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JP2018058062A - Reducer for organic compounds and water vapor - Google Patents

Reducer for organic compounds and water vapor Download PDF

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JP2018058062A
JP2018058062A JP2017182434A JP2017182434A JP2018058062A JP 2018058062 A JP2018058062 A JP 2018058062A JP 2017182434 A JP2017182434 A JP 2017182434A JP 2017182434 A JP2017182434 A JP 2017182434A JP 2018058062 A JP2018058062 A JP 2018058062A
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air
washing bottle
dew point
zeolite
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JP7142279B2 (en
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菊地　徹
Toru Kikuchi
徹 菊地
信哉 山口
Shinya Yamaguchi
信哉 山口
一男 工藤
Kazuo Kudo
一男 工藤
公太 工藤
Kota Kudo
公太 工藤
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Aomori Yukakogyo Co Ltd
Aomori Prefectural Industrial Technology Research Center
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Aomori Yukakogyo Co Ltd
Aomori Prefectural Industrial Technology Research Center
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Separation Of Gases By Adsorption (AREA)
  • Drying Of Gases (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

【課題】ガス状有機化合物と水蒸気を含む空気から安価、かつ高効率に捕集し、ガス状有機化合物濃度と水蒸気量を同時に低下させることが可能な有機化合物と水蒸気の低減剤を提供する。
【解決手段】有機化合物と水蒸気の低減剤は、モルデナイト型ゼオライト、クリノプチロライト型ゼオライトのうち、少なくとも１つの鉱物を含むゼオライトから成る。ガス状有機化合物と水蒸気を含む空気に、有機化合物と水蒸気の低減剤を接触させたることにより、空気に含まれるガス有機化合物と水蒸気の両方を捕集し、有機化合物濃度と水蒸気量を同時に低下させることができる。
【選択図】図１An organic compound and a water vapor reducing agent that can be collected from air containing a gaseous organic compound and water vapor at low cost and with high efficiency and can simultaneously reduce the concentration of the gaseous organic compound and the amount of water vapor.
An organic compound and a water vapor reducing agent comprise a zeolite containing at least one mineral among a mordenite type zeolite and a clinoptilolite type zeolite. By bringing an organic compound and water vapor reducing agent into contact with air containing a gaseous organic compound and water vapor, both the gas organic compound and water vapor contained in the air are collected, and the organic compound concentration and water vapor amount are simultaneously reduced. Can be made.
[Selection] Figure 1

Description

本発明は、ガス状有機化合物および水蒸気を気体から同時に捕集する技術に係り、ガス状有機化合物および水蒸気の両方を安価、かつ高効率に捕集し、気体のガス状有機化合物濃度および水蒸気量を同時に低下することのできる有機化合物と水蒸気の低減剤に関する。   The present invention relates to a technique for simultaneously collecting a gaseous organic compound and water vapor from a gas, and collects both the gaseous organic compound and water vapor at a low cost and with high efficiency. It is related with the organic compound and water vapor | steam reducing agent which can reduce simultaneously.

塗料、ＦＲＰ樹脂、接着剤等の工業材料や製品の中には、芳香族化合物や脂肪族化合物をはじめ、様々な有機化合物が含まれ、使用する際にそれらの一部がガス状になり、空気中に揮散している。これらの有機化合物の中には、人などの生物が呼吸等により摂取することにより、病気を誘引するものや環境中に放出されることにより生物に悪影響を及ぼすものが多数存在する。   Industrial materials and products such as paints, FRP resins and adhesives contain various organic compounds, including aromatic and aliphatic compounds, and some of them become gaseous when used. Volatilized in the air. Among these organic compounds, there are a large number of those that induce diseases by being ingested by living organisms such as human beings, and those that adversely affect the organisms when released into the environment.

また、私たちの周りに存在する空気に含まれる水蒸気は、冷たいものの表面で水蒸気が凝縮する現象である結露を起こす。ものの表面への結露は、塗装やＦＲＰライニングや他の物体との接着などの施工作業において、施工不良を引き起こす原因となっている。そして、また、水蒸気を多く含む空気は、作業員の体感温度を高くするなど作業員を不快にし、作業効率を低下させる原因の一つになっている。   In addition, water vapor contained in the air around us causes condensation, which is a phenomenon in which water vapor condenses on the surface of cold objects. Condensation on the surface of objects causes construction defects in construction work such as painting, FRP lining, and adhesion to other objects. Further, the air containing a lot of water vapor is one of the causes that make the worker uncomfortable, for example, increase the temperature of the worker's experience, and lower the work efficiency.

これまで、芳香族化合物や脂肪族化合物などのガス状有機化合物の除去・捕集方法として、活性炭等の吸着剤にガス状有機化合物を吸着させる方法があるが、高湿度の環境においては水蒸気がガス状有機化合物の吸着を阻害し、吸着能が低下してしまう問題がある。   Until now, as a method for removing and collecting gaseous organic compounds such as aromatic compounds and aliphatic compounds, there is a method of adsorbing gaseous organic compounds to an adsorbent such as activated carbon. There is a problem that the adsorption of the gaseous organic compound is hindered and the adsorption ability is lowered.

また、これまで、特許文献１に、Ｙ型ゼオライト変性物を用いて水蒸気を除去、捕集する方法が開示されている。
しかし、開示されているY型ゼオライト変性物は、薬品等によるY型ゼオライトの変性工程が必要であり、水蒸気の除去、捕集剤の製造コストが高くなる問題がある。そしてまた、該特許文献は、「有機化合物の除去、捕集」についても、「有機化合物と水蒸気との同時除去、同時捕集」についても、開示もしていないし、示唆もしていない。 In addition, Patent Document 1 discloses a method for removing and collecting water vapor using a modified Y-type zeolite.
However, the disclosed modified Y-type zeolite requires a modification step of the Y-type zeolite with chemicals or the like, and there is a problem that the cost for removing water vapor and the production of the collecting agent is increased. Further, the patent document does not disclose or suggest “removal and collection of organic compounds” or “simultaneous removal and simultaneous collection of organic compounds and water vapor”.

特願２０１４−１３６８４４号公報Japanese Patent Application No. 2014-136844

したがって、本発明の目的は、ガス状の有機化合物および水蒸気を同時に除去、捕集する性能に優れ、かつ安価な有機化合物と水蒸気の低減剤を提供することである。   Accordingly, an object of the present invention is to provide an organic compound and a water vapor reducing agent which are excellent in performance for removing and collecting a gaseous organic compound and water vapor at the same time and are inexpensive.

本発明は上記課題を解決するために鋭意検討を重ねた結果、天然からも産出する、モルデナイト型ゼオライト、クリノプチロライト型ゼオライトのうち、少なくとも１つの鉱物を含むゼオライトの含水率、水素の含有率を制御することにより、ガス状有機化合物を除去、捕集し、かつ同時に水蒸気も除去、捕集するという知見を見出し、本発明に至った。すなわち、上記課題を解決するための手段として本願で特許請求される発明、もしくは少なくとも開示される発明は以下の通りである。   As a result of intensive studies to solve the above-mentioned problems, the present invention naturally produces hydrated zeolite containing at least one mineral among mordenite-type zeolite and clinoptilolite-type zeolite, and contains hydrogen. By controlling the rate, the inventors have found that the gaseous organic compound is removed and collected, and at the same time, the water vapor is removed and collected, and the present invention has been achieved. That is, the invention claimed in the present application as means for solving the above-described problems, or at least the invention disclosed is as follows.

（１） モルデナイト型ゼオライト、クリノプチロライト型ゼオライトのうち、少なくとも１つの鉱物を含むゼオライトであることを特徴とするガス状有機化合物と水蒸気の低減剤。
（２） ガス状芳香族化合物と水蒸気を同時に捕集できることを特徴とする（１）に記載のガス状有機化合物と水蒸気の低減剤。
（３） ガス状脂肪族化合物、ガス状二硫化炭素のうち、少なくとも１つの有機化合物と水蒸気を同時に捕集できることを特徴とする（１）に記載のガス状有機化合物と水蒸気の低減剤。
（４） 含水率が６．２６質量％以下、水素の含有率が０．０３質量％を超えるゼオライトであることを特徴とする、（１）から（３）までのいずれかに記載のガス状有機化合物と水蒸気の低減剤。 (1) A gaseous organic compound and water vapor reducing agent characterized by being a zeolite containing at least one mineral among mordenite type zeolite and clinoptilolite type zeolite.
(2) The gaseous organic compound and water vapor reducing agent according to (1), wherein the gaseous aromatic compound and water vapor can be collected simultaneously.
(3) The gaseous organic compound and water vapor reducing agent according to (1), wherein at least one organic compound and water vapor can be simultaneously collected from the gaseous aliphatic compound and gaseous carbon disulfide.
(4) The gaseous state according to any one of (1) to (3), characterized in that it is a zeolite having a moisture content of 6.26% by mass or less and a hydrogen content exceeding 0.03% by mass. Reducer for organic compounds and water vapor.

なお、本発明の有機化合物とは、芳香族化合物、脂肪族化合物、二硫化炭素である。芳香族化合物とは、ベンゼン環、ピリジン環、ピリダジン環、イミダゾール環、フラン環、チオフェン環、ピロール環、ピラゾール環、ピリミジン環、ピラジン環、アズレン環、シクロペンタジエン環、トロピリウム環、トロポン環を、分子内の骨格に有する有機化合物のことであり、例えば、ベンゼン、エチルベンゼン、クメン、フェノール、ベンジルアルコール、クロロベンゼン、ジクロロベンゼン、トリクロロベンゼン、テトラクロロベンゼン、ペンタクロロベンゼン、ヘキサクロロベンゼン、アニソール、ベンズアルデヒド、トルエン、キシレン、スチレン、安息香酸、ケイ皮酸、アセトフェノン、ベンゼンスルホン酸、ニトロベンゼン、アニリン、チオフェノール、ベンゾニトリル、トルイジン、ジアミノトルエン、トリアミノトルエン、クレゾール、カテコール、レゾルシノール、ヒドロキノン、フタル酸、イソフタル酸、テレフタル酸、サリチル酸、ベンジルアミン、ピリジン、ピリダジン、イミダゾール、フラン、チオフェン、ピロール、ピラゾール、ピリミジン、ピラジン、アズレン、シクロペンタジエン、トロピリウム、トロポン、ナフタレン、ジベンゾフラン、ジベンゾ−ｐ−ジオキシン、ビフェニル、ベンゾフェノン、トリフェニルメタン、フェノールフタレイン、アントラセン、テトラセン、ペンタセン、フェナントレン、クリセン、トリフェニレン、テトラフェン、ピレン、ピセン、ペンタフェン、ペリレン、ヘリセン、コロネンなどがある。脂肪族化合物とは、飽和炭化水素、不飽和炭化水素のことであり、メタノール、エタノール、プロパン−１−オール、ブタン−１−オール、ペンタン−１−オール、ヘキサン−１−オール、ヘプタン−１−オール、オクタン−１−オール、2-メチルプロパン−１−オール（イソブチルアルコール）、3-メチルブタン−１−オール、プロパン−２−オール、ブタン−２−オール、ペンタン−２−オール、ヘキサン−２−オール、ヘプタン−２−オール、２−メチルブタン−１−オール、シクロヘキサノール、２−メチルプロパン−２−オール、２−メチルブタン−２−オール、２−メチルペンタン−２−オール、２−メチルヘキサン−２−オール、２−メチルヘプタン−２−オール、３−メチルペンタン−３−オール、３−メチルオクタン−３−オールなどのアルコール、ホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、ブタナール、ペンタナール、ヘキサナール、ヘプタナール、オクタナール、ノナナール、デカナール、蟻酸、酢酸、アクロレイン、グリオキサールなどのアルデヒド、エタン酸、プロパン酸、ブタン酸、ペンタン酸、ヘキサン酸、ヘプタン酸、オクタン酸、ノナン酸、デカン酸などのカルボン酸、無水酢酸、無水プロピオン酸などのカルボン酸無水物、酸化プロピレン、エピクロロヒドリン、エチレングリコールジグリシジルエーテル、１，４−ブタンジオールジグリシジルエーテルなどのエポキシド、メタン、エタン、プロパン、ブタン、ペンタン、ヘキサン、ヘプタン、オクタン、ノナン、デカン、ウンデカン、ドデカン、テトラデカン、ペンタデカン、ヘキサデカンなどのアルカン、エチレン、プロピレン、ブテン、ペンテン、ヘキセン、ヘプテン、オクテン、ノネン、デセンなどのアルケン、アセチレン、プロピン、ブチン、ペンチンなどのアルキン、シクロプロパン、シクロブタン、シクロペンタン、シクロヘキサン、シクロヘプタン、シクロオクタンなどのシクロアルカン、アセトン、メチルエチルケトン、ジエチルケトン、メチルプロピルケトン、メチルイソブチルケトン、メチルアミルケトン、シクロヘキサノン、イソホロンなどのケトン、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル、酢酸イソブチル、アセト酢酸メチル、アセト酢酸エチル、アセト酢酸プロピル、アセト酢酸ブチル、アセト酢酸イソブチルなどのカルボン酸エステル、クロロメタン、ブロモメタン、フルオロメタン、ジクロロメタン、ジブロモメタン、ジフルオロメタン、クロロホルム、ブロモホルム、フルオロホルム、テトラクロロメタン、テトラブロモメタン、テトラフルオロメタン、クロロエタン、ブロモエタン、フルオロエタン、ジクロロエタン、ジブロモエタン、ジフルオロエタン、トリクロロエタン、トリブロモエタン、トリフルオロエタン、テトラクロロエタン、テトラブロモエタン、テトラフルオロエタン、クロロエチレン、ブロモエチレン、フルオロエチレン、ジクロロエチレン、ジブロモエチレン、ジフルオロエチレン、トリクロロエチレン、トリブロモエチレン、トリフルオロエチレン、テトラクロロエチレン、テトラブロモエチレン、テトラフルオロエチレンなどの有機ハロゲン化合物、ジメチルエーテル、ジエチルエーテルなどのエーテル、１，４−ジオキサン、１，２−ジオキサン、１，３−ジオキサン、Ｎ，Ｎ−ジメチルホルムアミド、オキセタン、テトラヒドロフラン、テトラヒドロピランなどがある。   In addition, the organic compound of this invention is an aromatic compound, an aliphatic compound, and carbon disulfide. Aromatic compounds are benzene, pyridine, pyridazine, imidazole, furan, thiophene, pyrrole, pyrazole, pyrimidine, pyrazine, azulene, cyclopentadiene, tropylium, and tropone rings. An organic compound having a skeleton in the molecule, such as benzene, ethylbenzene, cumene, phenol, benzyl alcohol, chlorobenzene, dichlorobenzene, trichlorobenzene, tetrachlorobenzene, pentachlorobenzene, hexachlorobenzene, anisole, benzaldehyde, toluene, xylene , Styrene, benzoic acid, cinnamic acid, acetophenone, benzenesulfonic acid, nitrobenzene, aniline, thiophenol, benzonitrile, toluidine, diaminotoluene, triaminoto Ene, cresol, catechol, resorcinol, hydroquinone, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, benzylamine, pyridine, pyridazine, imidazole, furan, thiophene, pyrrole, pyrazole, pyrimidine, pyrazine, azulene, cyclopentadiene, tropylium, tropone , Naphthalene, dibenzofuran, dibenzo-p-dioxin, biphenyl, benzophenone, triphenylmethane, phenolphthalein, anthracene, tetracene, pentacene, phenanthrene, chrysene, triphenylene, tetraphen, pyrene, picene, pentaphen, perylene, helicene, coronene, etc. There is. Aliphatic compounds are saturated hydrocarbons and unsaturated hydrocarbons. Methanol, ethanol, propan-1-ol, butan-1-ol, pentan-1-ol, hexane-1-ol, heptane-1 -Ol, octan-1-ol, 2-methylpropan-1-ol (isobutyl alcohol), 3-methylbutan-1-ol, propan-2-ol, butan-2-ol, pentan-2-ol, hexane- 2-ol, heptan-2-ol, 2-methylbutan-1-ol, cyclohexanol, 2-methylpropan-2-ol, 2-methylbutan-2-ol, 2-methylpentan-2-ol, 2-methyl Hexan-2-ol, 2-methylheptan-2-ol, 3-methylpentane-3-ol, 3-methyloctane-3- Alcohols such as all, formaldehyde, acetaldehyde, propionaldehyde, butanal, pentanal, hexanal, heptanal, octanal, nonanal, decanal, aldehydes such as formic acid, acetic acid, acrolein, glyoxal, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexane Acids, carboxylic acids such as heptanoic acid, octanoic acid, nonanoic acid and decanoic acid, carboxylic acid anhydrides such as acetic anhydride and propionic anhydride, propylene oxide, epichlorohydrin, ethylene glycol diglycidyl ether, 1,4-butane Epoxides such as diol diglycidyl ether, methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tetradecane, penta Alkanes such as can and hexadecane, ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, alkene such as decene, alkynes such as acetylene, propyne, butyne, pentyne, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cyclo Cycloalkanes such as heptane, cyclooctane, acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, isophorone, ketone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, Carboxylic acid esters such as methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, isobutyl acetoacetate, chloromethane, , Fluoromethane, dichloromethane, dibromomethane, difluoromethane, chloroform, bromoform, fluoroform, tetrachloromethane, tetrabromomethane, tetrafluoromethane, chloroethane, bromoethane, fluoroethane, dichloroethane, dibromoethane, difluoroethane, trichloroethane, tribromo Ethane, trifluoroethane, tetrachloroethane, tetrabromoethane, tetrafluoroethane, chloroethylene, bromoethylene, fluoroethylene, dichloroethylene, dibromoethylene, difluoroethylene, trichloroethylene, tribromoethylene, trifluoroethylene, tetrachloroethylene, tetrabromoethylene, Organic halogen compounds such as tetrafluoroethylene, dimethyl ether, There are ethers such as diethyl ether, 1,4-dioxane, 1,2-dioxane, 1,3-dioxane, N, N-dimethylformamide, oxetane, tetrahydrofuran, tetrahydropyran and the like.

本発明の有機化合物と水蒸気の低減剤は上述のように構成されるため、これによれば、価格が安く、かつ容易に入手可能な天然の鉱物としても産出するゼオライトを、ガス状の有機化合物と水蒸気とを同時に低減する材料として用いることにより、気体に含まれるガス状有機化合物および水蒸気を、安価に、かつ効率的に捕集することができ、そして気体のガス状有機化合物濃度を低下させるとともに、気体の水蒸気量を低減して露点温度を０℃以下まで低下させることができる。   Since the organic compound and the water vapor reducing agent of the present invention are configured as described above, according to this, a zeolite that is produced as a natural mineral that is inexpensive and easily available is used as a gaseous organic compound. As a material that simultaneously reduces water vapor and water vapor, gaseous organic compounds and water vapor contained in gas can be collected at low cost and efficiently, and the concentration of gaseous organic compounds in gas is reduced. At the same time, the dew point temperature can be lowered to 0 ° C. or lower by reducing the amount of water vapor in the gas.

