass, for example. That is, the gas can flow into the concentrating chamber 21 from the outside of the concentrating chamber 21 through the inlet 26, pass through the concentrating chamber 21, and then flow out of the concentrating chamber 21 through the outlet 27. The direction in which the gas in the concentrating chamber 21 circulates, that is, the direction from the inlet 26 to the outlet 27 is also referred to as a flow direction hereinafter.

  The shape of the concentration chamber 21 is a cube or a rectangular parallelepiped. The arrangement surface 24 corresponds to one surface of a cube or a rectangular parallelepiped, and is configured by a bottom surface of a groove in the second substrate 232. In addition, the shape of the concentration chamber 21 is not limited to this.

  As described above, each of the first electrode 221 and the second electrode 222 is provided on the arrangement surface 24 in the concentration chamber 21. At least a part of each of the first electrode 221 and the second electrode 222 is interposed between the arrangement surface 24 and the adsorber 1. The material of each of the first electrode 221 and the second electrode 222 is, for example, gold, copper, platinum, or carbon.

  As described above, the adsorber 1 includes the base material 12 and the particulate adsorbent 10 fixed to the base material 12. The base material 12 is arranged on the arrangement surface 24 in the concentration chamber 21. The base material 12 is in contact with each of the first electrode 221 and the second electrode 222.

  The adsorbent 10 is needle-shaped particles, but may be particles having an appropriate shape such as a spherical shape as already described. The adsorbent 10 is dispersed in the base material 12. In the base material 12, the adsorbents 10 are connected by contacting each other. Further, the adsorbent 10 includes the adsorbent 10 in contact with the first electrode 221 and the adsorbent 10 in contact with the second electrode 222. For this reason, the adsorbent 10 is electrically connected to the first electrode 221 and the second electrode 222, and a current path composed of a series of adsorbents 10 is formed in the adsorber 1. In order to allow a current to flow through the adsorber 1 between the first electrode 221 and the second electrode 222, the electrical resistance value between the first electrode 221 and the second electrode 222 is not less than 10Ω and not more than 1 kΩ. Is preferred.

  The thickness of the adsorber 1, that is, the thickness of the base material 12, is, for example, not less than 0.1 μm and not more than 1000 μm.

  In addition, the structure of the adsorption device 1 demonstrated here is an example, and as already demonstrated, the adsorption device 1 can have a various structure.

  As shown in FIG. 3, a current supply circuit 29 that supplies a current to the adsorbent 10 by applying a voltage between the first electrode 221 and the second electrode 222 to the first electrode 221 and the second electrode 222. Is connected. A controller 28 that controls the current flowing through the adsorbent 10 by controlling the current supply circuit 29 is connected to the current supply circuit 29.

  The controller 28 is composed of, for example, a microcomputer having one or more processors and a memory. In other words, the controller 28 is realized by a computer system having one or more processors and a memory, and the computer system functions as the controller 28 when the one or more processors execute a program stored in the memory. . The program may be recorded in advance in each memory of the controller 28, or may be provided by being recorded on a non-temporary recording medium such as a memory card through an electronic communication line such as the Internet.

  The cooler 25 is provided so as to overlap the outer surface of the second substrate 232 that faces away from the arrangement surface 24. The cooler 25 is composed of, for example, a Peltier element. As shown in FIG. 3, the controller 28 is also connected to the cooler 25. The controller 28 also controls the cooling of the adsorbent 10 by controlling the operation of the cooler 25.

  In addition, the position of the cooler 25 may be anywhere as long as the adsorbent 10 can be cooled. For example, the cooler 25 may be provided on the first electrode 221 or the second electrode 222.

