WO2020013005A1 - Matériau de détection de gaz - Google Patents

Matériau de détection de gaz Download PDF

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Publication number
WO2020013005A1
WO2020013005A1 PCT/JP2019/026072 JP2019026072W WO2020013005A1 WO 2020013005 A1 WO2020013005 A1 WO 2020013005A1 JP 2019026072 W JP2019026072 W JP 2019026072W WO 2020013005 A1 WO2020013005 A1 WO 2020013005A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas
gas detection
detection material
glass
porous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2019/026072
Other languages
English (en)
Japanese (ja)
Inventor
雅人 辻口
丸尾　容子
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Electric Glass Co Ltd
Tohoku Institute of Technology
Original Assignee
Nippon Electric Glass Co Ltd
Tohoku Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2019019353A external-priority patent/JP7301284B2/ja
Application filed by Nippon Electric Glass Co Ltd, Tohoku Institute of Technology filed Critical Nippon Electric Glass Co Ltd
Priority to US17/042,249 priority Critical patent/US20210047229A1/en
Priority to CN201980031916.4A priority patent/CN112119305B/zh
Publication of WO2020013005A1 publication Critical patent/WO2020013005A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/59—Transmissivity
    • 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
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/483—Physical analysis of biological material
    • G01N33/497—Physical analysis of biological material of gaseous biological material, e.g. breath