なお、露点温度とは、大気圧下で、水蒸気を含む空気の中にある物体の温度を下げていったときに、物体の表面に水の凝結が起こり始める温度であり、露点温度０℃においては、１ｍ３の空気中に水蒸気が４．８ｇ含まれる。また、２５℃における相対湿度１５％、５０％、８０％においては、それぞれ１ｍ３の空気中に水蒸気が３．５ｇ、１１．５ｇ、１８．５ｇ含まれ、５℃相対湿度９０％においては１ｍ３の空気中に水蒸気が６．１ｇ、４０℃相対湿度８０％においては１ｍ３の空気中に水蒸気が４０．９ｇ含まれる。 The dew point temperature is a temperature at which condensation of water starts to occur on the surface of the object when the temperature of the object in the air containing water vapor is reduced under atmospheric pressure. 4.8 g of water vapor is contained in 1 m 3 of air. Also, at 15%, 50%, and 80% relative humidity at 25 ° C., 3.5 g, 11.5 g, and 18.5 g of water vapor are contained in 1 m 3 of air, respectively, and 1 m at 5% relative humidity of 90%. 3 g of water vapor is 6.1 g, and at 40 ° C. and a relative humidity of 80%, 1 m 3 of air contains 40.9 g of water vapor.

ゼオライト系低減剤を入れた洗浄瓶を通過した空気の露点温度の通気開始からの時間毎の変化を示した図である。（実施例１）It is the figure which showed the change for every time from the ventilation | gas_flowing start of the dew point temperature of the air which passed the washing bottle containing the zeolite type reducing agent. Example 1 ゼオライト系低減剤を入れた洗浄瓶を通過した空気の露点温度の通気開始からの時間毎の変化を示した図である。（実施例２）It is the figure which showed the change for every time from the ventilation | gas_flowing start of the dew point temperature of the air which passed the washing bottle containing the zeolite type reducing agent. (Example 2) ゼオライト系低減剤を入れた洗浄瓶を通過した空気の露点温度の通気開始からの時間毎の変化を示した図である。（実施例３）It is the figure which showed the change for every time from the ventilation | gas_flowing start of the dew point temperature of the air which passed the washing bottle containing the zeolite type reducing agent. (Example 3) ゼオライト系低減剤を入れた洗浄瓶を通過した空気の露点温度の通気開始からの時間毎の変化を示した図である。（実施例４）It is the figure which showed the change for every time from the ventilation | gas_flowing start of the dew point temperature of the air which passed the washing bottle containing the zeolite type reducing agent. Example 4 ゼオライト系低減剤を入れた洗浄瓶を通過した空気の露点温度の通気開始からの時間毎の変化を示した図である。（実施例５）It is the figure which showed the change for every time from the ventilation | gas_flowing start of the dew point temperature of the air which passed the washing bottle containing the zeolite type reducing agent. (Example 5) ゼオライト系低減剤を入れた洗浄瓶を通過した空気の露点温度の通気開始からの時間毎の変化を示した図である。（実施例６）It is the figure which showed the change for every time from the ventilation | gas_flowing start of the dew point temperature of the air which passed the washing bottle containing the zeolite type reducing agent. (Example 6) ゼオライト系低減剤を入れた洗浄瓶を通過した空気の露点温度の通気開始からの時間毎の変化を示した図である。（実施例７）It is the figure which showed the change for every time from the ventilation | gas_flowing start of the dew point temperature of the air which passed the washing bottle containing the zeolite type reducing agent. (Example 7) ゼオライト系低減剤を入れた洗浄瓶を通過した空気の露点温度の通気開始からの時間毎の変化を示した図である。（実施例８）It is the figure which showed the change for every time from the ventilation | gas_flowing start of the dew point temperature of the air which passed the washing bottle containing the zeolite type reducing agent. (Example 8) ゼオライト系低減剤を入れた洗浄瓶を通過した空気の露点温度の通気開始からの時間毎の変化を示した図である。（実施例９）It is the figure which showed the change for every time from the ventilation | gas_flowing start of the dew point temperature of the air which passed the washing bottle containing the zeolite type reducing agent. Example 9 ゼオライト系低減剤を入れた洗浄瓶を通過した空気の露点温度の通気開始からの時間毎の変化を示した図である。（実施例１０）It is the figure which showed the change for every time from the ventilation | gas_flowing start of the dew point temperature of the air which passed the washing bottle containing the zeolite type reducing agent. (Example 10) ゼオライト系低減剤を入れた洗浄瓶を通過した空気の露点温度の通気開始からの時間毎の変化を示した図である。（実施例１１）It is the figure which showed the change for every time from the ventilation | gas_flowing start of the dew point temperature of the air which passed the washing bottle containing the zeolite type reducing agent. (Example 11) ゼオライト系低減剤を入れた洗浄瓶を通過した空気の露点温度の通気開始からの時間毎の変化を示した図である。（実施例１２）It is the figure which showed the change for every time from the ventilation | gas_flowing start of the dew point temperature of the air which passed the washing bottle containing the zeolite type reducing agent. (Example 12) ゼオライト系低減剤を入れた洗浄瓶を通過した空気の露点温度の通気開始からの時間毎の変化を示した図である。（実施例１３）It is the figure which showed the change for every time from the ventilation | gas_flowing start of the dew point temperature of the air which passed the washing bottle containing the zeolite type reducing agent. (Example 13) ゼオライト系低減剤を入れた洗浄瓶を通過した空気の露点温度の通気開始からの時間毎の変化を示した図である。（実施例１４）It is the figure which showed the change for every time from the ventilation | gas_flowing start of the dew point temperature of the air which passed the washing bottle containing the zeolite type reducing agent. (Example 14) ゼオライト系低減剤を入れた洗浄瓶を通過した空気の露点温度の通気開始からの時間毎の変化を示した図である。（実施例１５）It is the figure which showed the change for every time from the ventilation | gas_flowing start of the dew point temperature of the air which passed the washing bottle containing the zeolite type reducing agent. (Example 15) ゼオライト系低減剤を入れた洗浄瓶を通過した空気の露点温度の通気開始からの時間毎の変化を示した図である。（実施例１６）It is the figure which showed the change for every time from the ventilation | gas_flowing start of the dew point temperature of the air which passed the washing bottle containing the zeolite type reducing agent. (Example 16) ゼオライト系低減剤を入れた洗浄瓶を通過した空気の露点温度の通気開始からの時間毎の変化を示した図である。（実施例１６）It is the figure which showed the change for every time from the ventilation | gas_flowing start of the dew point temperature of the air which passed the washing bottle containing the zeolite type reducing agent. (Example 16) ゼオライト系低減剤を入れた洗浄瓶を通過した空気の露点温度の通気開始からの時間毎の変化を示した図である。（実施例１６）It is the figure which showed the change for every time from the ventilation | gas_flowing start of the dew point temperature of the air which passed the washing bottle containing the zeolite type reducing agent. (Example 16)

本実施形態の有機化合物と水蒸気の低減剤（以下、「低減剤」という。）は、例えば、適当な粒径のゼオライトを乾燥すること、塊状のゼオライトを、乾燥した後、適宜の粒径まで粉砕すること、塊状のゼオライトを、常温から９００℃以下の温度で加熱処理した後、適宜の粒径まで粉砕することのいずれかの方法により製造できる。なお、乾燥または加熱処理工程前に、ゼオライトを適宜の粒径に粉砕して製造することもできる。   The organic compound and water vapor reducing agent of the present embodiment (hereinafter referred to as “reducing agent”) may be, for example, drying a zeolite having an appropriate particle size, or drying an agglomerated zeolite to an appropriate particle size. It can be produced by any of the methods of pulverizing and mass-treating the massive zeolite at a temperature from room temperature to 900 ° C. and then pulverizing to an appropriate particle size. In addition, the zeolite can be pulverized to an appropriate particle size before the drying or heat treatment step.

乾燥または加熱処理工程は、空気が存在する雰囲気、ロータリーポンプ等のポンプで気体を吸引した真空雰囲気、ヘリウムガス、ネオンガス、アルゴンガス、クリプトンガス、キセノンガス、窒素ガスなどの不活性ガス雰囲気、二酸化炭素雰囲気のいずれの雰囲気で行ってもよい。   The drying or heat treatment process includes an atmosphere in which air exists, a vacuum atmosphere in which gas is sucked by a pump such as a rotary pump, an inert gas atmosphere such as helium gas, neon gas, argon gas, krypton gas, xenon gas, nitrogen gas, You may perform in any atmosphere of a carbon atmosphere.

本発明の有機化合物と水蒸気の低減剤は、１ヘクトパスカル以下、２００℃１０時間真空加熱処理し、引き続き１ヘクトパスカル以下の条件で５０℃以下まで冷却した状態（以下、「乾燥状態」という。）において、水素元素を０．０３質量％を超えて含み、好ましくは０．８６質量％以上含み、より好ましくは０．９６質量％以上含む。乾燥状態における低減剤は、水素含有率が０．０３質量％以下では、ガス状有機化合物、水蒸気のどちらに対しても、除去、捕集する能力は低く、水素含有率が０．８６質量％以上では、ガス状有機化合物、水蒸気のどちらも、除去、捕集でき、さらに０．９６質量％以上では、ガス状有機化合物、水蒸気のどちらに対しても、高い除去、捕集能力を有するためである。   The organic compound and the water vapor reducing agent of the present invention are vacuum heat treated at 1 hectopascal or lower and 200 ° C. for 10 hours, and then cooled to 50 ° C. or lower under the condition of 1 hectopascal or lower (hereinafter referred to as “dry state”). , Containing more than 0.03 mass%, preferably 0.86 mass% or more, more preferably 0.96 mass% or more. When the hydrogen content is 0.03% by mass or less, the reducing agent in the dry state has a low ability to remove and collect both gaseous organic compounds and water vapor, and the hydrogen content is 0.86% by mass. In the above, both gaseous organic compounds and water vapor can be removed and collected. Further, at 0.96% by mass or more, both gaseous organic compounds and water vapor have high removal and collection ability. It is.

また、本発明の有機化合物と水蒸気の低減剤は、含水率が６．２６質量％以下、好ましくは１．３５質量％以下である。有機化合物と水蒸気の低減剤の含水率が６．２６質量％を超えると、水蒸気の除去、捕集能力は有するが、ガス状有機化合物の除去、捕集能力が大きく低下するためである。また、有機化合物と水蒸気の低減剤の含水率が１．３５質量％以下では、ガス状有機化合物、水蒸気のどちらに対しても、高い除去、捕集能力を有するためである。   The organic compound and water vapor reducing agent of the present invention have a moisture content of 6.26% by mass or less, preferably 1.35% by mass or less. This is because when the water content of the organic compound and the water vapor reducing agent exceeds 6.26% by mass, the water vapor removing and collecting ability is obtained, but the gaseous organic compound removing and collecting ability is greatly reduced. Further, when the water content of the organic compound and the water vapor reducing agent is 1.35% by mass or less, both the gaseous organic compound and the water vapor have high removal and collection ability.

なおまた、本発明の有機化合物と水蒸気の低減剤は、２．３５ｍ２／ｇを超えた比表面積値であることが好ましい。比表面積２．３５ｍ２／ｇ以下では、ガス状有機化合物、水蒸気のどちらに対しても、除去、捕集能力が低いためである。 In addition, the organic compound and the water vapor reducing agent of the present invention preferably have a specific surface area value exceeding 2.35 m 2 / g. This is because, when the specific surface area is 2.35 m 2 / g or less, the removal and collection ability is low for both the gaseous organic compound and water vapor.

なお、本発明でいう有機化合物と水蒸気の低減剤の含水率とは、有機化合物と水蒸気の低減剤を真空下、２００℃、１０時間処理した時、処理後の低減剤の質量に対する処理前と処理後の質量の差の質量百分率である。   The water content of the organic compound and water vapor reducing agent referred to in the present invention means that when the organic compound and water vapor reducing agent are treated at 200 ° C. for 10 hours under vacuum, before treatment with respect to the mass of the reducing agent after treatment. It is the mass percentage of the difference in mass after treatment.

次に、本発明の実施例を説明する。以下に示す調製例は、本発明の技術的思想を具体化するための有機化合物と水蒸気の低減剤の調製方法を例示するものであって、本発明の技術的思想は、原料として用いるゼオライトの粒度や加熱処理時の閉鎖空間内のガス雰囲気を下記のものに特定するものではない。また、以下に示す実施例１〜実施例１６では、本発明の技術的思想を具体化するために、特定の有機化合物、相対湿度に対する有機化合物と水蒸気の除去、捕集結果について例示的に説明するが、本発明で有機化合物と水蒸気の低減剤が除去、捕集する有機化合物とは、有機化合物すべてを示すものであり、また、水蒸気を除去、捕集する気体の相対湿度、すなわち気体に含まれる水蒸気の質量とは、すべての温度における相対湿度０％を超え、１００％以下の気体の状態を示すものであり、本発明の技術的思想は、有機化合物と水蒸気の低減剤が捕集する有機化合物、相対湿度の値を下記のものに特定するものではない。本発明の技術的思想は、特許請求の範囲に記載された請求項が規定する技術的範囲内において、種々の変更を加えることができる。また、温度や時間などのゼオライトを加熱処理する条件も、ゼオライト系低減剤の調製例１〜調製例３、実施例７での説明に限定されるものではない。以下において、本発明の有機化合物と水蒸気の低減剤を、ゼオライト系低減剤とも称する。
なお、実施例に係る各種試験は、次の方法で行った。 Next, examples of the present invention will be described. The following preparation examples exemplify methods for preparing an organic compound and a water vapor reducing agent to embody the technical idea of the present invention. The particle size and the gas atmosphere in the closed space at the time of heat treatment are not specified as follows. Further, in Examples 1 to 16 shown below, in order to embody the technical idea of the present invention, specific organic compounds, removal of organic compounds and water vapor relative to relative humidity, and collection results will be exemplarily described. However, in the present invention, the organic compound that is removed and collected by the organic compound and the water vapor reducing agent indicates all organic compounds, and the relative humidity of the gas from which the water vapor is removed and collected, that is, the gas, The mass of water vapor contained indicates a state of gas that exceeds 0% relative humidity at all temperatures and is 100% or less. The technical idea of the present invention is that organic compounds and water vapor reducing agents are collected. The values of organic compounds and relative humidity are not specified below. The technical idea of the present invention can be variously modified within the technical scope defined by the claims described in the claims. Also, the conditions for heat treatment of the zeolite such as temperature and time are not limited to those described in Preparation Examples 1 to 3 and Example 7 of the zeolite reducing agent. Hereinafter, the organic compound and water vapor reducing agent of the present invention is also referred to as a zeolitic reducing agent.
In addition, the various tests which concern on an Example were done with the following method.

（蛍光エックス線分析）
蛍光エックス線分析値は、蛍光エックス線分析用の分析試料を、１ヘクトパスカル以下で２００℃、１０時間処理し、引き続き１ヘクトパスカル以下で５０℃以下まで冷却した試料を、エネルギー分散型蛍光エックス線分析装置（ＥＤＸ−８００ＨＳ２、(株)島津製作所社）で原子番号１１のＮａから 原子番号９２のＵまで分析し、本装置付属のソフトウェアでファンダメンタルパラメーター法(標準試料無し)によって算出した値である。 (Fluorescence X-ray analysis)
The fluorescent X-ray analysis value is obtained by treating an analytical sample for fluorescent X-ray analysis at 200 ° C. for 10 hours at 1 hectopascal or less, and subsequently cooling the sample to 50 ° C. or less at 1 hectopascal or less. -800HS2, Shimadzu Corporation), from Na of atomic number 11 to U of atomic number 92, and calculated by the fundamental parameter method (without standard sample) with the software attached to this device.

（６００℃強熱減量率）
６００℃強熱減量率は、強熱減量率分析用の分析試料を１ヘクトパスカル以下で２００℃、１０時間処理し、引き続き１ヘクトパスカル以下で５０℃以下まで冷却した試料ｍｄ［ｇ］を、磁性ルツボに入れ、空気存在下、６００℃で１時間加熱した後、ガラスデシケータ中で室温まで冷却したときに磁性ルツボに残っていた残分の質量がｍｒ［ｇ］であるとき、下記式１により算出した値である 。 (600 ° C ignition loss rate)
The 600 ° C. ignition loss rate is obtained by treating an analysis sample for ignition loss analysis at 1 hectopascal or lower at 200 ° C. for 10 hours, and subsequently cooling the sample md [g] below 1 hectopascal to 50 ° C. or lower. And after heating at 600 ° C. for 1 hour in the presence of air and cooling to room temperature in a glass desiccator, when the mass of the residue remaining in the magnetic crucible is mr [g], the following calculation is performed. Is the value.

（数１）
６００℃強熱減量率［％］＝（ｍｄ−ｍｒ）／ｍｄ×１００・・・式１ (Equation 1)
600 ° C. ignition loss ratio [%] = (md−mr) / md × 100 Formula 1

（水素含有率）
水素含有率は、水素含有率分析用の分析試料を１ヘクトパスカル以下で１５０℃、１０時間処理し、引き続き１ヘクトパスカル以下で５０℃以下まで冷却した試料を、全自動元素分析装置（varioELcube、エレメンタール社）で炭素、水素、窒素、硫黄同時分析モードで分析し、本装置付属のソフトウェアで算出した値である。 (Hydrogen content)
The hydrogen content was determined by analyzing an analysis sample for hydrogen content analysis at 1 hectopascal or less at 150 ° C. for 10 hours, and then cooling the sample to 1 degree hectopascal or less to 50 ° C. or less to obtain a fully automatic elemental analyzer (varioELcube, Elemental This is a value calculated by the software attached to this device after analysis in the simultaneous analysis mode of carbon, hydrogen, nitrogen and sulfur.