  A method for concentrating chemical substances using the concentrator 2 will be described. The sample gas is sent into the concentration chamber 21. In order to send the sample gas into the concentrating chamber 21, for example, the sample gas flows into the concentrating chamber 21 from the outside of the concentrating chamber 21 through the inlet 26, and further from the inside of the concentrating chamber 21 to the outside of the concentrating chamber 21 through the outlet 27. An air flow is generated in the concentration chamber 21 so as to flow out into the concentration chamber 21. The airflow can be generated using an appropriate airflow generator such as a pump or a fan. When the airflow is generated in this way, the adsorber 1 is exposed to the sample gas, and the adsorbent 10 in the adsorber 1 adsorbs the chemical substance in the sample gas. Since the sample gas in the concentration chamber 21 is sequentially updated by the air flow, the adsorbent 10 can adsorb an amount of chemical substance corresponding to the time of exposure to the sample gas. That is, the adsorbent 10 can adsorb a chemical substance larger than the amount of the chemical substance in the sample gas having the same volume as the concentration chamber 21. Subsequently, the adsorbent 10 is heated. In other words, in the present embodiment, the adsorbent 10 generates heat when the current supply circuit 29 applies a voltage between the first electrode 221 and the second electrode 222. When the concentrator 2 includes a heater, the adsorbent 10 can be heated with the heater. When the adsorbent 10 is heated, the chemical substance adsorbed on the adsorbent 10 is desorbed from the adsorbent 10 and released into the concentration chamber 21. Thereby, the concentration of the chemical substance in the concentration chamber 21 can be higher than the concentration in the sample gas. Thereby, the adjustment gas in which the concentration of the chemical substance is higher than that of the sample gas can be generated in the concentration chamber 21. This adjustment gas is sent out of the concentration chamber 21. If the airflow is still generated in the concentration chamber 21, the adjustment gas can be sent out of the concentration chamber 21 through the outlet 27 by the airflow. When the adsorbent 10 is cooled by the cooler 25 as necessary after the adjustment gas is sent out of the concentration chamber 21, the adsorbent 10 can be quickly returned to a state in which the chemical substance can be adsorbed.

  The concentrator 2 may include a plurality of concentrating chambers 21 and the adsorber 1 disposed in each concentrating chamber 21. In this case, the concentrator 2 may include a single casing 23 including a plurality of concentrating chambers 21, or may include a plurality of casings 23 each including a single concentrating chamber 21. When the concentrator 2 includes a plurality of adsorbers 1, the concentrator 2 includes a first electrode 221 and a second electrode 222 corresponding to each of the plurality of adsorbers 1, or corresponds to each of the plurality of adsorbers 1. A heater can be provided. Further, the concentrator 2 may include a cooler 25 corresponding to each of the plurality of adsorbers 1.

  The modification of the concentrator 2 shown in FIG. 4 includes a plurality of concentrating chambers 21. The plurality of concentration chambers 21 are arranged in parallel so that the flow directions of the plurality of concentration chambers 21 are all in the same direction. One adsorber 1 is arranged in each concentration chamber 21.

  The modification of the concentrator 2 shown in FIG. 5 includes one concentrating chamber 21. A plurality of adsorbers 1 are arranged in the concentration chamber 21. The plurality of adsorbers 1 are arranged in a line along the flow direction of the concentration chamber 21.

  The modification of the concentrator 2 shown in FIG. 6 includes one concentrating chamber 21. A plurality of adsorbers 1 are arranged in the concentration chamber 21. The plurality of adsorbers 1 are arranged in a line along a direction orthogonal to the flow direction of the concentration chamber 21.

  When the concentrator 2 includes a plurality of adsorbers 1, the materials of the adsorbents 10 in the plurality of adsorbers 1 may be different from each other. If the materials of the adsorbents 10 are different from each other, the adsorbents 10 have different adsorption characteristics. Therefore, compared with the case where the adsorbent 10 is only one kind, the concentrator 234 can adsorb more kinds of chemical substances efficiently.

  The detection device 4 including the adsorber 1 will be described.

  The detection device 4 includes an adsorber 1 and a sensor unit 31 that detects a chemical substance adsorbed by the adsorber 1 and outputs a signal corresponding to the chemical substance. The detection device 4 may include the adsorber 1 by including the concentrator 2 described above. When the detection device 4 includes the concentrator 2, the sensor unit 31 can detect a chemical substance in the adjusted gas in which the concentration of the chemical substance is increased. In this case, the detection accuracy of the chemical substance by the detection device 4 can be increased, and for example, it is possible to accurately detect a chemical substance that is contained only in a trace amount in the sample gas.

  FIG. 7 shows an example of the detection device 4. The detection device 4 includes a detector 3 and a concentrator 2. The detector 3 includes a sensor unit 31. The concentrator 2 includes an adsorber 1. The configuration of the concentrator 2 is the same as in FIGS. 1 and 2 are denoted by the same reference numerals as those in FIGS. 1 and 2, and description thereof will be omitted as appropriate.

