JP7107494B2 - ガス検出器 - Google Patents
ガス検出器 Download PDFInfo
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- JP7107494B2 JP7107494B2 JP2021507369A JP2021507369A JP7107494B2 JP 7107494 B2 JP7107494 B2 JP 7107494B2 JP 2021507369 A JP2021507369 A JP 2021507369A JP 2021507369 A JP2021507369 A JP 2021507369A JP 7107494 B2 JP7107494 B2 JP 7107494B2
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- 239000007789 gas Substances 0.000 claims description 116
- 239000012528 membrane Substances 0.000 claims description 44
- 229920001197 polyacetylene Polymers 0.000 claims description 40
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 38
- 238000000926 separation method Methods 0.000 claims description 24
- 238000001179 sorption measurement Methods 0.000 claims description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims description 13
- 150000004706 metal oxides Chemical group 0.000 claims description 13
- 239000004065 semiconductor Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- -1 cyclic siloxane Chemical class 0.000 claims description 11
- 125000001424 substituent group Chemical group 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000012466 permeate Substances 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002356 single layer Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000007084 catalytic combustion reaction Methods 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims 1
- 239000010408 film Substances 0.000 description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 231100000572 poisoning Toxicity 0.000 description 5
- 230000000607 poisoning effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 150000002605 large molecules Chemical class 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 238000011045 prefiltration Methods 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229940077085 diagnostic agent for diabetes testing Drugs 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 210000000214 mouth Anatomy 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920003242 poly[1-(trimethylsilyl)-1-propyne] Polymers 0.000 description 1
- 229920001510 poly[2-(diisopropylamino)ethyl methacrylate] polymer Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- OBDBNHMDGCGLPU-UHFFFAOYSA-N trimethyl(prop-1-ynyl)germane Chemical compound CC#C[Ge](C)(C)C OBDBNHMDGCGLPU-UHFFFAOYSA-N 0.000 description 1
- UZRJWRFLYPENFH-UHFFFAOYSA-N trimethyl-[4-(2-phenylethynyl)phenyl]silane Chemical group C1=CC([Si](C)(C)C)=CC=C1C#CC1=CC=CC=C1 UZRJWRFLYPENFH-UHFFFAOYSA-N 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/128—Microapparatus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/108—Inorganic support material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/126—Composition of the body, e.g. the composition of its sensitive layer comprising organic polymers
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
- G01N33/0047—Organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7022—Aliphatic hydrocarbons
- B01D2257/7025—Methane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/06—Polluted air
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/20—Specific permeability or cut-off range
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/229—Integrated processes (Diffusion and at least one other process, e.g. adsorption, absorption)
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Immunology (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Pathology (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Description