（比表面積）
比表面積値は、比表面積分析用の分析試料を１ヘクトパスカル以下で１５０℃、１０時間処理し、引き続き１ヘクトパスカル以下で５０℃以下まで冷却した試料を、自動比表面積／細孔分布測定装置（ＢＥＬＳＯＲＰ−ｍｉｎｉII、日本ベル（株）社）を用いて窒素ＢＥＴ法で測定し、本装置付属のソフトウェアで解析した値である。 (Specific surface area)
The specific surface area value is obtained by processing an analysis sample for specific surface area analysis at 1 hectopascal or lower at 150 ° C. for 10 hours, and subsequently cooling the sample to 1 hectopascal or lower to 50 ° C. or lower. -Mini II, Nippon Bell Co., Ltd.), measured by the nitrogen BET method, and analyzed by software attached to this apparatus.

（含水率）
含水率は、含水率分析用の分析試料Ｍ［ｇ］を、１ヘクトパスカル以下、２００℃で１０時間加熱処理し、引き続き１ヘクトパスカル以下で５０℃以下まで冷却した重量がＭ１［ｇ］の時、式２に代入し算出した値である。 (Moisture content)
The moisture content was determined by heating the analysis sample M [g] for moisture content analysis to 1 hectopascal or less and 200 ° C. for 10 hours, and subsequently cooling to 1 hectopascal or less and 50 ° C. or less when the weight was M1 [g]. This is a value calculated by substituting into Equation 2.

（数２）
含水率［質量％］＝（（Ｍ−Ｍ１）／Ｍ１）×１００・・・式２ (Equation 2)
Moisture content [% by mass] = ((M−M1) / M1) × 100 Formula 2

（本実施例のゼオライト原料）
本実施例で使用するゼオライト原料は、宮城県から産出した粒径１．４〜６、１〜１．４ｍｍのモルデナイト型ゼオライト（以下、粒径１．４〜６ｍｍを「ＭＢ−ＮＨ」、粒径１〜１．４ｍｍを「ＭＳ−ＮＨ」という。）、秋田県能代市から産出した粒径１．５〜３ｍｍのクリブチロル型ゼオライト（以下、「ＦＵ−ＮＨ」という。）、北海道余市郡仁木町から産出した粒径１−２．６ｍｍのクリブチロル型ゼオライト（以下、「ＮＩ−ＮＨ」という。）である。表１に、ＭＳ−ＮＨ、ＦＵ−ＮＨ、ＮＩ−ＮＨの蛍光エックス線分析結果、６００℃強熱減量率を示した。また、比較例として使用した天然ゼオライトを原料とするアイリスオーヤマ（株）社「床下さらり」の蛍光エックス線分析結果、６００℃強熱減量率も、表１に示した。 (Zeolite raw material of this example)
The zeolite raw material used in this example is a mordenite type zeolite having a particle diameter of 1.4 to 6 and 1 to 1.4 mm produced from Miyagi Prefecture (hereinafter referred to as “MB-NH” having a particle diameter of 1.4 to 6 mm, 1 to 1.4 mm in diameter is referred to as "MS-NH"), 1.5 to 3 mm cribb tyrol type zeolite (hereinafter referred to as "FU-NH") produced from Noshiro City, Akita Prefecture, Niki, Yoichi-gun, Hokkaido It is a cribb tyrol type zeolite (hereinafter referred to as “NI-NH”) having a particle diameter of 1 to 2.6 mm produced from the town. Table 1 shows the results of X-ray fluorescence analysis of MS-NH, FU-NH, and NI-NH, and the 600 ° C. ignition loss rate. Table 1 also shows the results of fluorescent X-ray analysis of Iris Oyama Co., Ltd. “Shiori under the floor” made from natural zeolite used as a comparative example, and the 600 ° C. ignition loss rate.
































＜ゼオライト系低減剤の調製例１＞
ＭＢ−ＮＨを入れたセラミックス製耐熱容器を、真空ガス置換炉（ＫＡ−１３００Ｓ、アドバンテック東洋社）の炉内に入れ、真空ポンプを用いて炉内の空気の圧力を３０ヘクトパスカル以下にした後、１５０、２４７、３００、４００、４８０、５００、６００、７００、８００、９００、９４８、１０００℃のそれぞれの温度で１５分間加熱処理し、引き続き３０ヘクトパスカル以下を保持したまま炉内で５０℃以下まで冷却させて、各種ゼオライト系低減剤を得た（以下、１５０℃加熱処理ゼオライトを「ＭＢ−Ｖ１５０」、２４７℃加熱処理ゼオライトを「ＭＢ−Ｖ２４７」、３００℃加熱処理ゼオライトを「ＭＢ−Ｖ３００」、４００℃加熱処理ゼオライトを「ＭＢ−Ｖ４００」、４８０℃加熱処理ゼオライトを「ＭＢ−Ｖ４８０」、５００℃加熱処理ゼオライトを「ＭＢ−Ｖ５００」、６００℃加熱処理ゼオライトを「ＭＢ−Ｖ６００」、７００℃加熱処理ゼオライトを「ＭＢ−Ｖ７００」、８００℃加熱処理ゼオライトを「ＭＢ−Ｖ８００」、９００℃加熱処理ゼオライトを「ＭＢ−Ｖ９００」、９４８℃加熱処理ゼオライトを「ＭＢ−Ｖ９４８」、１０００℃加熱処理ゼオライトを「ＭＢ−Ｖ１０００」という。）。 <Zeolite-based reducing agent preparation example 1>
After putting the ceramic heat-resistant container containing MB-NH into the furnace of the vacuum gas replacement furnace (KA-1300S, Advantech Toyo Co., Ltd.), and reducing the pressure of the air in the furnace to 30 hectopascals using a vacuum pump, 150, 247, 300, 400, 480, 500, 600, 700, 800, 900, 948, and 1000 ° C. for 15 minutes, and then kept at 30 hectopascals or less to 50 ° C. or less in the furnace. After cooling, various zeolite-based reducing agents were obtained (hereinafter, 150 ° C. heat-treated zeolite was “MB-V150”, 247 ° C. heat-treated zeolite was “MB-V247”, and 300 ° C. heat-treated zeolite was “MB-V300”. , 400 ° C heat-treated zeolite is "MB-V400", 480 ° C heat-treated zeolite is "MB-V480" 500 ° C heat-treated zeolite "MB-V500", 600 ° C heat-treated zeolite "MB-V600", 700 ° C heat-treated zeolite "MB-V700", 800 ° C heat-treated zeolite "MB-V800", 900 The heat-treated zeolite at 0 ° C. is referred to as “MB-V900”, the heat-treated zeolite at 948 ° C. is referred to as “MB-V948”, and the heat-treated zeolite at 1000 ° C. is referred to as “MB-V1000”.

＜ゼオライト系低減剤の調製例２＞
ＭＳ−ＮＨを入れたセラミックス製耐熱容器を、真空ガス置換炉（ＫＡ−１３００Ｓ、アドバンテック東洋社）の炉内に入れ、真空ポンプを用いて炉内の空気の圧力を３０ヘクトパスカル以下にした後、１５０、２００、２４７、３００、４００、４８０℃のそれぞれの温度で１５分間加熱処理し、引き続き３０ヘクトパスカル以下を保持したまま炉内で５０℃以下まで冷却させて、各種ゼオライト系低減剤を得た（以下、１５０℃加熱処理ゼオライトを「ＭＳ−Ｖ１５０」、２００℃加熱処理ゼオライトを「ＭＳ−Ｖ２００」、２４７℃加熱処理ゼオライトを「ＭＳ−Ｖ２４７」、３００℃加熱処理ゼオライトを「ＭＳ−Ｖ３００」、４００℃加熱処理ゼオライトを「ＭＳ−Ｖ４００」、４８０℃加熱処理ゼオライトを「ＭＳ−Ｖ４８０」という。）。 <Zeolite-based reducing agent preparation example 2>
After putting the heat-resistant container made of ceramics containing MS-NH into the furnace of the vacuum gas replacement furnace (KA-1300S, Advantech Toyo Co., Ltd.), the pressure of the air in the furnace is reduced to 30 hectopascals or less using a vacuum pump, Heat treatment was performed at 150, 200, 247, 300, 400, and 480 ° C. for 15 minutes, followed by cooling to 50 ° C. or less in a furnace while maintaining 30 hectopascals or less to obtain various zeolite-based reducing agents. (Hereafter, 150 ° C heat-treated zeolite is "MS-V150", 200 ° C heat-treated zeolite is "MS-V200", 247 ° C heat-treated zeolite is "MS-V247", and 300 ° C heat-treated zeolite is "MS-V300". , 400 ° C heat-treated zeolite "MS-V400", 480 ° C heat-treated zeolite "MS-V480" Say.).

＜ゼオライト系低減剤の調製例３＞
ＭＢ−ＮＨを入れたセラミックス製耐熱容器を、真空ガス置換炉（ＫＡ−１３００Ｓ、アドバンテック東洋社）の炉内に入れ、常圧、空気存在下、２００、２４７、３００、４００、４８０、６００℃のそれぞれの温度で１５分間加熱処理し、常圧、空気存在下の炉内で５０℃以下まで冷却させて、各種ゼオライト系低減剤を得た（以下、１５０℃加熱処理ゼオライトを「ＭＢ−Ａ２００」、２４７℃加熱処理ゼオライトを「ＭＢ−Ａ２４７」、３００℃加熱処理ゼオライトを「ＭＢ−Ａ３００」、４００℃加熱処理ゼオライトを「ＭＢ−Ａ４００」、４８０℃加熱処理ゼオライトを「ＭＢ−Ａ４８０」、６００℃加熱処理ゼオライトを「ＭＢ−Ａ６００」という。）。 <Zeolite-based reducing agent preparation example 3>
The ceramic heat-resistant container containing MB-NH was placed in a furnace of a vacuum gas replacement furnace (KA-1300S, Advantech Toyo Co., Ltd.), 200, 247, 300, 400, 480, 600 ° C. in the presence of normal pressure and air. Were subjected to heat treatment at each temperature for 15 minutes, and cooled to 50 ° C. or lower in a furnace in the presence of atmospheric pressure and air to obtain various zeolite-based reducing agents (hereinafter, 150 ° C. heat-treated zeolite was referred to as “MB-A200 ”247 ° C. heat-treated zeolite“ MB-A247 ”, 300 ° C. heat-treated zeolite“ MB-A300 ”, 400 ° C. heat-treated zeolite“ MB-A400 ”, 480 ° C. heat-treated zeolite“ MB-A480 ”, The 600 ° C. heat-treated zeolite is referred to as “MB-A600”).

＜実施例１＞
ゼオライト系低減剤の調製例１のＭＢ−Ｖ１５０を１００ｍＬ入れた、Ｇ２球状ガラスフィルターを具備した１００ｍＬ木下式ねじ口ガス吸収洗滌瓶（以下、「洗浄瓶」という。）に、２５℃の温度下、ガス状スチレン濃度５５０ｐｐｍ、２５℃相対湿度８０％の空気を１分間に１Ｌの速度で通気した。洗浄瓶を通過した空気の２５℃相対湿度を温湿度データーロガー（ＲＨＴ−１０、アズワン（株）社）を用いて１０秒間隔で測定し、そして、洗浄瓶を通過した空気のスチレン濃度をスチレン検知管（Ｎｏ．１２４、（株）ガステック社）を用いて１５分間隔で測定した。また、ゼオライト系低減剤の調製例１のＭＢ−Ｖ２４７、ＭＢ−Ｖ３００、ＭＢ−Ｖ４００、ＭＢ−Ｖ４８０、ＭＢ−Ｖ５００、ＭＢ−Ｖ６００、ＭＢ−Ｖ７００、ＭＢ−Ｖ８００、ＭＢ−Ｖ９００、ＭＢ−Ｖ９４８、ＭＢ−Ｖ１０００についても同じ実験を行った。表２に、各ゼオライト系低減剤のガス状スチレン捕集時間、水素含有率、含水率、比表面積、露点温度が０℃以下に達するまでの通気開始からの時間（以下、「露点温度０℃到達時間」という。）、ゼオライト系低減剤の使用量を示した。また、ＭＢ−Ｖ４８０、ＭＢ−Ｖ９００について、洗浄瓶を通過した空気の露点温度の通気開始からの時間毎の変化を図１に示した。図１の横軸は洗浄瓶に通気し始めた時からの経過時間、縦軸は露点温度である。 <Example 1>
Preparation of zeolite-based reducing agent MB-V150 of Preparation Example 1 100 mL A 100 mL Kinoshita type screw mouth gas absorption washing bottle (hereinafter referred to as “washing bottle”) equipped with a G2 spherical glass filter was heated at 25 ° C. Then, air having a gaseous styrene concentration of 550 ppm and 25 ° C. and a relative humidity of 80% was aerated at a rate of 1 L per minute. The relative humidity of the air passing through the washing bottle was measured at 10 second intervals using a temperature / humidity data logger (RHT-10, ASONE Co., Ltd.), and the styrene concentration of the air passing through the washing bottle was measured with styrene. Measurements were made at 15 minute intervals using a detector tube (No. 124, Gastec Co., Ltd.). Moreover, MB-V247, MB-V300, MB-V400, MB-V480, MB-V500, MB-V600, MB-V700, MB-V800, MB-V900, MB-V948 of Preparation Example 1 of zeolite reducing agent The same experiment was conducted for MB-V1000. Table 2 shows gaseous styrene collection time, hydrogen content, water content, specific surface area, and time from the start of aeration until the dew point temperature reaches 0 ° C. or lower (hereinafter referred to as “dew point temperature 0 ° C.”). The amount of use of the zeolitic reducing agent is indicated. Moreover, about MB-V480 and MB-V900, the change for every time from the ventilation | gas_flowing start of the dew point temperature of the air which passed the washing bottle was shown in FIG. The horizontal axis in FIG. 1 is the elapsed time from the start of aeration into the washing bottle, and the vertical axis is the dew point temperature.

なお、ゼオライト系低減剤の調製例１の各ゼオライト系低減剤は、洗浄瓶に入れる前に、１ヘクトパスカル以下、１５０℃の条件下で、１０時間処理し、引き続き１ヘクトパスカル以下で５０℃以下まで冷却する処理を行った。   Each zeolite-based reducing agent in Preparation Example 1 of the zeolite-based reducing agent was treated for 10 hours under the conditions of 1 hectopascal or less and 150 ° C. before being put in the washing bottle, and subsequently 1 hectopascal or less to 50 ° C. or less. The cooling process was performed.

そして、なお、ガス状スチレン捕集時間は、検知限度１ｐｐｍであるスチレン検知管（Ｎｏ．１２４、（株）ガステック社）を用いて洗浄瓶通過後の空気を測定した時に、スチレン検知管により検知されなかった通気開始後からの１５分間隔の時間であり、水素含有率は、ゼオライト系低減剤を元素分析用の分析試料として、水素含有率試験を行った値であり、含水率は、洗浄瓶に入れた低減剤と同じものを含水率分析用の分析試料として、含水率試験を行った値であり、比表面積は、ゼオライト系低減剤を比表面積分析用の分析試料として、比表面積試験を行った値である。   And the gaseous styrene collection time is measured by the styrene detector tube when the air after passing through the washing bottle is measured using a styrene detector tube (No. 124, Gastec Co., Ltd.) having a detection limit of 1 ppm. It was a time of 15 minutes after the start of aeration that was not detected, and the hydrogen content is a value obtained by performing a hydrogen content test using a zeolite-based reducing agent as an analysis sample for elemental analysis. It is the value obtained by conducting the moisture content test using the same reducing agent placed in the washing bottle as the analysis sample for moisture content analysis, and the specific surface area is the specific surface area using the zeolite-based reducing agent as the analysis sample for specific surface area analysis. It is the value which carried out the test.


























図１に示したとおり、ＭＢ−Ｖ４８０を入れた洗浄瓶を通過した空気は、通気開始から４８０秒間経過後に露点温度０℃以下に達した後、洗浄瓶を通過した空気中にスチレン検知管によりスチレンが検知されなかった通気開始からの経過時間まで、露点温度０℃以下を維持したが、ＭＢ−Ｖ９００を入れた洗浄瓶を通過した空気は、露点温度の低下がみられたが、露点温度０℃まで達することなく、すぐに露点温度の上昇がみられた。また、ＭＢ−Ｖ１５０、ＭＢ−Ｖ２４７、ＭＢ−Ｖ３００、ＭＢ−Ｖ４００、ＭＢ−Ｖ５００、ＭＢ−Ｖ６００、ＭＢ−Ｖ７００、ＭＢ−Ｖ８００をそれぞれ入れた洗浄瓶を通過した空気は、ＭＢ−Ｖ４８０と同じように、表２の各露点温度０℃到達時間に示した通気開始からの経過時間に露点温度０℃以下に達した後、洗浄瓶を通過した空気中にスチレン検知管によりスチレンが検知されなかった通気開始からの経過時間まで、露点温度０℃以下を維持し、そして、ＭＢ−Ｖ９４８、ＭＢ−Ｖ１０００は、ＭＢ−Ｖ９００と同じように、洗浄瓶を通過した空気は、露点温度の低下がみられたが、露点温度０℃まで達することなく、すぐに露点温度の上昇がみられた。   As shown in FIG. 1, the air that passed through the cleaning bottle containing MB-V480 reached a dew point temperature of 0 ° C. or less after 480 seconds from the start of ventilation, and then passed through the cleaning bottle by a styrene detector tube. The dew point temperature was maintained at 0 ° C. or lower until the elapsed time from the start of ventilation where no styrene was detected, but the air that passed through the washing bottle containing MB-V900 showed a decrease in the dew point temperature. The dew point temperature immediately increased without reaching 0 ° C. In addition, the air passing through the washing bottles containing MB-V150, MB-V247, MB-V300, MB-V400, MB-V500, MB-V600, MB-V700, MB-V800, respectively, is the same as MB-V480. As described above, after reaching the dew point temperature of 0 ° C. or less during the elapsed time from the start of ventilation shown in each dew point temperature of 0 ° C. in Table 2, styrene is not detected by the styrene detector tube in the air that has passed through the washing bottle. Until the elapsed time from the start of ventilation, the dew point temperature is maintained at 0 ° C. or lower, and the MB-V948 and MB-V1000 have the same dew point temperature as the MB-V900. As a result, the dew point temperature was immediately increased without reaching the dew point temperature of 0 ° C.

含水率０．００質量％、水素含有率０．０３％以下、比表面積２．３５ｍ２／ｇ以下のＭＢ−Ｖ９００、ＭＢ−Ｖ９４８、ＭＢ−Ｖ１０００は、ガス状スチレン捕集時間が１５分間未満であり、また、通気後の空気の露点温度が０℃以下に達することはなかった。 MB-V900, MB-V948, and MB-V1000 having a water content of 0.00 mass%, a hydrogen content of 0.03% or less, and a specific surface area of 2.35 m 2 / g or less have a gaseous styrene collection time of less than 15 minutes. In addition, the dew point temperature of the air after ventilation did not reach 0 ° C. or lower.