Definitions

  • the present invention relates to a gas detection material.
  • Lung cancer is one of the highest mortality cancers. This is because it is difficult to detect lung cancer early with chest x-ray, which is the current main examination method. Therefore, a method of diagnosing lung cancer at an early stage by analyzing a component that specifically increases in lung cancer patients from exhaled breath is being studied.
  • Non-Patent Document 1 the result of analyzing the breath of a lung cancer patient using a gas chromatography mass spectrometer (GC-MS) and disclosing the result that an aldehyde-based gas such as nonanal is contained at a higher concentration than a healthy person is disclosed.
  • GC-MS gas chromatography mass spectrometer
  • GC-MS is problematic in that it is large-scale and very expensive, and it takes a long time for analysis.
  • the present invention has been made in view of such circumstances, and has as its object to provide a gas detection material which is small and inexpensive and can detect an aldehyde-based gas.
  • the gas detection material of the present invention is preferably a porous glass in which the porous body contains 85 to 100% of SiO 2 by mass%.
  • the gas detection agent preferably contains vanillin and / or a derivative of vanillin.
  • a small and inexpensive gas detection material capable of detecting an aldehyde-based gas can be provided.
  • the gas detection material of the present invention has a porous body having pores, an alkaline compound, and a gas detection agent. Both the alkaline compound and the gas detector are supported in the pores of the porous body.
  • B 2 O 3 / SiO 2 is preferably from 0.3 to 0.5, 0.35 to 0.48, 0.38 to 0.46, particularly preferably 0.4 to 0.45. If B 2 O 3 / SiO 2 is too small, internal stress is likely to be generated in the step of removing the SiO 2 colloid with an alkaline aqueous solution described later, so that the porous glass is likely to be cracked. On the other hand, if B 2 O 3 / SiO 2 is too large, the mechanical strength tends to decrease in the step of removing the SiO 2 colloid with an alkaline aqueous solution described later, so that the porous glass is likely to crack. “B 2 O 3 / SiO 2 ” indicates a value obtained by dividing the content of B 2 O 3 by the content of SiO 2 .
  • ZnO is a component that increases the ZrO 2 content in the silica-rich phase and improves weather resistance.
  • the content of ZnO is preferably 0 to 20%, 0 to 10%, particularly preferably 0 to less than 3%. If the content of ZnO is too large, phase separation becomes difficult.
  • the obtained glass base material preferably has an aspect ratio of 2 to 1000, particularly preferably 5 to 500. If the aspect ratio is too small, in the step of removing the boron oxide-rich phase with an acid to be described later, a large difference appears in the speed of removing the boron oxide-rich phase between the surface and the inside of the glass base material. The porous glass is easily broken. On the other hand, if the aspect ratio is too large, handling becomes difficult.
  • the aspect ratio is calculated by the following equation.
  • the bottom area and the thickness of the obtained glass base material may be appropriately adjusted so as to have the above aspect ratio.
  • the bottom area is preferably 1 to 1000 mm 2 , particularly preferably 5 to 500 mm 2
  • the thickness is preferably 0.1 to 1 mm, particularly preferably 0.2 to 0.5 mm.
  • the SiO 2 colloid can be removed with, for example, an alkaline aqueous solution.
  • an alkali sodium hydroxide, potassium hydroxide and the like can be used. Note that these alkalis may be mixed and used.
  • the immersion time of the alkaline aqueous solution is preferably 10 minutes or more, particularly preferably 30 minutes or more. If the immersion time is too short, it becomes difficult to remove the SiO 2 colloid.
  • the upper limit of the immersion time is not particularly limited, but is practically 100 hours or less.
  • the immersion temperature is preferably 15 ° C. or higher, particularly preferably 20 ° C. or higher. If the immersion temperature is too low, it becomes difficult to remove the SiO 2 colloid.
  • the upper limit of the immersion temperature is not particularly limited, but is actually 95 ° C. or less.
  • the obtained porous glass preferably contains 85 to 100% of SiO 2 by mass%.
  • Al 2 O 3 , ZrO 2 and the like may be contained.
  • an alkaline compound and a gas detector are mixed with a solvent such as water to obtain a mixed solution containing the alkaline compound and the gas detector.
  • the concentration of the alkaline compound in the mixture is preferably 0.1 to 10N, more preferably 0.25 to 5N. If the concentration of the alkaline compound is too low, the reaction between the gas and the gas detector may not proceed sufficiently. On the other hand, if the concentration of the alkaline compound is too high, it tends to react with the porous body, and the mechanical strength of the porous body may be reduced.
  • the porous body is immersed in the obtained mixed solution to obtain a gas detection material in which the pores of the porous body carry the alkaline compound and the gas detection agent. It is preferable that 0.01 g to 10 kg (preferably 10 g to 10 kg) of the porous body is dipped in 0.01 to 100 L (preferably 0.1 to 10 L) of the mixed solution, and the dipping time is 1 hour. It is preferably from minutes to 50 hours. After the porous body is immersed, moisture may be volatilized by natural drying or the like.
  • the support of the alkaline compound and the gas detecting agent may be carried out by immersing the porous body in the mixed solution a plurality of times.