・ poly[1-(trimethylsilil)-1-propyne](PTMSP),poly[1-(trimethylgermyl)-1-propyne](PTMGP)など、Si,Ge等のヘテロ原子を(CH3)3Si-,(CH3)3Ge-等の置換基として含むもの。
・ poly[4-(methyl)-2-pentyne](PMP),poly[1,2-diphenyl acetylene](PDPA)など、ヘテロ原子を含まず、かつiso-propyl基,フェニル基などの大きな置換基を含むもの。
・ poly[1,4,5-(CF3)3-phenylacetylene],poly[1,5-(CF3)2-phenylacetylene]など、CF3基を含む大きな置換基を持つもの。
・ poly[1-phenyl-2-[(p-trimethylsilyl)phenyl]acetylene](PTMSDPA)など、(CH3)3Si-,(CH3)3Ge-等の置換基とフェニル基とを含むもの。特にPTMSDPAは、p-トリメチルシリル-フェニル基とフェニル基とを含むので大きな細孔を持ち、検知対象ガスへの透過性と大型の環状シロキサン化合物をブロックする性能の2点で好ましい。
環状シロキサン(D4)1ppmに1時間暴露した前後での、CH4及びH2に対するガスセンサ2の応答の変化を観察した。ガスセンサ2の金属酸化物半導体膜8は膜厚40μmのSnO2膜で、動作条件は30秒毎に0.1秒間、最高加熱温度約430℃まで加熱する間欠加熱である。ガスセンサ2に負荷抵抗を接続し、加熱終了時の金属酸化物半導体8の抵抗値を測定した。多孔質PTFE膜上に膜厚10μm程度のPTMSDPA膜を積層したものをガス分離膜14とし、実施例ではガス分離膜14を設け、比較例ではガス分離膜14の代わりに単なる多孔質PTFE膜を設けた。ガスセンサ数は実施例では3、比較例では2で、検知対象ガスはCH4(図4)及びH2(図5)で、濃度は共に1000-9000ppmである。図4,図5の上段は実施例の結果を、下段は比較例の結果を示す。図4,図5から、ガス分離膜14によりシロキサンの影響を緩和できることが分かる。
置換ポリアセチレン膜は、ガス選択透過膜の中では、自由容積が大きくかつ親油性が高い。膜のガス選択性には、
・ 細孔サイズとガス分子のサイズとの相対的な値による選択性と、
・ 膜内にガス分子が溶解する溶解度、溶解したガス分子の拡散速度による選択性、
の2つの機構が考えられる。細孔サイズを利用する機構では、細孔サイズよりも大きなガス分子は細孔に侵入できないことを利用する。溶解度等を利用する機構では、大きなサイズのガス分子は膜内に溶解した後、比較的大きな細孔にトラップされ、膜内を透過しにくいことを利用する。置換ポリアセチレン膜では、細孔サイズとシロキサン分子のサイズとの違いによる選択性に加え、膜内に溶解したシロキサン分子の拡散が遅いことが寄与している、と考えられる。また置換ポリアセチレン膜では、小さなガス分子はこのような細孔にトラップされず速やかに膜を透過し、ガスセンサの検出速度への影響が小さい。
4 Siチップ
5 キャビテイ
6 支持膜
8 金属酸化物半導体膜
10,24 ベース
11 メタライズ部
12,28 カバー
13,34 通気孔
14 ガス分離膜
25 ピン
26 基板
30 吸着フィルタ
32 多孔質膜
42 スマートフォン
45 ガス導入孔
46 排気孔
48 ガスセンサ
Claims (8)
- 主鎖の2重結合炭素原子に置換基が結合している置換ポリアセチレンから成るガス分離膜と、
ガス分離膜を透過したガスを検出するセンシング要素、とを備え、
前記センシング要素は金属酸化物半導体式あるいは接触燃焼式のセンシング要素であり、
前記ガス分離膜は、環状シロキサンを遮断し、検出対象ガスを透過させるガス検出器。 - ガス分離膜は支持膜の無い単層膜であることを特徴とする、請求項1のガス検出器。
- センシング要素は、ガスにより抵抗値が変化する金属酸化物半導体膜を支持するMEMSチップであることを特徴とする、請求項1または2のガス検出器。
- 人の呼気中の水蒸気をガス分離膜により遮断するように構成されていることを特徴とする、請求項1~3のいずれかのガス検出器。
- 環境中のVOC(揮発性有機物)を検出対象ガスとすることを特徴とする、請求項1~3のいずれかのガス検出器。
- ガス分離膜を透過したガスから、検出対象以外のガスを吸着する吸着フィルタをさらに備えていることを特徴とする、請求項1~3のいずれかのガス検出器。
- ガス分離膜が吸着フィルタの外気側カバーを兼ねていることを特徴とする、請求項6のガス検出器。
- 検出対象ガスがメタンで、前記吸着フィルタにより、エタノール、スチレン及びピネンを吸着することを特徴とする、請求項6のガス検出器。
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JP2019050582 | 2019-03-19 | ||
JP2019050582 | 2019-03-19 | ||
PCT/JP2020/011690 WO2020189675A1 (ja) | 2019-03-19 | 2020-03-17 | ガス検出器 |
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JPWO2020189675A1 JPWO2020189675A1 (ja) | 2020-09-24 |
JPWO2020189675A5 JPWO2020189675A5 (ja) | 2022-01-18 |
JP7107494B2 true JP7107494B2 (ja) | 2022-07-27 |
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US (1) | US20220163474A1 (ja) |
JP (1) | JP7107494B2 (ja) |
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US11977007B2 (en) * | 2019-05-17 | 2024-05-07 | Figaro Engineering Inc. | Gas detection device and gas detection method |
DE102021103897A1 (de) * | 2021-02-18 | 2022-08-18 | Infineon Technologies Ag | Gassensor mit einem hohlraum und einer gasdurchlassstruktur mit einem selektiv gasdurchlässigem element |
IT202200006020A1 (it) * | 2022-03-28 | 2023-09-28 | Airgloss S R L | Cartuccia multigas digitale basata su array di sensori mems ad ossido di metallo per il riconoscimento di pattern relativi alla composizione dell’aria e relativo metodo di stabilizzazione |
WO2024027486A1 (zh) * | 2022-08-02 | 2024-02-08 | 杭州三花研究院有限公司 | 检测组件、传感装置以及传感装置的制造方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2010104045A1 (ja) | 2009-03-09 | 2010-09-16 | 住友化学株式会社 | 重合体 |
WO2010110051A1 (ja) | 2009-03-24 | 2010-09-30 | シャープ株式会社 | 化学物質検出装置 |
JP2013242269A (ja) | 2012-05-22 | 2013-12-05 | Figaro Eng Inc | ガスセンサ |
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