含水率０．８６質量％以下、水素含有率０．８６質量％以上、比表面積３９．７ｍ２／ｇ以上のＭＢ−Ｖ１５０、ＭＢ−Ｖ２４７、ＭＢ−Ｖ３００、ＭＢ−Ｖ４００、ＭＢ−Ｖ４８０、ＭＢ−Ｖ５００、ＭＢ−Ｖ６００、ＭＢ−Ｖ７００、ＭＢ−Ｖ８００は、ガス状スチレン捕集時間が６０分間以上であり、また、通気開始から１８０〜４２０秒後に、通気後の空気の露点温度が０℃に達した後、洗浄瓶を通過した空気中にスチレン検知管によりスチレンが検知されなかった通気開始からの経過時間まで、露点温度０℃以下を維持した。特に、含水率０．８６質量％未満、水素含有率１．０９質量％以上、比表面積６７．１ｍ２／ｇ以上のＭＢ−Ｖ１５０、ＭＢ−Ｖ２００、ＭＢ−Ｖ２４７、ＭＢ−Ｖ３００、ＭＢ−Ｖ４００、ＭＢ−Ｖ５００、ＭＢ−Ｖ７００では、ガス状スチレンを１５０分間以上捕集した。 MB-V150, MB-V247, MB-V300, MB-V400, MB-V480, MB having a water content of 0.86% by mass or less, a hydrogen content of 0.86% by mass or more, and a specific surface area of 39.7 m 2 / g or more. -V500, MB-V600, MB-V700, MB-V800 have a gaseous styrene collection time of 60 minutes or more, and the dew point temperature of the air after ventilation is 0 ° C. after 180 to 420 seconds from the start of ventilation. Then, the dew point temperature was maintained at 0 ° C. or lower until the elapsed time from the start of aeration when styrene was not detected by the styrene detector tube in the air that passed through the washing bottle. Particularly, MB-V150, MB-V200, MB-V247, MB-V300, MB-V400 having a water content of less than 0.86% by mass, a hydrogen content of 1.09% by mass or more, and a specific surface area of 67.1 m 2 / g or more. In MB-V500 and MB-V700, gaseous styrene was collected for 150 minutes or more.

なお、含水率１１．２質量％であるＭＢ−ＮＨをそのまま用いて実施例１と同じ実験を行った結果、ガス状スチレンの捕集時間は１５分間未満であり、また、通気後の空気の露点温度が０℃以下に達することはなかった。   In addition, as a result of conducting the same experiment as Example 1 using MB-NH having a water content of 11.2% by mass as it was, the collection time of gaseous styrene was less than 15 minutes, and the air after aeration The dew point temperature never reached 0 ° C. or lower.

＜実施例２＞
含水率が異なるゼオライト系低減剤の調製例１のＭＢ−Ｖ４８０を１００ｍＬ入れた、Ｇ２球状ガラスフィルターを具備した１００ｍＬ木下式ねじ口ガス吸収洗滌瓶（以下、「洗浄瓶」という。）に、２５℃の温度下、ガス状スチレン濃度５５０ｐｐｍ、２５℃相対湿度８０％の空気を１分間に１Ｌの速度で通気した。洗浄瓶を通過した空気の温度および相対湿度を温湿度データーロガー（ＲＨＴ−１０、アズワン（株）社）を用いて１０秒間隔で測定し、また、スチレン濃度をスチレン検知管（Ｎｏ．１２４、（株）ガステック社）を用いて１５分間隔で測定した。表３に、それぞれの含水率が異なるＭＢ−Ｖ４８０のガス状スチレン捕集時間、露点温度０℃到達時間を示し、図２に、洗浄瓶を通過した空気の露点温度の時間毎の変化示した。図２の横軸は洗浄瓶に通気し始めた時からの経過時間、縦軸は露点温度である。 <Example 2>
25 in a 100 mL Kinoshita-type screw mouth gas absorption cleaning bottle (hereinafter referred to as “cleaning bottle”) equipped with a G2 spherical glass filter containing 100 mL of MB-V480 of Preparation Example 1 of zeolite-type reducing agent having different water contents. Under a temperature of ° C., air with a gaseous styrene concentration of 550 ppm and 25 ° C. and a relative humidity of 80% was aerated at a rate of 1 L per minute. The temperature and relative humidity of the air passing through the washing bottle were measured at intervals of 10 seconds using a temperature / humidity data logger (RHT-10, ASONE Co., Ltd.), and the styrene concentration was measured with a styrene detector tube (No. 124, (Gastech Co., Ltd.) was measured at intervals of 15 minutes. Table 3 shows the gaseous styrene collection time and dew point temperature reaching time of 0 ° C. for MB-V480 having different moisture contents, and FIG. 2 shows the change of the dew point temperature of the air passing through the washing bottle over time. . The horizontal axis in FIG. 2 is the elapsed time from the start of aeration into the washing bottle, and the vertical axis is the dew point temperature.

なお、含水率が異なるＭＢ−Ｖ４８０は、室温、大気圧下で吸湿させたＭＢ−Ｖ４８０を、適宜、１ヘクトパスカル以下、１１０℃以下の温度で２時間加熱処理することで調製した。また、加熱処理した含水率が異なるＭＢ−Ｖ４８０は、温度が５０℃以下であることを確認した後、大気を導入して取り出し、直ちに洗浄瓶に入れて実験を行った。   In addition, MB-V480 having different moisture contents was prepared by appropriately heat-treating MB-V480 absorbed at room temperature and atmospheric pressure at a temperature of 1 hectopascal or lower and 110 ° C or lower for 2 hours. In addition, after confirming that the heat-treated MB-V480 having a different water content had a temperature of 50 ° C. or less, the atmosphere was introduced and taken out, and the experiment was conducted immediately after putting it in a washing bottle.

なおまた、ガス状スチレン捕集時間は、検知限度１ｐｐｍであるスチレン検知管（Ｎｏ．１２４、（株）ガステック社）を用いて洗浄瓶通過後の空気を測定した時に、スチレン検知管により検知されなかった通気開始後からの１５分間隔の時間であり、含水率は、洗浄瓶に入れた低減剤と同じものを含水率分析用の分析試料として、含水率試験を行った値である。   In addition, the gaseous styrene collection time is detected by the styrene detector tube when the air after passing through the washing bottle is measured using a styrene detector tube (No. 124, Gastec Co., Ltd.) having a detection limit of 1 ppm. This is a time of 15 minutes after the start of aeration, and the moisture content is a value obtained by conducting a moisture content test using the same reducing agent put in the washing bottle as an analysis sample for moisture content analysis.
















ＭＢ−Ｖ４８０の含水率が低下するに従い、ガス状スチレン捕集時間が長くなり、含水率１．３５質量％以下ではガス状スチレン捕集時間は１５０分間以上、含水率１．９０質量％ではガス状スチレン捕集時間は９０分間、含水率３．３１質量％、５．５３質量％ではガス状スチレン捕集時間は６０分間であったが、含水率６．５３質量％になるとガス状スチレン捕集時間は１５分間になった。また、洗浄瓶を通過した空気の露点温度は、含水率０．８２〜６．５３質量％のすべてのＭＢ−Ｖ４８０で０℃まで到達したが、含水率６．５３質量％のＭＢ−Ｖ４８０の露点温度が０℃に到達するまでの通気開始からの経過時間は、６５０秒間であり、他の含水率が異なるＭＢ−Ｖ４８０の中で最も時間が長かった含水率５．５３質量％のＭＢ−Ｖ４８０の３１０秒間の２倍以上の時間であった。   As the moisture content of MB-V480 decreases, the gaseous styrene collection time becomes longer. When the moisture content is 1.35% by mass or less, the gaseous styrene collection time is 150 minutes or more, and when the moisture content is 1.90% by mass, the gas is collected. The gaseous styrene collection time was 90 minutes, and when the moisture content was 3.31% by mass and 5.53% by mass, the gaseous styrene was collected for 60 minutes. However, when the moisture content was 6.53% by mass, the gaseous styrene was collected. The collection time was 15 minutes. The dew point temperature of the air that passed through the washing bottle reached 0 ° C. in all MB-V480 having a moisture content of 0.82 to 6.53 mass%, but the dew point temperature of MB-V480 having a moisture content of 6.53 mass% The elapsed time from the start of aeration until the dew point temperature reaches 0 ° C. is 650 seconds, and the MB-V 480 having the longest time among other MB-V 480 having different water contents has an MB- content of 5.53% by mass. It was more than twice as long as 310 seconds of V480.

図２に示したとおり、各含水率が異なるＭＢ−Ｖ４８０を入れた洗浄瓶を通過した空気は、表３の露点温度０℃到達時間に示した通気開始からの経過時間に、露点温度０℃以下に達した後、洗浄瓶を通過した空気中にスチレン検知管によりスチレンが検知されなかった通気開始からの経過時間まで、露点温度０℃以下を維持した。   As shown in FIG. 2, the air that passed through the washing bottles containing MB-V480 having different moisture contents had a dew point temperature of 0 ° C. in the elapsed time from the start of aeration shown in Table 3 at the time when the dew point temperature reached 0 ° C. After reaching the following, the dew point temperature was maintained at 0 ° C. or lower until the elapsed time from the start of aeration when styrene was not detected by the styrene detector tube in the air that passed through the washing bottle.

＜実施例３＞
ゼオライト系低減剤の調製例１のＭＢ−Ｖ４８０を１００ｍＬ入れた、Ｇ２球状ガラスフィルターを具備した１００ｍＬ木下式ねじ口ガス吸収洗滌瓶（以下、「洗浄瓶」という。）に、２５℃の温度下、ガス状スチレン濃度５５０ｐｐｍ、２５℃相対湿度１５、５０％それぞれの空気を１分間に１Ｌの速度で通気した。洗浄瓶を通過した空気の温度および相対湿度を温湿度データーロガー（ＲＨＴ−１０、アズワン（株）社）を用いて１０秒間隔で測定し、また、スチレン濃度をスチレン検知管（Ｎｏ．１２４、（株）ガステック社）を用いて１５分間隔で測定した。表４に、２５℃相対湿度１５、５０％それぞれのガス状スチレン捕集時間、露点温度０℃到達時間、ＭＢ−Ｖ４８０の含水率を示し、図３に、洗浄瓶を通過した空気の露点温度の時間毎の変化示した。図３の横軸は洗浄瓶に通気し始めた時からの経過時間、縦軸は露点温度である。 <Example 3>
Preparation of zeolite-based reducing agent MB-V480 of Preparation Example 1 100 mL In a 100 mL Kinoshita type screw mouth gas absorption cleaning bottle (hereinafter referred to as “cleaning bottle”) equipped with a G2 spherical glass filter, at a temperature of 25 ° C. Then, air with a gaseous styrene concentration of 550 ppm, 25 ° C. relative humidity of 15 and 50% was aerated at a rate of 1 L per minute. The temperature and relative humidity of the air passing through the washing bottle were measured at intervals of 10 seconds using a temperature / humidity data logger (RHT-10, ASONE Co., Ltd.), and the styrene concentration was measured with a styrene detector tube (No. 124, (Gastech Co., Ltd.) was measured at intervals of 15 minutes. Table 4 shows the collection time of gaseous styrene at 25 ° C. relative humidity of 15 and 50%, the dew point temperature reaching time of 0 ° C., the moisture content of MB-V480, and FIG. 3 shows the dew point temperature of the air passing through the washing bottle. The change with time. The horizontal axis in FIG. 3 is the elapsed time from the start of aeration into the washing bottle, and the vertical axis is the dew point temperature.

なお、ＭＢ−Ｖ４８０は、洗浄瓶に入れる前に、１ヘクトパスカル以下、１５０℃１０時間処理し、引き続き１ヘクトパスカル以下で５０℃以下まで冷却する処理を行った。   MB-V480 was treated at 1 hectopascal or lower at 150 ° C. for 10 hours and then cooled to 1 ° hectopascal or lower and 50 ° C. or lower before being put in a washing bottle.

なおまた、ガス状スチレン捕集時間は、検知限度１ｐｐｍであるスチレン検知管（Ｎｏ．１２４、（株）ガステック社）を用いて洗浄瓶通過後の空気を測定した時に、スチレン検知管により検知されなかった通気開始後からの１５分間隔の時間であり、含水率は、洗浄瓶に入れた低減剤と同じものを含水率分析用の分析試料として、含水率試験を行った値である。   In addition, the gaseous styrene collection time is detected by the styrene detector tube when the air after passing through the washing bottle is measured using a styrene detector tube (No. 124, Gastec Co., Ltd.) having a detection limit of 1 ppm. This is a time of 15 minutes after the start of aeration, and the moisture content is a value obtained by conducting a moisture content test using the same reducing agent put in the washing bottle as an analysis sample for moisture content analysis.














なお、そして、表４、図３の２５℃相対湿度８０％は、実施例１のＭＢ−Ｖ４８０のデータである。   The 25 ° C. relative humidity of 80% in Table 4 and FIG. 3 is the data of MB-V480 of Example 1.

ガス状スチレンが含まれる２５℃、相対湿度１５、５０、８０％の空気をそれぞれＭＢ−Ｖ４８０を入れた洗浄瓶に通過させた場合のガス状スチレン捕集時間は、それぞれ４８０、１９５、１８０分間であり、２５℃相対湿度が低下するに従い、ガス状スチレン捕集時間が長くなり、特に２５℃相対湿度が５０％から１５％に低下するとガス状スチレン捕集時間が２．５倍程度と、顕著に長くなった。   Gaseous styrene collection times when air containing 25 ° C. and 15%, 50%, and 80% relative humidity containing gaseous styrene are passed through washing bottles containing MB-V480 are 480, 195, and 180 minutes, respectively. As the 25 ° C. relative humidity decreases, the gaseous styrene collection time becomes longer. In particular, when the 25 ° C. relative humidity decreases from 50% to 15%, the gaseous styrene collection time is about 2.5 times, Remarkably long.

ガス状スチレンが含まれる２５℃、相対湿度１５、５０、８０％の空気をそれぞれＭＢ−Ｖ４８０を入れた洗浄瓶に通過させた場合は、通気開始からそれぞれ２７０、１５０、２７０秒間経過後に露点温度０℃以下に達した後、洗浄瓶を通過した空気中にスチレン検知管によりスチレンが検知されなかった通気開始からの経過時間まで、露点温度０℃以下を維持した。   When air of 25 ° C and relative humidity of 15, 50, and 80% containing gaseous styrene was passed through a washing bottle containing MB-V480, dew point temperatures were passed after 270, 150, and 270 seconds respectively from the start of ventilation. After reaching 0 ° C. or lower, the dew point temperature was maintained at 0 ° C. or lower until the elapsed time from the start of ventilation where styrene was not detected by the styrene detector tube in the air that passed through the washing bottle.

＜実施例４＞
ゼオライト系低減剤の調製例１のＭＢ−Ｖ４８０を１００ｍＬ入れた、Ｇ２球状ガラスフィルターを具備した１００ｍＬ木下式ねじ口ガス吸収洗滌瓶（以下、「洗浄瓶」という。）に、５℃の温度下、ガス状スチレン濃度５５０ｐｐｍ、５℃相対湿度９０％の空気を１分間に１Ｌの速度で通気した。洗浄瓶を通過した空気の温度および相対湿度を温湿度データーロガー（ＲＨＴ−１０、アズワン（株）社）を用いて１０秒間隔で測定し、また、スチレン濃度をスチレン検知管（Ｎｏ．１２４、（株）ガステック社）を用いて１５分間隔で測定した。また、５℃の温度下、ガス状スチレン濃度５５０ｐｐｍ、５℃相対湿度９０％の空気の条件の代わりに、４０℃の温度下、ガス状スチレン濃度５５０ｐｐｍ、４０℃相対湿度８０％の空気を用いて、同じ通気試験を行った。表５に、５℃相対湿度９０％、４０℃相対湿度８０％それぞれのガス状スチレン捕集時間、ＭＢ−Ｖ４８０の含水率を示し、図４に、洗浄瓶を通過した空気の露点温度の時間毎の変化示した。図４の横軸は洗浄瓶に通気し始めた時からの経過時間、縦軸は露点温度である。 <Example 4>
Preparation of zeolite-based reducing agent MB-V480 of Preparation Example 1 100 mL In a 100 mL Kinoshita type screw mouth gas absorption cleaning bottle (hereinafter referred to as “cleaning bottle”) equipped with a G2 spherical glass filter, at a temperature of 5 ° C. Then, air having a gaseous styrene concentration of 550 ppm and a relative humidity of 90 ° C. was aerated at a rate of 1 L per minute. The temperature and relative humidity of the air passing through the washing bottle were measured at intervals of 10 seconds using a temperature / humidity data logger (RHT-10, ASONE Co., Ltd.), and the styrene concentration was measured with a styrene detector tube (No. 124, (Gastech Co., Ltd.) was measured at intervals of 15 minutes. Also, air having a gaseous styrene concentration of 550 ppm and 40 ° C. and a relative humidity of 80% was used at a temperature of 40 ° C. instead of air having a gaseous styrene concentration of 550 ppm and a relative humidity of 90 ° C. at a temperature of 5 ° C. The same aeration test was conducted. Table 5 shows the gaseous styrene collection time and MB-V480 moisture content at 5 ° C. relative humidity 90% and 40 ° C. relative humidity 80%, respectively, and FIG. 4 shows the time of dew point temperature of the air passed through the washing bottle. Shown every change. The horizontal axis in FIG. 4 is the elapsed time from the start of aeration in the washing bottle, and the vertical axis is the dew point temperature.

なお、５℃、相対湿度９０％の通気試験のＭＢ−Ｖ４８０は、洗浄瓶に入れる前に、１ヘクトパスカル以下、１５０℃１０時間処理し、引き続き１ヘクトパスカル以下で５０℃以下まで冷却をする処理した。なおまた、４０℃、相対湿度８０％の通気試験のＭＢ−Ｖ４８０は、洗浄瓶に入れる前に、１ヘクトパスカル以下、１５０℃１０時間処理し、引き続き１ヘクトパスカル以下で５０℃以下まで冷却をした後、さらに室内で２時間放置する処理をした。   In addition, MB-V480 of the aeration test at 5 ° C. and 90% relative humidity was treated at 1 hectopascal or lower and 150 ° C. for 10 hours and then cooled to 50 ° C. or lower at 1 hectopascal or lower before being put into a washing bottle. . In addition, the MB-V480 of the ventilation test at 40 ° C. and 80% relative humidity was treated at 1 hectopascal or lower and 150 ° C. for 10 hours before being put into a washing bottle, and subsequently cooled to 50 ° C. or lower at 1 hectopascal or lower. Furthermore, it was processed to be left indoors for 2 hours.