  The detector 3 has a housing 33 and a detection chamber 32 in the housing 33. The housing 33 is made of resin, for example. The housing 33 includes a passage 34 that allows the inside of the detection chamber 32 and the outside of the detection chamber 32 to pass therethrough. The casing 33 of the detector 3 and the casing 23 of the concentrator 2 are connected so that the passage 34 in the casing 33 of the detector 3 leads to the outlet 27 in the casing 23 of the concentrator 2. Yes. That is, the concentration chamber 21 and the detection chamber 32 communicate with each other through the outlet 27 of the concentrator 2 and the communication port 34 of the detector 3. In this embodiment, the casing 33 of the detector 3 and the casing 23 of the concentrator 2 are separate members, but the casing 23 of the detector 3 and the casing 23 of the concentrator 2 are integrated. One member may be configured.

  The detector 3 preferably includes a discharge port 35 for discharging the gas in the detection chamber 32 from the detection chamber 32. In the present embodiment, a pump that is an airflow generator 36 is connected to the discharge port 35. The pump operates to suck the gas in the detection chamber 32 through the discharge port 35. For this reason, the airflow generator 36 can generate an airflow. This airflow flows from outside the concentrating chamber 21 into the concentrating chamber 21 through the inlet 26 of the concentrator 2, and from the concentrating chamber 21 through the outlet 27 of the concentrator 2 and the outlet 34 of the detector 3. It flows in and flows out of the detection chamber 32 through the discharge port 35. As long as this air flow can be generated, the air flow generator 36 is not limited to a pump, and may be a blower fan, for example.

  When detecting the chemical substance in the gas using the detection device 4, for example, the inlet 26 of the concentrator 2 is first disposed in the sample gas outside the concentration chamber 21. By operating the airflow generator 36 in this state, an airflow is generated in the detection device 4. By this air flow, the sample gas flows from the outside of the concentrating chamber 21 into the concentrating chamber 21 through the inlet 26 of the concentrator 2, and further from the concentrating chamber 21 to the outlet 27 of the concentrator 2 and the outlet of the detector 3. It flows into the detection chamber 32 through 34 and is further discharged out of the detection chamber 32 through the discharge port 35.

  In this state, when the concentrator 2 operates as described above, the adjustment gas is generated in the concentration chamber 21, and the adjustment gas flows into the detection chamber 32. The sensor unit 31 can detect a chemical substance in the adjustment gas flowing into the detection chamber 32 and output a signal corresponding to the chemical substance. In this case, since the concentration of the chemical substance in the adjustment gas can be made higher than that in the sample gas, the detection accuracy of the chemical substance is improved by detecting the chemical substance in the sample gas by the sensor unit 31.

1. Preparation of adsorber 1 1-1 Sample 1
As the adsorbent 10, spherical particles of tungsten oxide (average particle diameter 1 μm) were prepared.

  As a raw material of polydimethylsiloxane which is a hydrophobic resin, a main agent and a curing agent included in SYLGARD 184 SILICONE ELASTOMER KIT were prepared. The main agent and the curing agent were mixed at a mass ratio of 10: 1, and the adsorbent 10 was further mixed to prepare a raw material liquid. The amount of the adsorbent 10 contained in 100 mL of the raw material liquid is 10 g.

  The raw material liquid was deposited on the substrate 13 by spin coating at 4500 rpm for 90 seconds, and then heated at 95 ° C. for 40 minutes to cure the raw material liquid. As a result, a sample 1 having a size of 2 mm in length × 20 mm in width and about 20 μm in thickness as the adsorber 1 was obtained. In FIG. 8, the electron micrograph of the cross section of the sample 1 is shown.

1-2 Sample 2
As the adsorbent 10, copper oxide spherical particles (average particle size: 1 μm) were prepared instead of tungsten oxide spherical particles. The sample 2 which is the adsorption machine 1 was obtained on the same conditions as the case of the sample 1 except that. In FIG. 9, the electron micrograph of the cross section of the sample 2 is shown.

1-3 Sample 3
As the adsorbent 10, tin oxide spherical particles (average particle diameter: 1 μm) were prepared instead of tungsten oxide spherical particles. Except that, sample 3 as adsorber 1 was obtained under the same conditions as in sample 1. In FIG. 10, the electron micrograph of the cross section of the sample 3 is shown.

2. Adsorption test Each sample prepared in “1. Preparation of adsorber 1” was heated at 200 ° C. for 5 minutes and then cooled to room temperature. Subsequently, in a state where the adsorber 1 was placed in the glass tube, human breath previously collected in the glass tube was circulated at a flow rate of 50 mL / min for 20 minutes.