  • concentration of the alkaline compound in the mixed solution is increased as the stage after the immersion step.
  • a porous body is first immersed in a mixture of an alkaline compound and a gas detector at a concentration of 0.01 to 0.5N, and then a mixture of an alkaline compound and a gas detector at a concentration of 0.1 to 10N. It is preferable to immerse in the water.
  • the alkaline compound and the gas detector may be separately loaded.
  • a gas detector is mixed with a dispersion medium such as water to obtain a gas detector dispersion.
  • a porous body carrying the gas detection agent is obtained.
  • the alkaline compound is mixed with a solvent such as water to obtain an alkaline compound solution.
  • a gas detecting material supporting the gas detecting agent and the alkaline compound is obtained.
  • the absorbance of the gas detection material at a specific wavelength is measured by a spectrophotometer or the like.
  • the gas detection material is placed in a tetra bag or the like in which the measurement gas is sealed, and left for 1 minute to 5 hours to expose the measurement gas to the gas detection material.
  • the gas detection material after exposure may be heated at 50 to 200 ° C. for 5 minutes to 1 hour.
  • the absorbance at a specific wavelength of the gas detection material after the exposure is measured by a spectrophotometer or the like. If the absorbance of the gas detection material is different from the absorbance of the gas detection material previously measured, the measurement gas contains an aldehyde-based gas. Become. If a calibration curve is prepared using a standard gas having a known amount of the aldehyde-based gas in advance, the amount of the aldehyde-based gas can be determined from the difference in absorbance of the gas detection material before and after exposure.
  • Example 1 Preparation of porous glass
  • raw materials prepared so as to have a glass composition of 53% by mass of SiO 2 , 23% of B 2 O 3 , 7% of Na 2 O, 6% of ZrO 2 , 3% of Al 2 O 3 , and 8% of CaO by mass%.
  • After putting in a platinum crucible it was melted at 1400 ° C. for 6 hours.
  • the mixture was stirred using a platinum stirrer to homogenize.
  • the molten glass was poured out onto a carbon plate, formed into a plate shape, and then gradually cooled at 500 ° C. for 30 minutes to obtain a glass base material.
  • the obtained glass base material was heat-treated at 675 ° C. for 72 hours in an electric furnace to separate phases.
  • the glass base material after the phase separation was cut and polished to 5 mm ⁇ 5 mm ⁇ 0.5 mm (thickness).
  • the film was immersed in 1 N nitric acid (90 ° C.) for 48 hours, and then immersed in 3 N sulfuric acid (90 ° C.) for 48 hours. Then, it was washed with ion-exchanged water to obtain a porous glass.
  • the composition of the obtained porous glass was 93% of SiO 2 , 4% of ZrO 2 , and 3% of Al 2 O 3 by mass%, and the median diameter of the pore distribution was 80 nm.
  • the light transmittance at a wavelength of 400 nm and a thickness of 0.5 mm was 0.1%.
  • composition was measured with an energy dispersive X-ray analyzer (EX-250 manufactured by Horiba, Ltd.).
  • UV-3100 manufactured by Shimadzu Corporation
  • the gas detection material was placed in a tetrabag filled with a gas containing 2.5 ppm of nonanal and left for 4 hours to expose the gas to the gas detection material.
  • the exposed gas detection material was heated at 100 ° C. for 20 minutes.
  • the absorbance of the heated gas detection material at a wavelength of 420 nm was measured with a spectrophotometer.
  • the absorbance was 4.5, which was 0.3 larger than the absorbance before exposure.
  • the absorbance after gas exposure was higher than that before exposure. The value was increased by about 0.1 in comparison. From this, it was found that nonanal can be detected on the order of ppm.
  • Example 2 Preparation of porous glass
  • the glass base material produced in the same manner as in Example 1 was heat-treated at 675 ° C. for 36 hours in an electric furnace to separate phases.
  • the glass base material after the phase separation was subjected to cutting, polishing, acid treatment, and washing with ion-exchanged water in the same manner as in Example 1 to obtain a porous glass.
  • the obtained porous glass had a skeleton structure based on spinodal phase separation, and the median diameter of the pore distribution was 50 nm.
  • the light transmittance at a wavelength of 400 nm and a thickness of 0.5 mm was 1%.
  • 1 g of the porous glass is immersed in 100 ml of a mixed solution having a sodium hydroxide concentration of 0.5 N for 2 hours, and then left in the air for 24 hours to evaporate water. Soaked in sodium solution for 2 hours. Thereafter, the porous glass was allowed to stand in the air for 24 hours to evaporate water, thereby obtaining a gas detection material.
  • the absorbance of the gas detection material at a wavelength of 420 nm was measured with a spectrophotometer (UV-3100, manufactured by Shimadzu Corporation), and the absorbance was 3.1.
  • the gas detection material was placed in a tetrabag filled with a gas containing 2.5 ppm of nonanal and left for 4 hours to expose the gas to the gas detection material.
  • the exposed gas detection material was heated at 100 ° C. for 20 minutes.
  • the gas detection material of the present invention is suitable for a wide range of applications such as breath diagnosis, skin gas measurement, bad breath checker, environmental monitoring, and work environment management.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • General Physics & Mathematics (AREA)
  • General Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Analytical Chemistry (AREA)
  • Molecular Biology (AREA)
  • Biophysics (AREA)
  • Glass Compositions (AREA)