なおまた、ガス状スチレン捕集時間は、検知限度１ｐｐｍであるスチレン検知管（Ｎｏ．１２４、（株）ガステック社）を用いて洗浄瓶通過後の空気を測定した時に、スチレン検知管により検知されなかった通気開始後からの１５分間隔の時間であり、含水率は、洗浄瓶に入れた低減剤と同じものを含水率分析用の分析試料として、含水率試験を行った値である。   In addition, the gaseous styrene collection time is detected by the styrene detector tube when the air after passing through the washing bottle is measured using a styrene detector tube (No. 124, Gastec Co., Ltd.) having a detection limit of 1 ppm. This is a time of 15 minutes after the start of aeration, and the moisture content is a value obtained by conducting a moisture content test using the same reducing agent put in the washing bottle as an analysis sample for moisture content analysis.









ガス状スチレンが含まれる５℃、相対湿度９０％の空気を、含水率０．７０質量％のＭＢ−Ｖ４８０を入れた洗浄瓶に通過させた場合のガス状スチレン捕集時間は、２１０分間であった。また、１ｍ３の空気に含まれる水蒸気量が２５℃相対湿度８０％の２倍を超える４０℃相対湿度８０％のガス状スチレンを含む空気を、含水率３．５４質量％の比較的含水率が高いＭＢ−Ｖ４８０を入れた洗浄瓶に通過させた場合においてもガス状スチレン捕集時間３０分間であり、ガス状スチレンの捕集能力を有していた。 Gaseous styrene collection time when air containing gaseous styrene at 5 ° C. and relative humidity 90% was passed through a washing bottle containing MB-V480 having a moisture content of 0.70 mass% was 210 minutes. there were. In addition, air containing gaseous styrene having a relative humidity of 3.54% by mass of air containing 40% relative humidity of 80% relative to the amount of water vapor contained in 1 m 3 of air exceeds twice the 25 ° C. relative humidity of 80%. Even when it was passed through a washing bottle containing MB-V480 having a high value, the gaseous styrene collection time was 30 minutes, and it had the ability to collect gaseous styrene.

ガス状スチレンが含まれる５℃、相対湿度９０％の空気をＭＢ−Ｖ４８０を入れた洗浄瓶に通過させた場合は、通気開始から１７０秒間経過後に露点温度０℃以下に達した後、洗浄瓶を通過した空気中にスチレン検知管によりスチレンが検知されなかった通気開始からの経過時間まで、露点温度０℃以下を維持した。また、ガス状スチレンが含まれる４０℃、相対湿度８０％の空気をＭＢ−Ｖ４８０を入れた洗浄瓶に通過させた場合は、１ｍ３の空気に含まれる水蒸気量が２５℃相対湿度８０％の２倍を超えるにもかかわらず、通気開始から１８０秒後には露点温度１０℃に達し、そして引き続き露点温度は低下を続けガス状スチレン捕集時間である１８００秒後には露点温度４．２℃に達した。 When air containing gaseous styrene at 5 ° C and relative humidity of 90% is passed through a washing bottle containing MB-V480, the dew point reaches 0 ° C or less after 170 seconds from the start of ventilation, and then the washing bottle The dew point temperature was maintained at 0 ° C. or lower until the elapsed time from the start of ventilation where styrene was not detected by the styrene detector tube in the air that passed through. In addition, when air containing gaseous styrene at 40 ° C. and 80% relative humidity is passed through a washing bottle containing MB-V480, the amount of water vapor contained in 1 m 3 of air is 25 ° C. and 80% relative humidity. Despite exceeding twice, the dew point temperature reached 10 ° C. 180 seconds after the start of aeration, and the dew point temperature continued to decrease, and after 1800 seconds, which is the gaseous styrene collection time, the dew point temperature reached 4.2 ° C. Reached.

＜実施例５＞
ゼオライト系低減剤の調製例２のゼオライト系低減剤、ＭＳ−ＮＨを入れた、Ｇ２球状ガラスフィルターを具備した１００ｍＬ木下式ねじ口ガス吸収洗滌瓶（以下、「洗浄瓶」という。）に、２５℃の温度下、ガス状スチレン濃度５５０ｐｐｍ、２５℃相対湿度８０％の空気を１分間に１Ｌの速度で通気した。洗浄瓶を通過した空気の温度および相対湿度を温湿度データーロガー（ＲＨＴ−１０、アズワン（株）社）を用いて１０秒間隔で測定し、また、スチレン濃度をスチレン検知管（Ｎｏ．１２４、（株）ガステック社）を用いて１５分間隔で測定した。表６に、各ゼオライト系低減剤のガス状スチレン捕集時間、水素含有率、含水率、比表面積、露点温度０℃到達時間を示し、また、ＭＳ−ＮＨ、ＭＳ−Ｖ１５０、ＭＳ−Ｖ３００について、洗浄瓶を通過した空気の露点温度の時間毎の変化を図５に示した。図５の横軸は洗浄瓶に通気し始めた時からの経過時間、縦軸は露点温度である。 <Example 5>
Preparation of Zeolite Reducing Agent Into a 100 mL Kinoshita type screw mouth gas absorption washing bottle (hereinafter referred to as “washing bottle”) having a G2 spherical glass filter containing the zeolite reducing agent of Preparation Example 2 and MS-NH. Under a temperature of ° C., air with a gaseous styrene concentration of 550 ppm and 25 ° C. and a relative humidity of 80% was aerated at a rate of 1 L per minute. The temperature and relative humidity of the air passing through the washing bottle were measured at intervals of 10 seconds using a temperature / humidity data logger (RHT-10, ASONE Co., Ltd.), and the styrene concentration was measured with a styrene detector tube (No. 124, (Gastech Co., Ltd.) was measured at intervals of 15 minutes. Table 6 shows the gaseous styrene collection time, hydrogen content, water content, specific surface area, and dew point temperature 0 ° C. arrival time for each zeolite-based reducing agent, and for MS-NH, MS-V150, and MS-V300. FIG. 5 shows the change of the dew point temperature of the air passing through the washing bottle over time. The horizontal axis in FIG. 5 is the elapsed time from the start of aeration into the washing bottle, and the vertical axis is the dew point temperature.

なお、ＭＳ−ＮＨを除くゼオライト系低減剤は、洗浄瓶に入れる前に、１ヘクトパスカル以下、１５０℃１０時間処理し、引き続き１ヘクトパスカル以下で５０℃以下まで冷却する処理を行った。   In addition, the zeolitic reducing agent except MS-NH was treated at 1 hectopascal or lower at 150 ° C. for 10 hours and then cooled to 50 ° C. or lower at 1 hectopascal or lower before being placed in the washing bottle.

なおまた、ガス状スチレン捕集時間は、検知限度１ｐｐｍであるスチレン検知管（Ｎｏ．１２４、（株）ガステック社）を用いて洗浄瓶通過後の空気を測定した時に、スチレン検知管により検知されなかった通気開始後からの１５分間隔の時間であり、含水率は、洗浄瓶に入れた低減剤と同じものを含水率分析用の試料として、含水率試験を行った値である。   In addition, the gaseous styrene collection time is detected by the styrene detector tube when the air after passing through the washing bottle is measured using a styrene detector tube (No. 124, Gastec Co., Ltd.) having a detection limit of 1 ppm. It was a time of 15 minutes after the start of aeration, and the moisture content is a value obtained by conducting a moisture content test using the same reducing agent put in the washing bottle as a sample for moisture content analysis.



















なお、水素含有率、比表面積の値を決定するための試験において、各試験の分析試料に真空下、１５０℃加熱の前処理を行っていることから、表６に記載したＭＳ−ＮＨの水素含有率、比表面積の値は、ＭＳ−Ｖ１５０の値である。   In addition, in the test for determining the values of the hydrogen content and the specific surface area, the analysis sample of each test was pretreated by heating at 150 ° C. under vacuum. The value of content rate and specific surface area is the value of MS-V150.

図５に示すとおり、ＭＳ−Ｖ１５０、ＭＳ−Ｖ３００をそれぞれ入れた洗浄瓶を通過した空気は、通気開始からそれぞれ２６０、２５０秒間経過後に露点温度０℃以下に達した後、洗浄瓶を通過した空気中にスチレン検知管によりスチレンが検知されなかった通気開始からの経過時間まで、露点温度０℃以下を維持したが、ＭＳ−ＮＨを入れた洗浄瓶を通過した空気は、露点温度０℃に達しなかった。また、ＭＳ−Ｖ２００、ＭＳ−Ｖ２４７、ＭＳ−Ｖ４００、ＭＳ−Ｖ４８０をそれぞれ入れた洗浄瓶を通過した空気は、ＭＳ−Ｖ１５０、ＭＳ−Ｖ３００と同じように、表６の各露点温度０℃到達時間に示した通気開始からの経過時間に露点温度０℃以下に達した後、各洗浄瓶を通過した空気中にスチレン検知管によりスチレンが検知されなかった通気開始からの経過時間まで、露点温度０℃以下を維持した。   As shown in FIG. 5, the air that passed through the cleaning bottles containing MS-V150 and MS-V300 respectively reached the dew point of 0 ° C. or less after 260 and 250 seconds from the start of ventilation, and then passed through the cleaning bottles. The dew point temperature was maintained at 0 ° C. or less until the elapsed time from the start of ventilation when styrene was not detected by the styrene detector tube in the air, but the air that passed through the washing bottle containing MS-NH reached the dew point temperature of 0 ° C. Did not reach. In addition, the air that passed through the cleaning bottles containing MS-V200, MS-V247, MS-V400, and MS-V480 reached each dew point temperature of 0 ° C. in Table 6 as in MS-V150 and MS-V300. After the dew point temperature reached 0 ° C or less during the elapsed time from the start of ventilation shown in the time, the dew point temperature until the elapsed time from the start of ventilation when styrene was not detected by the styrene detector tube in the air that passed through each washing bottle Maintained below 0 ° C.

また、表２と表６の同じ真空下加熱処理温度のゼオライトを比べると、すべての真空下加熱処理温度で、粒径の小さなゼオライトを原料として用いている表６記載のゼオライトの方がガス状スチレンを長く捕集した。   Further, comparing zeolites having the same heat treatment temperature under vacuum in Tables 2 and 6, the zeolites shown in Table 6 using a small particle size zeolite as a raw material at all heat treatment temperatures under vacuum are more gaseous. Styrene was collected for a long time.

＜実施例６＞
ゼオライト系低減剤の調製例３のゼオライト系低減剤を１００ｍＬ入れた、Ｇ２球状ガラスフィルターを具備した１００ｍＬ木下式ねじ口ガス吸収洗滌瓶（以下、「洗浄瓶」という。）に、２５℃の温度下、ガス状スチレン濃度５５０ｐｐｍ、２５℃相対湿度８０％の空気を１分間に１Ｌの速度で通気した。洗浄瓶を通過した空気の温度および相対湿度を温湿度データーロガー（ＲＨＴ−１０、アズワン（株）社）を用いて１０秒間隔で測定し、また、スチレン濃度をスチレン検知管（Ｎｏ．１２４、（株）ガステック社）を用いて１５分間隔で測定した。表７に、各ゼオライト系低減剤のガス状スチレン捕集時間、水素含有率、含水率、比表面積、露点温度０℃到達時間を示し、また、図６に、ＭＢ−Ａ２００、ＭＢ−Ａ２４７、ＭＢ−Ａ３００、ＭＢ−Ａ４００をそれぞれ入れた洗浄瓶を通過した空気の露点温度の時間毎の変化を示した。図６の横軸は洗浄瓶に通気し始めた時からの経過時間、縦軸は露点温度である。 <Example 6>
Preparation of zeolite-based reducing agent 100 mL of the zeolite-based reducing agent of Preparation Example 3 and a 100 mL Kinoshita type screw mouth gas absorption washing bottle equipped with a G2 spherical glass filter (hereinafter referred to as “washing bottle”) at a temperature of 25 ° C. Below, air having a gaseous styrene concentration of 550 ppm and 25 ° C. and a relative humidity of 80% was aerated at a rate of 1 L per minute. The temperature and relative humidity of the air passing through the washing bottle were measured at intervals of 10 seconds using a temperature / humidity data logger (RHT-10, ASONE Co., Ltd.), and the styrene concentration was measured with a styrene detector tube (No. 124, (Gastech Co., Ltd.) was measured at intervals of 15 minutes. Table 7 shows the gaseous styrene collection time, hydrogen content, water content, specific surface area, and dew point temperature reaching time of 0 ° C. for each zeolite reducing agent, and FIG. 6 shows MB-A200, MB-A247, The change with time of the dew point temperature of the air which passed the washing bottle which put MB-A300 and MB-A400, respectively was shown. The horizontal axis in FIG. 6 is the elapsed time from the start of aeration in the washing bottle, and the vertical axis is the dew point temperature.

なお、ゼオライト系低減剤の調製例３のゼオライト系低減剤は、洗浄瓶に入れる前に、１ヘクトパスカル以下、１５０℃１０時間処理し、引き続き１ヘクトパスカル以下で５０℃以下まで冷却する処理を行った。   The zeolite-based reducing agent in Preparation Example 3 of the zeolite-based reducing agent was treated at 1 hectopascal or lower at 150 ° C. for 10 hours and subsequently cooled to 50 ° C. or lower at 1 hectopascal or lower before being placed in the washing bottle. .

なおまた、ガス状スチレン捕集時間は、検知限度１ｐｐｍであるスチレン検知管（Ｎｏ．１２４、（株）ガステック社）を用いて洗浄瓶通過後の空気を測定した時に、スチレン検知管により検知されなかった通気開始後からの１５分間隔の時間であり、含水率は、洗浄瓶に入れた低減剤と同じものを含水率分析用の試料として、含水率試験を行った値である。   In addition, the gaseous styrene collection time is detected by the styrene detector tube when the air after passing through the washing bottle is measured using a styrene detector tube (No. 124, Gastec Co., Ltd.) having a detection limit of 1 ppm. It was a time of 15 minutes after the start of aeration, and the moisture content is a value obtained by conducting a moisture content test using the same reducing agent put in the washing bottle as a sample for moisture content analysis.

















図６に示すとおり、含水率０．８５質量％以下、比表面積３９．７ｍ２／ｇ以上、水素含有率０．８６質量％以上のゼオライト系低減剤であるＭＢ−Ａ２００、ＭＢ−Ａ２４７、ＭＢ−Ａ３００、ＭＢ−Ａ４００をそれぞれ入れた洗浄瓶を通過した空気は、表７の各露点温度０℃到達時間に示した通気開始からの経過時間に、露点温度０℃以下に達した後、洗浄瓶を通過した空気中にスチレン検知管によりスチレンが検知されなかった通気開始からの経過時間まで、露点温度０℃以下を維持した。また、ＭＢ−Ａ４８０、ＭＢ−Ａ６００をそれぞれ入れた洗浄瓶を通過した空気も同じように、表７の各露点温度０℃到達時間に示した通気開始からの経過時間に、露点温度０℃以下に達した後、洗浄瓶を通過した空気中にスチレン検知管によりスチレンが検知されなかった通気開始からの経過時間まで、露点温度０℃以下を維持した。 As shown in FIG. 6, MB-A200, MB-A247, MB, which are zeolite-based reducing agents having a water content of 0.85% by mass or less, a specific surface area of 39.7m 2 / g or more, and a hydrogen content of 0.86% by mass or more. -The air that passed through the washing bottles containing A300 and MB-A400 reached the dew point temperature of 0 ° C or less in the elapsed time from the start of ventilation indicated in each dew point temperature of 0 ° C in Table 7, and then washed. The dew point temperature was maintained at 0 ° C. or lower until the elapsed time from the start of ventilation where styrene was not detected by the styrene detector tube in the air that passed through the bottle. Similarly, the air that has passed through the washing bottles containing MB-A480 and MB-A600 respectively has a dew point temperature of 0 ° C. or less at the elapsed time from the start of aeration shown in Table 7 at the time when each dew point temperature reaches 0 ° C. Then, the dew point temperature was maintained at 0 ° C. or lower until the elapsed time from the start of aeration when styrene was not detected by the styrene detector tube in the air that passed through the washing bottle.

含水率０．８５質量％以下、比表面積３９．７ｍ２／ｇ以上、水素含有率０．８６質量％以上のゼオライト系低減剤であるＭＢ−Ａ２００、ＭＢ−Ａ２４７、ＭＢ−Ａ３００、ＭＢ−Ａ４００、ＭＢ−Ａ４８０、ＭＢ−Ａ６００は、ガス状スチレンを１２０分間以上捕集した。 MB-A200, MB-A247, MB-A300, MB-A400 which are zeolite-based reducing agents having a water content of 0.85% by mass or less, a specific surface area of 39.7m 2 / g or more, and a hydrogen content of 0.86% by mass or more. MB-A480 and MB-A600 collected gaseous styrene for 120 minutes or more.