  Then, model number OPTIC4 which is a multifunctional inlet was attached to model GCMS-QP2020 which is a gas chromatograph mass spectrometer manufactured by Shimadzu Corporation. A sample was placed at this multi-function inlet, and the sample was heated at 200 ° C. for 3 minutes to desorb the chemical substance from the sample, and then the chemical substance was injected into the gas chromatograph mass spectrometer to obtain a chromatogram. .

  In the measurement, SH-Rtx-200 MS manufactured by Shimadzu Corporation was used as the column. The column temperature was raised at 40 ° C. for 4 minutes, then raised to 100 ° C. at a rate of 10 ° C./min, and then raised to 260 ° C. at a rate of 20 ° C./min. And then maintained at 260 ° C. for 4 minutes. The conditions of the microjet cryotrap were -100 ° C. and 3 minutes.

3. Test Results According to the chromatogram obtained in the above adsorption test, in any of Sample 1, Sample 2 and Sample 3, a plurality of peaks indicating chemical substances were observed in the chromatogram. For this reason, it was confirmed that Sample 1, Sample 2 and Sample 3 can adsorb plural kinds of chemical substances.

  In order to confirm this tendency in more detail, FIGS. 11, 12, and 13 are presented. FIGS. 11, 12 and 13 show phenol, 5-ethyl-2-methyl-pyridine and germane D ((1E, 6E, 8S) -1-methyl in the chromatograms for Sample 1, Sample 2 and Sample 3, respectively. -5-methylene-8-isopropyl-1,6-cyclodecadiene) peaks are shown respectively. In addition, the arrow in a figure shows the position where each peak appears.

  As shown in FIGS. 11, 12, and 13, the peaks of phenol, 5-ethyl-2-methyl-pyridine, and germane D are observed in the chromatogram in any of Sample 1, Sample 2, and Sample 3. It was.

  Moreover, as shown in FIG. 11, the peak of phenol is strong in the order of sample 1, sample 3, and sample 2. Further, as shown in FIG. 12, the peak of 5-ethyl-2-methyl-pyridine is weaker in the case of sample 1 and in the case of sample 2 than in the case of sample 3, and in the case of sample 1 and sample 2 The intensity of the peak is similar. In addition, as shown in FIG. 13, the peak of germancrene D is stronger in the case of sample 1 and sample 2 than in the case of sample 3, and the peak intensity in the case of sample 1 and sample 2 is the same. Degree.

  According to the above results, the chemical substances that are easily adsorbed differ depending on the type of the adsorbent 10. Therefore, it can be confirmed that the adsorption characteristics of the adsorber 1 can be designed by selecting the type of adsorbent 10 and using a plurality of adsorbents 10.

  The base material 12 in each of the above samples contains polydimethylsiloxane which is a hydrophobic resin. However, even if the resin contained in the base material 12 is a hydrophobic resin other than polydimethylsiloxane and a hydrophilic resin, the same result as the above sample can be expected if the resin has gas permeability.

  Further, when the adsorbent 10 is buried in the base material 12 as in the above sample, when the adsorption performance of the adsorbent 10 is affected by moisture, the base material 12 suppresses the influence of moisture, so that the adsorbent 10 Can be expected to exhibit particularly good adsorption performance.

DESCRIPTION OF SYMBOLS 1 Adsorber 10 Adsorbent 12 Base material 2 Concentrator 21 Concentration chamber 31 Sensor part 4 Detection apparatus

Claims (9)

A base material having gas permeability, and a particulate adsorbent fixed to the base material,
Adsorber. The adsorbent is dispersed in at least a portion of the base material;
The adsorber according to claim 1. The base material has a portion containing a hydrophobic resin,
The adsorber according to claim 1 or 2. The base material has a portion containing a hydrophilic resin,
The adsorber according to any one of claims 1 to 3. The adsorbent contains a metal oxide,
The adsorber according to any one of claims 1 to 4. The adsorbent includes acicular particles,
The adsorber according to any one of claims 1 to 5. At least some of the adsorbents are connected by contacting each other,
The adsorber according to any one of claims 1 to 6. A concentration chamber;
The adsorber according to any one of claims 1 to 7, which is disposed in the concentration chamber.
Concentrator. The adsorber according to any one of claims 1 to 7,
A sensor unit that detects a chemical substance adsorbed by the adsorber and outputs a signal corresponding to the chemical substance;
Detection device.