Abstract

L'invention concerne un matériau de détection de gaz qui est de petite taille et peu coûteux, et qui peut détecter un gaz à base d'aldéhyde. Un matériau de détection de gaz est caractérisé en ce qu'il comprend un corps poreux ayant des pores, un composé alcalin transporté dans les pores, et un agent de détection de gaz.
PCT/JP2019/026072 2018-07-13 2019-07-01 Matériau de détection de gaz Ceased WO2020013005A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US17/042,249 US20210047229A1 (en) 2018-07-13 2019-07-01 Gas detection material
CN201980031916.4A CN112119305B (zh) 2018-07-13 2019-07-01 气体检测材料

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2018-132856 2018-07-13
JP2018132856 2018-07-13
JP2019019353A JP7301284B2 (ja) 2018-07-13 2019-02-06 アルデヒド系ガス検出用材料及びノナナールガス検出用材料
JP2019-019353 2019-02-06

Publications (1)

Publication Number Publication Date
WO2020013005A1 true WO2020013005A1 (fr) 2020-01-16

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Application Number Title Priority Date Filing Date
PCT/JP2019/026072 Ceased WO2020013005A1 (fr) 2018-07-13 2019-07-01 Matériau de détection de gaz

Country Status (1)

Country Link
WO (1) WO2020013005A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022014268A1 (fr) * 2020-07-13 2022-01-20 日本電気硝子株式会社 Élément en verre poreux

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS545792A (en) * 1977-06-10 1979-01-17 Warren Teed Lab Measurement of aromatic amino caboxylic acid
JP2003254959A (ja) * 2001-12-26 2003-09-10 Wako Pure Chem Ind Ltd 新規なホルムアルデヒド測定用キット
JP2005274288A (ja) * 2004-03-24 2005-10-06 Tokai Univ ホルムアルデヒドの検知方法および検知材料
JP2010261811A (ja) * 2009-05-07 2010-11-18 Nippon Telegr & Teleph Corp <Ntt> ガス測定装置および方法
JP2012076988A (ja) * 2010-09-06 2012-04-19 Hyogo Prefecture イオン伝導性薄膜材料及びその製造方法
JP2012525832A (ja) * 2009-05-07 2012-10-25 ウニヴェルシダド デ サラゴサ 微生物検出用のスマート包装
JP2018035025A (ja) * 2016-08-30 2018-03-08 国立研究開発法人産業技術総合研究所 多孔質ガラス材料

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS545792A (en) * 1977-06-10 1979-01-17 Warren Teed Lab Measurement of aromatic amino caboxylic acid
JP2003254959A (ja) * 2001-12-26 2003-09-10 Wako Pure Chem Ind Ltd 新規なホルムアルデヒド測定用キット
JP2005274288A (ja) * 2004-03-24 2005-10-06 Tokai Univ ホルムアルデヒドの検知方法および検知材料
JP2010261811A (ja) * 2009-05-07 2010-11-18 Nippon Telegr & Teleph Corp <Ntt> ガス測定装置および方法
JP2012525832A (ja) * 2009-05-07 2012-10-25 ウニヴェルシダド デ サラゴサ 微生物検出用のスマート包装
JP2012076988A (ja) * 2010-09-06 2012-04-19 Hyogo Prefecture イオン伝導性薄膜材料及びその製造方法
JP2018035025A (ja) * 2016-08-30 2018-03-08 国立研究開発法人産業技術総合研究所 多孔質ガラス材料

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DOI, vol. 240, 1992, pages 382 - 388, DOI: 10.11451/mukimate1953 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022014268A1 (fr) * 2020-07-13 2022-01-20 日本電気硝子株式会社 Élément en verre poreux
JPWO2022014268A1 (fr) * 2020-07-13 2022-01-20
CN115461314A (zh) * 2020-07-13 2022-12-09 日本电气硝子株式会社 多孔玻璃材料
JP7741479B2 (ja) 2020-07-13 2025-09-18 日本電気硝子株式会社 多孔質ガラス部材

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