＜実施例７＞
粒径１．５〜３ｍｍの非加熱処理クリノプチロル型ゼオライト（秋田県能代市産出）（以下、「ＦＵ−ＮＨ」という。）、ＦＵ−ＮＨを１ヘクトパスカル以下で、１５０、９００℃のそれぞれの温度で１５分間加熱処理をしたゼオライト系低減剤（以下、１５０℃加熱処理ゼオライトを「ＦＵ−Ｖ１５０」、９００℃加熱処理ゼオライトを「ＦＵ−Ｖ９００」という。）、粒径１−２．６ｍｍのクリノプチロル型ゼオライト（北海道余市郡仁木町産出）（以下、「ＮＩ−ＮＨ」という。）、ＮＩ−ＮＨを１ヘクトパスカル以下で、１５０、９００℃のそれぞれの温度で１５分間加熱処理をしたゼオライト系低減剤（以下、１５０℃加熱処理ゼオライトを「ＮＩ−Ｖ１５０」、９００℃加熱処理ゼオライトを「ＮＩ−Ｖ９００」という。）のいずれかを１００ｍＬ入れた、Ｇ２球状ガラスフィルターを具備した１００ｍＬ木下式ねじ口ガス吸収洗滌瓶（以下、「洗浄瓶」という。）に、２５℃の温度下、ガス状スチレン濃度５５０ｐｐｍ、２５℃相対湿度８０％の空気を１分間に１Ｌの速度で通気した。洗浄瓶を通過した空気の温度および相対湿度を温湿度データーロガー（ＲＨＴ−１０、アズワン（株）社）を用いて１０秒間隔で測定し、また、スチレン濃度をスチレン検知管（Ｎｏ．１２４、（株）ガステック社）を用いて１５分間隔で測定した。表８に、各ゼオライト系低減剤のガス状スチレン捕集時間、水素含有率、含水率、比表面積、露点温度０℃到達時間を示し、また、図７に、洗浄瓶を通過した空気の露点温度の時間毎の変化示した。図７の横軸は洗浄瓶に通気し始めた時からの経過時間、縦軸は露点温度である。 <Example 7>
Non-heat treated clinoptilolite type zeolite (produced by Noshiro City, Akita Prefecture) with a particle size of 1.5-3 mm (hereinafter referred to as “FU-NH”), FU-NH of 1 hectopascal or less at temperatures of 150 and 900 ° C. Zeolitic reducing agent heat treated for 15 minutes (hereinafter, 150 ° C. heat-treated zeolite is referred to as “FU-V150”, 900 ° C. heat-treated zeolite is referred to as “FU-V900”), clinoptilol having a particle size of 1-2.6 mm Type zeolite (produced in Niki-cho, Yoichi-gun, Hokkaido) (hereinafter referred to as “NI-NH”), a zeolite-type reducing agent obtained by heat-treating NI-NH at a temperature of 1 hectopascal or less at 150 and 900 ° C. for 15 minutes. (Hereafter, 150 ° C. heat-treated zeolite is referred to as “NI-V150”, and 900 ° C. heat-treated zeolite is referred to as “NI-V900”.) Into a 100 mL Kinoshita type screw mouth gas absorption cleaning bottle (hereinafter referred to as “cleaning bottle”) equipped with a G2 spherical glass filter containing 100 mL of this, a gaseous styrene concentration of 550 ppm, relative to 25 ° C., at a temperature of 25 ° C. Air having a humidity of 80% was aerated at a rate of 1 L per minute. The temperature and relative humidity of the air passing through the washing bottle were measured at intervals of 10 seconds using a temperature / humidity data logger (RHT-10, ASONE Co., Ltd.), and the styrene concentration was measured with a styrene detector tube (No. 124, (Gastech Co., Ltd.) was measured at intervals of 15 minutes. Table 8 shows the gaseous styrene collection time, hydrogen content, moisture content, specific surface area, dew point temperature reaching time of 0 ° C. for each zeolite reducing agent, and FIG. 7 shows the dew point of the air that passed through the washing bottle. The change of temperature with time was shown. The horizontal axis in FIG. 7 is the elapsed time from the start of aeration in the washing bottle, and the vertical axis is the dew point temperature.

なお、ＦＵ−Ｖ１５０、ＦＵ−Ｖ９００、ＮＩ−Ｖ１５０、ＮＩ−Ｖ９００は、洗浄瓶に入れる前に、１ヘクトパスカル以下、１５０℃１０時間処理し、引き続き１ヘクトパスカル以下で５０℃以下まで冷却する処理を行った。   In addition, FU-V150, FU-V900, NI-V150, NI-V900 are processed at 1 hectopascal or lower at 150 ° C. for 10 hours and then cooled to 50 ° C. or lower at 1 hectopascal or lower before being placed in the washing bottle. went.

なおまた、ガス状スチレン捕集時間は、検知限度１ｐｐｍであるスチレン検知管（Ｎｏ．１２４、（株）ガステック社）を用いて洗浄瓶通過後の空気を測定した時に、スチレン検知管により検知されなかった通気開始後からの１５分間隔の時間であり、含水率は、洗浄瓶に入れた低減剤と同じものを含水率分析用の試料として、含水率試験を行った値である。   In addition, the gaseous styrene collection time is detected by the styrene detector tube when the air after passing through the washing bottle is measured using a styrene detector tube (No. 124, Gastec Co., Ltd.) having a detection limit of 1 ppm. It was a time of 15 minutes after the start of aeration, and the moisture content is a value obtained by conducting a moisture content test using the same reducing agent put in the washing bottle as a sample for moisture content analysis.

















なお、水素含有率、比表面積の値を決定するための試験において、各試験の分析試料に真空下、１５０℃加熱の前処理を行っていることから、表８に記載したＦＵ−ＮＨ、ＮＩ−ＮＨそれぞれの水素含有率、比表面積の値は、それぞれＦＵ−Ｖ１５０、ＮＩ−Ｖ１５０の値である。   In the tests for determining the values of hydrogen content and specific surface area, the analysis samples of each test were pretreated by heating at 150 ° C. under vacuum, so that FU-NH, NI described in Table 8 were used. The values of hydrogen content and specific surface area of —NH are the values of FU-V150 and NI-V150, respectively.

水素含有率０．９６質量％、含水率０．４９質量％、比表面積２０．４ｍ２／ｇのゼオライトであるＦＵ-Ｖ１５０は、ガス状スチレンを１５０分間捕集したが、ＦＵ−Ｖ１５０の原料であり含水率９．４１質量％のＦＵ−ＮＨ、水素含有率０．０８質量％、含水率０．００質量％、比表面積３．２３ｍ２／ｇのＦＵ−Ｖ９００はどちらもガス状スチレン捕集時間が１５分間未満であった。水素含有率１．１１質量％、含水率０．７６質量％、比表面積３０．５ｍ２／ｇのゼオライトであるＮＩ-Ｖ１５０は、ガス状スチレンを２２５分間捕集したが、ＮＩ−Ｖ１５０の原料であり含水率が１１．０質量％であるＮＩ−ＮＨ、水素含有率０．０７質量％、含水率０．００質量％、比表面積２．８６ｍ２／ｇのＮＩ−Ｖ９００はどちらもガス状スチレン捕集時間が１５分間未満であった。 FU-V150, which is a zeolite having a hydrogen content of 0.96% by mass, a water content of 0.49% by mass, and a specific surface area of 20.4 m 2 / g, collected gaseous styrene for 150 minutes. FU-NH900 having a moisture content of 9.41% by mass, hydrogen content of 0.08% by mass, moisture content of 0.00% by mass, and specific surface area of 3.23 m 2 / g are both gas styrene traps. The collection time was less than 15 minutes. NI-V150, which is a zeolite having a hydrogen content of 1.11% by mass, a water content of 0.76% by mass, and a specific surface area of 30.5 m 2 / g, collected gaseous styrene for 225 minutes. NI-NH900 having a water content of 11.0% by mass, a hydrogen content of 0.07% by mass, a water content of 0.00% by mass, and a specific surface area of 2.86 m 2 / g are both gaseous. The styrene collection time was less than 15 minutes.

図７に示すとおり、水素含有率０．９６質量％、含水率０．４９質量％、比表面積２０．４ｍ２／ｇのゼオライトであるＦＵ-Ｖ１５０、水素含有率１．１１質量％、含水率０．７６質量％、比表面積３０．５ｍ２／ｇのゼオライトであるＮＩ-Ｖ１５０をそれぞれ入れた洗浄瓶を通過した空気は、通気開始からそれぞれ３４０、１５０秒間経過後に露点温度０℃以下に達した後、洗浄瓶を通過した空気中にスチレン検知管によりスチレンが検知されなかった通気開始からの経過時間まで、露点温度０℃以下を維持した。ＦＵ−Ｖ１５０の原料であり含水率９．４１質量％のＦＵ−ＮＨを入れた洗浄瓶を通過した空気は通気開始から２９０秒経過後に最低露点温度８．９℃に達した後、通気開始から９００秒経過後には露点温度９．２℃まで微増した。水素含有率０．０８質量％、含水率０．００質量％、比表面積３．２３ｍ２／ｇのＦＵ−Ｖ９００を入れた洗浄瓶を通過した空気は通気開始から１４０秒経過後に最低露点温度１３．２℃に達した後、通気開始から９００秒経過後には露点温度１８℃まで上昇した。ＮＩ−Ｖ１５０の原料であり含水率１１．０質量％のＮＩ−ＮＨを入れた洗浄瓶を通過した空気は通気開始から２１０秒経過後に最低露点温度９．８℃に達した後、通気開始から９００秒経過後には露点温度１０℃まで微増した。水素含有率０．０７質量％、含水率０．００質量％、比表面積２．８６ｍ２／ｇのＮＩ−Ｖ９００を入れた洗浄瓶を通過した空気は露点温度２５．８℃からほとんど変化せず、通気開始から９００秒経過後においても２５．５℃であった。 As shown in FIG. 7, FU-V150 which is a zeolite having a hydrogen content of 0.96% by mass, a water content of 0.49% by mass and a specific surface area of 20.4 m 2 / g, a hydrogen content of 1.11% by mass, and a water content of The air that passed through the washing bottles containing NI-V150, a zeolite with a specific surface area of 30.5 m 2 / g, reached 0.70% by mass after 340 and 150 seconds from the start of ventilation. After that, the dew point temperature was maintained at 0 ° C. or lower until the elapsed time from the start of ventilation where styrene was not detected by the styrene detector tube in the air that passed through the washing bottle. The air that has passed through the washing bottle containing FU-NH, which is a raw material of FU-V150 and has a moisture content of 9.41% by mass, reaches the lowest dew point temperature of 8.9 ° C. after 290 seconds from the start of ventilation, After 900 seconds, the dew point temperature slightly increased to 9.2 ° C. The air that passed through the washing bottle containing FU-V900 having a hydrogen content of 0.08% by mass, a water content of 0.00% by mass, and a specific surface area of 3.23 m 2 / g had a minimum dew point of 13 seconds after 140 seconds from the start of ventilation. After reaching 2.degree. C., the dew point temperature rose to 18.degree. C. after 900 seconds from the start of aeration. After passing through a washing bottle containing NI-NH having a water content of 11.0% by mass as the raw material of NI-V150, after reaching the lowest dew point temperature of 9.8 ° C. after 210 seconds from the start of ventilation, After 900 seconds, the dew point temperature slightly increased to 10 ° C. The air that passed through the washing bottle containing NI-V900 having a hydrogen content of 0.07% by mass, a water content of 0.00% by mass, and a specific surface area of 2.86 m 2 / g hardly changed from the dew point temperature of 25.8 ° C. The temperature was 25.5 ° C. even after 900 seconds had elapsed from the start of ventilation.

＜実施例８＞
実施例７のＦＵ−Ｖ１５０、ＮＩ−Ｖ１５０を、室温、大気圧下で吸湿させ、含水率６．２１質量％に調製したＦＵ−Ｖ１５０、含水率６．２６質量％に調製したＮＩ−Ｖ１５０のいずれかを１００ｍＬ入れた、Ｇ２球状ガラスフィルターを具備した１００ｍＬ木下式ねじ口ガス吸収洗滌瓶（以下、「洗浄瓶」という。）に、２５℃の温度下、ガス状スチレン濃度５５０ｐｐｍ、２５℃相対湿度８０％の空気を１分間に１Ｌの速度で通気した。洗浄瓶を通過した空気の温度および相対湿度を温湿度データーロガー（ＲＨＴ−１０、アズワン（株）社）を用いて１０秒間隔で測定し、また、スチレン濃度をスチレン検知管（Ｎｏ．１２４、（株）ガステック社）を用いて１５分間隔で測定した。表９に、各ゼオライトのガス状スチレン捕集時間、水素含有率、比表面積、含水率、露点温度０℃到達時間を示し、また、図８に、含水率６．２１質量％ＦＵ−Ｖ１５０、含水率６．２６質量％ＮＩ−Ｖ１５０それぞれを入れた洗浄瓶を通過した空気の露点温度の時間毎の変化示した。図８の横軸は洗浄瓶に通気し始めた時からの経過時間、縦軸は露点温度である。 <Example 8>
FU-V150 and NI-V150 of Example 7 were absorbed at room temperature and atmospheric pressure, FU-V150 prepared to a moisture content of 6.21% by mass, and NI-V150 prepared to a moisture content of 6.26% by mass A 100 mL Kinoshita type screw mouth gas absorption cleaning bottle (hereinafter referred to as “cleaning bottle”) equipped with a G2 spherical glass filter containing either 100 mL, at a temperature of 25 ° C., a gaseous styrene concentration of 550 ppm, relative to 25 ° C. Air having a humidity of 80% was aerated at a rate of 1 L per minute. The temperature and relative humidity of the air passing through the washing bottle were measured at intervals of 10 seconds using a temperature / humidity data logger (RHT-10, ASONE Co., Ltd.), and the styrene concentration was measured with a styrene detector tube (No. 124, (Gastech Co., Ltd.) was measured at intervals of 15 minutes. Table 9 shows the gaseous styrene collection time, hydrogen content, specific surface area, water content, and dew point temperature arrival time of 0 ° C. for each zeolite, and FIG. 8 shows a water content of 6.21% by mass FU-V150. The change with time of the dew point temperature of the air which passed the washing | cleaning bottle containing each water content 6.26 mass% NI-V150 was shown. The horizontal axis in FIG. 8 is the elapsed time from the start of aeration into the washing bottle, and the vertical axis is the dew point temperature.












なお、表９、図８の含水率０．４９質量％のＦＵ−Ｖ１５０、含水率０．７６質量％のＮＩ−Ｖ１５０は、実施例７のデータである。   The FU-V150 with a moisture content of 0.49% by mass and NI-V150 with a moisture content of 0.76% by mass in Table 9 and FIG.

含水率０．４９質量％、６．２１質量％それぞれのＦＵ−Ｖ１５０のガス状スチレン捕集時間は、それぞれ１５０分間、６０分間であり、含水率が高くなると捕集時間が短くなった。また、含水率０．７６質量％、６．２６質量％それぞれのＮＩ−Ｖ１５０のガス状スチレン捕集時間は、それぞれ２２５分間、４５分間であり、ＦＵ−Ｖ１５０と同じく、含水率が高くなると捕集時間が短くなった。   Gaseous styrene collection times of FU-V150 with water content of 0.49% by mass and 6.21% by mass were 150 minutes and 60 minutes, respectively, and the collection time became shorter as the water content increased. In addition, the NI-V150 gaseous styrene collection times of 0.76% by mass and 6.26% by mass, respectively, were 225 minutes and 45 minutes, respectively. As with FU-V150, when the moisture content increased, The gathering time has been shortened.

図８に示したとおり、含水率が異なるＦＵ−Ｖ１５０、ＮＩ−Ｖ１５０を入れた洗浄瓶を通過した空気は、表９の露点温度０℃到達時間に示した通気開始からの経過時間に、露点温度０℃以下に達した後、洗浄瓶を通過した空気中にスチレン検知管によりスチレンが検知されなかった通気開始からの経過時間まで、露点温度０℃以下を維持した。   As shown in FIG. 8, the air that passed through the washing bottles containing FU-V150 and NI-V150 having different moisture contents had a dew point at the elapsed time from the start of ventilation shown in Table 9 at the time when the dew point temperature reached 0 ° C. After the temperature reached 0 ° C. or lower, the dew point temperature was maintained at 0 ° C. or lower until the elapsed time from the start of aeration when styrene was not detected by the styrene detector tube in the air that passed through the washing bottle.

＜比較例１＞
天然ゼオライトを原料とするアイリスオーヤマ（株）社「床下さらり」を粗粉砕し、粒径１−１．７ｍｍにしたゼオライト（以下、「ＡＩ−ＮＨ」という。）を容量で１００ｍＬ、重量では８３．９ｇ入れた、Ｇ２球状ガラスフィルターを具備した１００ｍＬ木下式ねじ口ガス吸収洗滌瓶（以下、「洗浄瓶」という。）に、２５℃の温度下、ガス状スチレン濃度５５０ｐｐｍ、２５℃相対湿度８０％の空気を１分間に１Ｌの速度で通気した。洗浄瓶を通過した空気の温度および相対湿度を温湿度データーロガー（ＲＨＴ−１０、アズワン（株）社）を用いて１０秒間隔で測定し、また、スチレン濃度をスチレン検知管（Ｎｏ．１２４、（株）ガステック社）を用いて１５分間隔で測定した。 <Comparative Example 1>
Iris Oyama Co., Ltd. “floor under floor” made of natural zeolite is coarsely pulverized to give a zeolite having a particle size of 1 to 1.7 mm (hereinafter referred to as “AI-NH”) in a volume of 100 mL and a weight of 83 In a 100 mL Kinoshita-type screw mouth gas absorption washing bottle (hereinafter referred to as “washing bottle”) equipped with a G2 spherical glass filter in an amount of .9 g, a gaseous styrene concentration of 550 ppm and a relative humidity of 80 at 25 ° C. % Air was aerated at a rate of 1 L per minute. The temperature and relative humidity of the air passing through the washing bottle were measured at intervals of 10 seconds using a temperature / humidity data logger (RHT-10, ASONE Co., Ltd.), and the styrene concentration was measured with a styrene detector tube (No. 124, (Gastech Co., Ltd.) was measured at intervals of 15 minutes.

ＡＩ−ＮＨは、比表面積３０．７ｍ２／ｇ、水素含有率１．０３質量％、含水率１４．４質量％であり、また、ガス状スチレン捕集時間が１５分間未満と、ガス状スチレンの捕集能が極めて低く、また、水蒸気の捕集能も、通気開始時における温湿度計設置箇所の初発露点温度１５．５℃から通気開始後すぐに露点温度が上昇する結果を示し、水蒸気の捕集能は極めて低かった。なお、1ヘクトパスカル、１５０℃１０時間加熱処理した比表面積３０．７ｍ２／ｇ、水素含有率１．０３質量％、含水率０．７０質量％のＡＩ−ＮＨは、ガス状スチレン捕集能、水蒸気捕集能のどちらにも顕著な能力の向上が認められた。 AI-NH has a specific surface area of 30.7 m 2 / g, a hydrogen content of 1.03 mass%, a water content of 14.4 mass%, and a gaseous styrene collection time of less than 15 minutes. The trapping ability of water vapor is extremely low, and the steam trapping ability also shows a result that the dew point temperature rises immediately after the start of ventilation from the initial dew point temperature of 15.5 ° C at the location of the thermo-hygrometer at the start of ventilation. The collection ability of was extremely low. In addition, AI-NH having a specific surface area of 30.7 m 2 / g, a hydrogen content of 1.03% by mass, and a water content of 0.70% by mass, heated at 150 ° C. for 10 hours at 1 hectopascal, is capable of collecting gaseous styrene, A marked improvement in capacity was observed for both water vapor collection capacities.

＜実施例９＞
１ヘクトパスカル以下、１５０℃１０時間加熱処理したゼオライト系低減剤の調製例１のＭＢ−Ｖ４８０を入れた、Ｇ２球状ガラスフィルターを具備した１００ｍＬ木下式ねじ口ガス吸収洗滌瓶（以下、「洗浄瓶」という。）に、２５℃の温度下、ガス状トルエン濃度６００ｐｐｍ、２５℃相対湿度８０％の空気を１分間に１Ｌの速度で通気した。洗浄瓶を通過した空気の温度および相対湿度を温湿度データーロガー（ＲＨＴ−１０、アズワン（株）社）を用いて１０秒間隔で測定し、また、ガス状トルエン濃度をトルエン検知管（Ｎｏ．１２２、（株）ガステック社）を用いて１５分間隔で測定した。また、ガス状トルエンの代わりに、ガス状キシレン、ガス状オルトージクロロベンゼン、ガス状アニリン、ガス状ピリジンを用いて同様な実験を行った。表１０に、ガス状トルエン、ガス状キシレン、ガス状オルトージクロロベンゼン、ガス状アニリン、ガス状ピリジンの濃度を測定するために用いたそれぞれのガステック社製検知管、使用したガステック社製検知管の検知限度、洗浄瓶に導入したガス状トルエン、ガス状キシレン、ガス状オルトージクロロベンゼン、ガス状アニリン、ガス状ピリジンそれぞれの初発濃度、ガス状トルエン、ガス状キシレン、ガス状オルトージクロロベンゼン、ガス状アニリン、ガス状ピリジンそれぞれの捕集時間、洗浄瓶に入れたＭＢ−Ｖ４８０の含水率、露点温度０℃到達時間、洗浄瓶に入れたＭＢ−Ｖ４８０の重量を示した。また、図９に、ガス状トルエン、ガス状キシレン、ガス状オルトージクロロベンゼン、ガス状アニリン、ガス状ピリジンを含むそれぞれの空気が洗浄瓶を通過した後の空気の露点温度の時間毎の変化を示した。図９の横軸は洗浄瓶に通気し始めた時からの経過時間、縦軸は露点温度である。 <Example 9>
100 mL Kinoshita-type screw mouth gas absorption washing bottle (hereinafter referred to as “washing bottle”) equipped with a G2 spherical glass filter containing MB-V480 of Preparation Example 1 of zeolite-based reducing agent heat-treated at 150 ° C. for 10 hours or less at 1 hectopascal. The air having a gaseous toluene concentration of 600 ppm and a relative humidity of 25% at a temperature of 25 ° C. was aerated at a rate of 1 L per minute. The temperature and relative humidity of the air that passed through the washing bottle were measured at intervals of 10 seconds using a temperature / humidity data logger (RHT-10, ASONE Co., Ltd.), and the gaseous toluene concentration was measured with a toluene detector tube (No. 122, Gastec Co., Ltd.) at intervals of 15 minutes. Similar experiments were conducted using gaseous xylene, gaseous orthodichlorobenzene, gaseous aniline and gaseous pyridine instead of gaseous toluene. Table 10 shows the gas-tech detector tubes used to measure the concentrations of gaseous toluene, gaseous xylene, gaseous orthodichlorobenzene, gaseous aniline, and gaseous pyridine, and the gas-tech detectors used. Tube detection limit, gaseous toluene introduced into the washing bottle, gaseous xylene, gaseous orthodichlorobenzene, gaseous aniline, initial concentration of gaseous pyridine, gaseous toluene, gaseous xylene, gaseous orthodichlorobenzene, The collection time of gaseous aniline and gaseous pyridine, the water content of MB-V480 in the washing bottle, the dew point temperature reaching time of 0 ° C., and the weight of MB-V480 in the washing bottle are shown. In addition, FIG. 9 shows the change over time in the dew point temperature of air after each air containing gaseous toluene, gaseous xylene, gaseous orthodichlorobenzene, gaseous aniline, and gaseous pyridine passes through the washing bottle. Indicated. The horizontal axis in FIG. 9 is the elapsed time from the start of aeration into the washing bottle, and the vertical axis is the dew point temperature.















なお、含水率は、ガス状トルエン、ガス状キシレン、ガス状オルトージクロロベンゼン、ガス状アニリン、ガス状ピリジンをそれぞれ含む空気を通過させた洗浄瓶に入れた低減剤と同じものを含水率分析用の試料として含水率試験を行った値である。ガス状トルエンの捕集時間は、検知限度１ｐｐｍであるトルエン検知管（Ｎｏ．１２２、（株）ガステック社）を用いて洗浄瓶通過後の空気を測定した時に、トルエン検知管により検知されなかった通気開始後からの１５分間隔の時間であり、ガス状キシレンの捕集時間は、検知限度１ｐｐｍであるキシレン検知管（Ｎｏ．１２３、（株）ガステック社）を用いて洗浄瓶通過後の空気を測定した時に、キシレン検知管により検知されなかった通気開始後からの１５分間隔の時間であり、ガス状オルトージクロロベンゼンの捕集時間は検知限度１ｐｐｍであるオルトージクロロベンゼン検知管（Ｎｏ．１２７、（株）ガステック社）を用いて洗浄瓶通過後の空気を測定した時に、オルトージクロロベンゼン検知管により検知されなかった通気開始後からの１５分間隔の時間である。ガス状アニリンの捕集時間は、検知限度０．２５ｐｐｍであるアニリン検知管（Ｎｏ．１８１、（株）ガステック社）を用いて洗浄瓶通過後の空気を測定した時に、通気開始から３６０分間経過後においてアニリン検知管により検知されなかったことを示し、ガス状ピリジンの捕集時間は、検知限度０．１ｐｐｍであるピリジン検知管（Ｎｏ．１８２、（株）ガステック社）を用いて洗浄瓶通過後の空気を測定した時に、通気開始から３６０分間経過後においてピリジン検知管により検知されなかったことを示す。   The moisture content is the same as that of the reducing agent placed in the washing bottle through which air containing gaseous toluene, gaseous xylene, gaseous orthodichlorobenzene, gaseous aniline and gaseous pyridine has been passed. It is the value which performed the moisture content test as a sample of this. The collection time of gaseous toluene is not detected by the toluene detector tube when the air after passing through the washing bottle is measured using a toluene detector tube (No. 122, Gastec Co., Ltd.) having a detection limit of 1 ppm. 15 minutes after the start of ventilation, and the collection time of gaseous xylene is after passing through the washing bottle using a xylene detector tube (No. 123, Gastec Co., Ltd.) having a detection limit of 1 ppm. This is a period of 15 minutes from the start of ventilation that was not detected by the xylene detector tube when the air was measured, and the collection time of gaseous orthodichlorobenzene was a detection limit of 1 ppm. 127, Gastech Co., Ltd.) was used to measure the air after passing through the washing bottle, and venting was not detected by the ortho-dichlorobenzene detector tube. Is the time of 15-minute intervals from the post. The collection time of gaseous aniline was 360 minutes from the start of ventilation when the air after passing through the washing bottle was measured using an aniline detector tube (No.181, Gastec Co., Ltd.) having a detection limit of 0.25 ppm. After the lapse of time, it was not detected by the aniline detector tube, and the collection time of gaseous pyridine was cleaned using a pyridine detector tube (No. 182; Gastec Co., Ltd.) with a detection limit of 0.1 ppm. When the air after passing through the bottle was measured, it was not detected by the pyridine detector tube after 360 minutes from the start of ventilation.

トルエン、キシレン、オルト−ジクロロベンゼンすべての芳香族系有機溶剤において、ＭＢ−Ｖ４８０は、ガス状芳香族系有機溶剤を捕集し、また、露点温度０℃に通気開始から２３０〜７００秒で到達した後、各洗浄瓶を通過した空気中に各芳香族系有機溶剤用の検知管により芳香族系有機溶剤が検知されなかった通気開始からの経過時間まで、露点温度０℃以下を維持した。アニリン、キシレンにおいては、ＭＢ−Ｖ４８０は、ガス状のアニリン、ピリジンともに３６０分間以上捕集し、また、露点温度０℃に通気開始から４１０、１２２０秒後にそれぞれ到達した後、通気開始から１８２２０、１６８７０秒後まで露点温度０℃以下を維持した。   In all aromatic organic solvents such as toluene, xylene, and ortho-dichlorobenzene, MB-V480 collects gaseous aromatic organic solvents and reaches a dew point of 0 ° C in 230 to 700 seconds from the start of aeration. After that, the dew point temperature was maintained at 0 ° C. or lower until the elapsed time from the start of aeration when the aromatic organic solvent was not detected by the detector tube for each aromatic organic solvent in the air that passed through each washing bottle. In aniline and xylene, MB-V480 collects both gaseous aniline and pyridine for 360 minutes or more, and reaches a dew point of 0 ° C. 410, 1220 seconds after the start of aeration, then 18220, The dew point temperature was maintained at 0 ° C. or lower until 16870 seconds.

＜実施例１０＞
１ヘクトパスカル以下、１５０℃１０時間加熱処理したゼオライト系低減剤の調製例２のＭＳ−Ｖ１５０を入れた、Ｇ２球状ガラスフィルターを具備した１００ｍＬ木下式ねじ口ガス吸収洗滌瓶（以下、「洗浄瓶」という。）に、２５℃の温度下、ガス状テトラヒドロフラン濃度８００ｐｐｍ、２５℃相対湿度８０％の空気を１分間に１Ｌの速度で通気した。洗浄瓶を通過した空気の温度および相対湿度を温湿度データーロガー（ＲＨＴ−１０、アズワン（株）社）を用いて１０秒間隔で測定し、また、ガス状テトラヒドロフラン濃度をテトラヒドロフラン検知管（Ｎｏ．１５９、（株）ガステック社）を用いて１５分間隔で測定した。なお、ガス状テトラヒドロフランの濃度を測定するために用いたガステック社製テトラヒドロフラン検知管（Ｎｏ．１５９）の検知限度は２ｐｐｍ、洗浄瓶に導入したガス状テトラヒドロフランの初発濃度は８００ｐｐｍ、洗浄瓶に入れたＭＳ−Ｖ１５０の水素含有率は１．０８質量％、含水率は０．７３質量％、比表面積１９９ｍ２／ｇ、洗浄瓶に入れたＭＳ−Ｖ１５０の重量は６０．０ｇである。図１０に、ガス状テトラヒドロフランを含む空気が洗浄瓶を通過した後の空気の露点温度の時間毎の変化を示した。図１０の横軸は洗浄瓶に通気し始めた時からの経過時間、縦軸は露点温度である。 <Example 10>
100 mL Kinoshita type screw mouth gas absorption washing bottle (hereinafter referred to as “washing bottle”) equipped with a G2 spherical glass filter containing MS-V150 of Preparation Example 2 of zeolite-based reducing agent heat-treated at 150 ° C. for 10 hours or less at 1 hectopascal. The air at a temperature of 25 ° C. was aerated at a rate of 1 L per minute with a gaseous tetrahydrofuran concentration of 800 ppm and 25 ° C. and a relative humidity of 80%. The temperature and relative humidity of the air that passed through the washing bottle were measured at intervals of 10 seconds using a temperature / humidity data logger (RHT-10, ASONE Co., Ltd.), and the gaseous tetrahydrofuran concentration was measured using a tetrahydrofuran detector tube (No. 159, Gastec Co., Ltd.) and measured at intervals of 15 minutes. The detection limit of the tetrahydrofuran detector tube (No. 159) manufactured by GASTEC, which was used to measure the concentration of gaseous tetrahydrofuran, was 2 ppm, and the initial concentration of gaseous tetrahydrofuran introduced into the cleaning bottle was 800 ppm. MS-V150 has a hydrogen content of 1.08% by mass, a water content of 0.73% by mass, a specific surface area of 199 m 2 / g, and the weight of MS-V150 in a washing bottle is 60.0 g. FIG. 10 shows the change over time in the dew point temperature of the air after the air containing gaseous tetrahydrofuran has passed through the washing bottle. The horizontal axis in FIG. 10 is the elapsed time from the start of aeration into the washing bottle, and the vertical axis is the dew point temperature.

なお、含水率は、ガス状テトラヒドロフランを含む空気を通過させた洗浄瓶に入れた低減剤と同じものを含水率分析用の試料として含水率試験を行った値である。   The water content is a value obtained by conducting a water content test using the same reducing agent as that contained in a washing bottle through which air containing gaseous tetrahydrofuran has been passed, as a sample for water content analysis.

ＭＳ−Ｖ１５０は、検知限度２ｐｐｍであるテトラヒドロフラン検知管（Ｎｏ．１５９、（株）ガステック社）を用いて、１５分間隔で洗浄瓶通過後の空気のテトラヒドロフラン濃度を測定した結果、通気開始後から１８０分間ガス状テトラヒドロフランを検知管の検知限度未満の濃度にし、また通気開始後から４５０秒で洗浄瓶通過後の空気の露点温度を０℃にした後、少なくとも洗浄瓶を通過した空気中にテトラヒドロフラン検知管によりテトラヒドロフランが検知されなかった通気開始からの経過時間まで、露点温度０℃以下を維持した。   MS-V150 measured the tetrahydrofuran concentration of the air after passing the washing bottle at intervals of 15 minutes using a tetrahydrofuran detector tube (No. 159, Gastec Co., Ltd.) having a detection limit of 2 ppm. After 180 minutes from the start of ventilation, the gaseous tetrahydrofuran is made to a concentration lower than the detection limit of the detector tube, and after 450 seconds from the start of ventilation, the dew point temperature of the air after passing through the washing bottle is set to 0 ° C., and at least in the air passing through the washing bottle The dew point temperature was maintained at 0 ° C. or lower until the elapsed time from the start of aeration when tetrahydrofuran was not detected by the tetrahydrofuran detector tube.

＜実施例１１＞
含水率が異なるゼオライト系低減剤の調製例２のＭＳ−Ｖ１５０を１００ｍＬ入れた、Ｇ２球状ガラスフィルターを具備した１００ｍＬ木下式ねじ口ガス吸収洗滌瓶（以下、「洗浄瓶」という。）に、２５℃の温度下、ガス状ヘキサン濃度６００ｐｐｍ、２５℃相対湿度８０％の空気を１分間に１Ｌの速度で通気した。洗浄瓶を通過した空気の温度および相対湿度を温湿度データーロガー（ＲＨＴ−１０、アズワン（株）社）を用いて１０秒間隔で測定し、また、ヘキサン濃度をヘキサン検知管（Ｎｏ．１０２Ｌ、（株）ガステック社）を用いて１５分間隔で測定した。表１１に、それぞれの含水率が異なるＭＳ−Ｖ１５０のガス状ヘキサン捕集時間、露点温度０℃到達時間、洗浄瓶に入れたＭＳ−Ｖ１５０の重量を示し、図１１に、洗浄瓶を通過した空気の露点温度の時間毎の変化示した。図１１の横軸は洗浄瓶に通気し始めた時からの経過時間、縦軸は露点温度である。 <Example 11>
25 in a 100 mL Kinoshita-type screw mouth gas absorption cleaning bottle (hereinafter referred to as “cleaning bottle”) equipped with a G2 spherical glass filter containing 100 mL of MS-V150 of Preparation Example 2 of zeolite-based reducing agent having different water contents. Under a temperature of ° C., air having a gaseous hexane concentration of 600 ppm and 25 ° C. and a relative humidity of 80% was aerated at a rate of 1 L per minute. The temperature and relative humidity of the air that passed through the washing bottle were measured at 10 second intervals using a temperature / humidity data logger (RHT-10, ASONE Co., Ltd.), and the hexane concentration was measured with a hexane detector tube (No. 102L, (Gastech Co., Ltd.) was measured at intervals of 15 minutes. Table 11 shows the gaseous hexane collection time of MS-V150 having different moisture contents, the dew point temperature reaching time of 0 ° C., and the weight of MS-V150 in the washing bottle, and FIG. 11 passed through the washing bottle. The change of the dew point temperature of air with time was shown. The horizontal axis in FIG. 11 is the elapsed time from the start of aeration into the washing bottle, and the vertical axis is the dew point temperature.

なお、含水率が異なるＭＳ−Ｖ１５０は、室温、大気圧下で吸湿させたＭＳ−Ｖ１５０を、適宜、１ヘクトパスカル以下、１１０℃以下の温度で２時間加熱処理することで調製した。また、加熱処理した含水率が異なるＭＳ−Ｖ１５０は、温度が５０℃以下であることを確認した後、大気を導入して取り出し、直ちに洗浄瓶に入れて実験を行った。   MS-V150 having different moisture contents was prepared by appropriately heat-treating MS-V150 that had been absorbed at room temperature and atmospheric pressure at a temperature of 1 hectopascal or lower and 110 ° C. or lower for 2 hours. Moreover, after confirming that the heat-treated MS-V150 having a different moisture content had a temperature of 50 ° C. or less, the atmosphere was introduced and taken out, and the experiment was performed immediately after putting it in a washing bottle.

なおまた、ガス状ヘキサン捕集時間は、検知限度１ｐｐｍであるヘキサン検知管（Ｎｏ．１０２Ｌ、（株）ガステック社）を用いて洗浄瓶通過後の空気を測定した時に、ヘキサン検知管により検知されなかった通気開始後からの１５分間隔の時間であり、含水率は、洗浄瓶に入れた低減剤と同じものを含水率分析用の分析試料として、含水率試験を行った値である。   In addition, the gaseous hexane collection time is detected by the hexane detector tube when the air after passing through the washing bottle is measured using a hexane detector tube (No. 102L, Gastec Co., Ltd.) having a detection limit of 1 ppm. This is a time of 15 minutes after the start of aeration, and the moisture content is a value obtained by conducting a moisture content test using the same reducing agent put in the washing bottle as an analysis sample for moisture content analysis.


ＭＳ−Ｖ１５０の含水率が低下するに従い、ガス状ヘキサン捕集時間が長くなり、含水率０．７６質量％ではガス状ヘキサン捕集時間７５分間、含水率１．８７質量％ではガス状ヘキサン捕集時間４５分間、含水率４．６０質量％ではガス状ヘキサン捕集時間１５分間であった。また、図１１に示したとおり、各含水率が異なるＭＳ−Ｖ１５０を入れた洗浄瓶を通過した空気は、表１１の露点温度０℃到達時間に示した通気開始からの経過時間に露点温度０℃に達した後、少なくとも洗浄瓶を通過した空気中にヘキサン検知管によりヘキサンが検知されなかった通気開始からの経過時間まで、露点温度０℃以下を維持した。   As the moisture content of MS-V150 decreases, the gaseous hexane collection time becomes longer. When the moisture content is 0.76% by mass, the gaseous hexane is collected for 75 minutes, and when the moisture content is 1.87% by mass, the gaseous hexane is collected. At a collection time of 45 minutes and a moisture content of 4.60% by mass, gaseous hexane was collected for 15 minutes. In addition, as shown in FIG. 11, the air that passed through the washing bottles containing MS-V150 having different moisture contents had a dew point temperature of 0 at the elapsed time from the start of aeration shown in Table 11 at the time when the dew point temperature reached 0 ° C. After reaching 0 ° C., the dew point temperature was maintained at 0 ° C. or lower until at least the elapsed time from the start of ventilation where hexane was not detected by the hexane detector tube in the air that passed through the washing bottle.

＜実施例１２＞
ゼオライト系低減剤の調製例２のＭＳ−Ｖ１５０を１００ｍＬ入れた、Ｇ２球状ガラスフィルターを具備した１００ｍＬ木下式ねじ口ガス吸収洗滌瓶（以下、「洗浄瓶」という。）に、２５℃の温度下、ガス状ヘキサン濃度６００ｐｐｍ、２５℃相対湿度１５、５０％それぞれの空気を１分間に１Ｌの速度で通気した。洗浄瓶を通過した空気の温度および相対湿度を温湿度データーロガー（ＲＨＴ−１０、アズワン（株）社）を用いて１０秒間隔で測定し、また、ガス状ヘキサン濃度をヘキサン検知管（Ｎｏ．１０２Ｌ、（株）ガステック社）を用いて１５分間隔で測定した。表１２に、２５℃相対湿度１５、５０％それぞれのガス状ヘキサン捕集時間、ＭＳ−Ｖ１５０の含水率、露点温度０℃到達時間、洗浄瓶に入れたＭＳ−Ｖ１５０の重量を示し、図１２に、洗浄瓶を通過した空気の露点温度の時間毎の変化示した。図１２の横軸は洗浄瓶に通気し始めた時からの経過時間、縦軸は露点温度である。 <Example 12>
Preparation of zeolite-based reducing agent MS-V150 of Preparation Example 2 in 100 mL Kinoshita type screw mouth gas absorption washing bottle (hereinafter referred to as “washing bottle”) equipped with a G2 spherical glass filter at a temperature of 25 ° C. In addition, air of gaseous hexane concentration of 600 ppm, 25 ° C. relative humidity of 15 and 50% was aerated at a rate of 1 L per minute. The temperature and relative humidity of the air that passed through the washing bottle were measured at intervals of 10 seconds using a temperature / humidity data logger (RHT-10, ASONE Co., Ltd.), and the gaseous hexane concentration was measured with a hexane detector tube (No. 102L, Gastec Co., Ltd.) and measured at intervals of 15 minutes. Table 12 shows the gaseous hexane collection time at 25 ° C. relative humidity of 15 and 50%, the moisture content of MS-V150, the dew point temperature reaching time of 0 ° C., and the weight of MS-V150 in the washing bottle. The change of the dew point temperature of the air which passed the washing bottle for every time was shown. The horizontal axis in FIG. 12 is the elapsed time from the start of aeration in the washing bottle, and the vertical axis is the dew point temperature.

なお、ＭＳ−Ｖ１５０は、洗浄瓶に入れる前に、１ヘクトパスカル以下、１５０℃１０時間処理し、引き続き１ヘクトパスカル以下で５０℃以下まで冷却する処理を行った。   MS-V150 was treated at 1 hectopascal or lower at 150 ° C. for 10 hours and then cooled to 50 ° C. or lower at 1 hectopascal or lower before being placed in a washing bottle.

なおまた、ガス状ヘキサン捕集時間は、検知限度１ｐｐｍであるヘキサン検知管（Ｎｏ．１０２Ｌ、（株）ガステック社）を用いて洗浄瓶通過後の空気を測定した時に、ヘキサン検知管により検知されなかった通気開始後からの１５分間隔の時間であり、含水率は、洗浄瓶に入れた低減剤と同じものを含水率分析用の分析試料として、含水率試験を行った値である。   In addition, the gaseous hexane collection time is detected by the hexane detector tube when the air after passing through the washing bottle is measured using a hexane detector tube (No. 102L, Gastec Co., Ltd.) having a detection limit of 1 ppm. This is a time of 15 minutes after the start of aeration, and the moisture content is a value obtained by conducting a moisture content test using the same reducing agent put in the washing bottle as an analysis sample for moisture content analysis.



なお、そして、表１２、図１２の２５℃相対湿度８０％は、実施例１１の含水率０．７６質量％のＭＳ−Ｖ１５０のデータである。   And the 25 degreeC relative humidity 80% of Table 12, FIG. 12 is the data of MS-V150 of the water content of 0.76 mass% of Example 11. FIG.

ガス状ヘキサンが含まれる２５℃相対湿度１５、５０、８０％の空気をそれぞれＭＳ−Ｖ１５０を入れた洗浄瓶に通過させた場合のガス状ヘキサン捕集時間は、それぞれ９０、７５、７５分間であった。また、ガス状ヘキサンが含まれる２５℃相対湿度１５、５０、８０％の空気をそれぞれＭＳ−Ｖ１５０を入れた洗浄瓶に通過させた場合は、通気開始からそれぞれ２８０、４６０、４００秒間経過後に露点温度０℃以下に達した後、少なくとも洗浄瓶を通過した空気中にヘキサン検知管によりヘキサンが検知されなかった通気開始からの経過時間まで、露点温度０℃以下を維持した。   Gaseous hexane collection time when air of 25 ° C relative humidity 15, 50, and 80% containing gaseous hexane is passed through a washing bottle containing MS-V150 is 90, 75, and 75 minutes, respectively. there were. In addition, when air at 25 ° C. and a relative humidity of 15, 50, and 80% containing gaseous hexane is passed through a washing bottle containing MS-V150, the dew points are 280, 460, and 400 seconds after the start of ventilation, respectively. After reaching the temperature of 0 ° C. or lower, the dew point temperature of 0 ° C. or lower was maintained until at least the elapsed time from the start of aeration when hexane was not detected by the hexane detector tube in the air that passed through the washing bottle.

＜実施例１３＞
ゼオライト系低減剤の調製例２のＭＳ−Ｖ１５０を１００ｍＬ入れた、Ｇ２球状ガラスフィルターを具備した１００ｍＬ木下式ねじ口ガス吸収洗滌瓶（以下、「洗浄瓶」という。）に、５℃の温度下、ガス状ヘキサン濃度６００ｐｐｍ、５℃相対湿度９０％の空気を１分間に１Ｌの速度で通気した。洗浄瓶を通過した空気の温度および相対湿度を温湿度データーロガー（ＲＨＴ−１０、アズワン（株）社）を用いて１０秒間隔で測定し、また、ヘキサン濃度をヘキサン検知管（Ｎｏ．１０２Ｌ、（株）ガステック社）を用いて１５分間隔で測定した。また、５℃の温度下、ガス状ヘキサン濃度６００ｐｐｍ、５℃相対湿度９０％の空気の条件の代わりに、４０℃の温度下、ガス状ヘキサン濃度６００ｐｐｍ、４０℃相対湿度８０％の空気を用いて、同じ通気試験を行った。表１３に、５℃相対湿度９０％、４０℃相対湿度８０％それぞれのガス状ヘキサン捕集時間、ＭＳ−Ｖ１５０の含水率、露点温度０℃到達時間、洗浄瓶に入れたＭＳ−Ｖ１５０の重量を示し、図１３に、洗浄瓶を通過した空気の露点温度の時間毎の変化示した。図１３の横軸は洗浄瓶に通気し始めた時からの経過時間、縦軸は露点温度である。 <Example 13>
Preparation of zeolite-based reducing agent MS-V150 of Preparation Example 2 100 mL Kinoshita type screw mouth gas absorption washing bottle equipped with a G2 spherical glass filter (hereinafter referred to as “washing bottle”) at a temperature of 5 ° C. Then, air having a gaseous hexane concentration of 600 ppm and a relative humidity of 90 ° C. was aerated at a rate of 1 L per minute. The temperature and relative humidity of the air that passed through the washing bottle were measured at 10 second intervals using a temperature / humidity data logger (RHT-10, ASONE Co., Ltd.), and the hexane concentration was measured with a hexane detector tube (No. 102L, (Gastech Co., Ltd.) was measured at intervals of 15 minutes. Also, instead of air having a gaseous hexane concentration of 600 ppm and 5 ° C. relative humidity of 90% at a temperature of 5 ° C., air having a gaseous hexane concentration of 600 ppm and 40 ° C. and a relative humidity of 80% is used at a temperature of 40 ° C. The same aeration test was conducted. Table 13 shows the collection time for gaseous hexane at 5 ° C. relative humidity of 90% and 40 ° C. relative humidity of 80%, MS-V150 moisture content, dew point temperature reaching time of 0 ° C., and weight of MS-V150 in the washing bottle. FIG. 13 shows changes in the dew point temperature of the air that has passed through the washing bottle over time. The horizontal axis in FIG. 13 is the elapsed time from the start of aeration into the washing bottle, and the vertical axis is the dew point temperature.

なお、５℃相対湿度９０％の通気試験および４０℃相対湿度８０％の通気試験それぞれに使用したＭＳ−Ｖ１５０は、洗浄瓶に入れる前に、１ヘクトパスカル以下、１５０℃１０時間処理し、引き続き１ヘクトパスカル以下で５０℃以下まで冷却をする処理した。   The MS-V150 used in each of the 5 ° C. relative humidity 90% aeration test and the 40 ° C. relative humidity 80% aeration test was treated at 1 hectopascal or less at 150 ° C. for 10 hours before being put into the washing bottle. The process which cooled to 50 degrees C or less below hectopascal was performed.

なおまた、ガス状ヘキサン捕集時間は、検知限度１ｐｐｍであるヘキサン検知管（Ｎｏ．１０２Ｌ、（株）ガステック社）を用いて洗浄瓶通過後の空気を測定した時に、ヘキサン検知管により検知されなかった通気開始後からの１５分間隔の時間であり、含水率は、洗浄瓶に入れた低減剤と同じものを含水率分析用の分析試料として、含水率試験を行った値である。   In addition, the gaseous hexane collection time is detected by the hexane detector tube when the air after passing through the washing bottle is measured using a hexane detector tube (No. 102L, Gastec Co., Ltd.) having a detection limit of 1 ppm. This is a time of 15 minutes after the start of aeration, and the moisture content is a value obtained by conducting a moisture content test using the same reducing agent put in the washing bottle as an analysis sample for moisture content analysis.

なお、そして、表１３、図１３の２５℃相対湿度８０％は、実施例１１の含水率０．７６質量％のＭＳ−Ｖ１５０のデータである。   The 25 ° C. relative humidity of 80% in Table 13 and FIG. 13 is data of MS-V150 of Example 11 having a moisture content of 0.76% by mass.



ガス状ヘキサンが含まれる５℃相対湿度９０％の空気を、含水率０．７９質量％のＭＳ−Ｖ１５０を入れた洗浄瓶に通過させた場合のガス状ヘキサン捕集時間は、１０５分間であった。また、１ｍ３の空気に含まれる水蒸気量が２５℃相対湿度８０％の２倍を超える４０℃相対湿度８０％のガス状ヘキサンを含む空気を、含水率０．７３質量％のＭＳ−Ｖ１５０を入れた洗浄瓶に通過させた場合においてもガス状ヘキサン捕集時間６０分間であり、ガス状ヘキサンの捕集能力を有していた。 The collection time of gaseous hexane was 105 minutes when air containing 90% relative humidity at 5 ° C containing gaseous hexane was passed through a washing bottle containing MS-V150 with a moisture content of 0.79 mass%. It was. Moreover, the amount of water vapor contained in 1 m 3 of air is more than twice the 25 ° C. relative humidity of 80%, and the air containing gaseous hexane at 40 ° C. relative humidity of 80% is replaced with MS-V150 having a moisture content of 0.73 mass%. Even when it was passed through the washing bottle, the gaseous hexane collection time was 60 minutes, and it had the ability to collect gaseous hexane.

ガス状ヘキサンが含まれる５℃相対湿度９０％の空気をＭＳ−Ｖ１５０を入れた洗浄瓶に通過させた場合は、通気開始から１２０秒間経過後に露点温度０℃以下に達した後、少なくとも洗浄瓶を通過した空気中にヘキサン検知管によりヘキサンが検知されなかった通気開始からの経過時間まで、露点温度０℃以下を維持した。また、ガス状ヘキサンが含まれる４０℃相対湿度８０％の空気をＭＳ−Ｖ１５０を入れた洗浄瓶に通過させた場合は、１ｍ３の空気に含まれる水蒸気量が２５℃相対湿度８０％の２倍を超えるにもかかわらず、通気開始から１４６０秒後に露点温度０℃に達し、その後少なくとも洗浄瓶を通過した空気中にヘキサン検知管によりヘキサンが検知されなかった通気開始からの経過時間まで、露点温度０℃以下を維持した。 When air with a relative humidity of 90% containing gaseous hexane is passed through a washing bottle containing MS-V150, at least the washing bottle after reaching the dew point temperature of 0 ° C. or less after 120 seconds from the start of aeration. The dew point temperature was maintained at 0 ° C. or lower until the elapsed time from the start of aeration when hexane was not detected by the hexane detector tube in the air that passed through. In addition, when air at 40 ° C. and a relative humidity of 80% containing gaseous hexane is passed through a washing bottle containing MS-V150, the amount of water vapor contained in 1 m 3 of air is 2 at 25 ° C. and a relative humidity of 80%. In spite of exceeding the doubling time, the dew point reached 0 ° C. after 1460 seconds from the start of ventilation, and at least until the elapsed time from the start of ventilation where hexane was not detected by the hexane detector tube in the air that passed through the washing bottle. The temperature was maintained at 0 ° C. or lower.

＜実施例１４＞
ゼオライト系低減剤の調製例２のＭＳ−Ｖ１５０を１００ｍＬ入れた、Ｇ２球状ガラスフィルターを具備した１００ｍＬ木下式ねじ口ガス吸収洗滌瓶（以下、「洗浄瓶」という。）に、２５℃の温度下、ガス状酢酸エチル濃度８００ｐｐｍ、２５℃相対湿度１５、５０％それぞれの空気を１分間に１Ｌの速度で通気した。洗浄瓶を通過した空気の温度および相対湿度を温湿度データーロガー（ＲＨＴ−１０、アズワン（株）社）を用いて１０秒間隔で測定し、また、ガス状酢酸エチル濃度を酢酸エチル検知管（Ｎｏ．１４１Ｌ、（株）ガステック社）を用いて１５分間隔で測定した。表１４に、２５℃相対湿度１５、５０％それぞれのガス状酢酸エチル捕集時間、ＭＳ−Ｖ１５０の含水率、露点温度０℃到達時間、洗浄瓶に入れたＭＳ−Ｖ１５０の重量を示し、図１４に、２５℃、相対湿度１５％および２５℃、相対湿度８０％のガス状酢酸エチルを含む空気が洗浄瓶を通過した後の空気の露点温度の時間毎の変化示した。図１４の横軸は洗浄瓶に通気し始めた時からの経過時間、縦軸は露点温度である。 <Example 14>
Preparation of zeolite-based reducing agent MS-V150 of Preparation Example 2 in 100 mL Kinoshita type screw mouth gas absorption washing bottle (hereinafter referred to as “washing bottle”) equipped with a G2 spherical glass filter at a temperature of 25 ° C. In addition, air having a gaseous ethyl acetate concentration of 800 ppm, 25 ° C. and a relative humidity of 15 and 50% was aerated at a rate of 1 L per minute. The temperature and relative humidity of the air that passed through the washing bottle were measured at intervals of 10 seconds using a temperature / humidity data logger (RHT-10, ASONE Co., Ltd.), and the gaseous ethyl acetate concentration was measured with an ethyl acetate detector tube ( No. 141L, Gastec Co., Ltd.) was measured at intervals of 15 minutes. Table 14 shows the gaseous ethyl acetate collection time at 25 ° C. relative humidity of 15 and 50%, the moisture content of MS-V150, the dew point temperature reaching time of 0 ° C., and the weight of MS-V150 in the washing bottle. Fig. 14 shows changes in the dew point temperature of the air after the passage of air containing gaseous ethyl acetate at 25 ° C, 15% relative humidity and 25 ° C, 80% relative humidity after passing through the washing bottle. The horizontal axis of FIG. 14 is the elapsed time from the start of aeration into the washing bottle, and the vertical axis is the dew point temperature.

なお、ＭＳ−Ｖ１５０は、洗浄瓶に入れる前に、１ヘクトパスカル以下、１５０℃１０時間処理し、引き続き１ヘクトパスカル以下で５０℃以下まで冷却する処理を行った。   MS-V150 was treated at 1 hectopascal or lower at 150 ° C. for 10 hours and then cooled to 50 ° C. or lower at 1 hectopascal or lower before being placed in a washing bottle.

なおまた、ガス状酢酸エチル捕集時間は、検知限度５ｐｐｍである酢酸エチル検知管（Ｎｏ．１４１Ｌ、（株）ガステック社）を用いて洗浄瓶通過後の空気を測定した時に、酢酸エチル検知管により検知されなかった通気開始後からの１５分間隔の時間であり、含水率は、洗浄瓶に入れた低減剤と同じものを含水率分析用の分析試料として、含水率試験を行った値である。   In addition, the gaseous ethyl acetate collection time was detected when the air passed through the washing bottle was measured using an ethyl acetate detector tube (No. 141L, Gastec Co., Ltd.) having a detection limit of 5 ppm. It is a time of 15 minutes interval after the start of aeration that was not detected by the pipe, and the moisture content was a value obtained by conducting a moisture content test using the same reducing agent placed in the washing bottle as an analysis sample for moisture content analysis. It is.

ガス状酢酸エチルが含まれる２５℃相対湿度１５、５０、８０％の空気をそれぞれＭＳ−Ｖ１５０を入れた洗浄瓶に通過させた場合のガス状酢酸エチル捕集時間は、それぞれ２１０、１５０、１３５分間であった。また、ガス状酢酸エチルが含まれる２５℃、相対湿度１５、５０、８０％の空気をそれぞれＭＳ−Ｖ１５０を入れた洗浄瓶に通過させた場合は、通気開始からそれぞれ３３０、４５０、５００秒間経過後に露点温度０℃以下に達した後、少なくとも洗浄瓶を通過した空気中に酢酸エチル検知管により酢酸エチルが検知されなかった通気開始からの経過時間まで、露点温度０℃以下を維持した。   Gaseous ethyl acetate collection times when air containing gaseous ethyl acetate at 25 ° C. and a relative humidity of 15, 50, and 80% were passed through washing bottles containing MS-V150 were 210, 150, and 135, respectively. For minutes. In addition, when air of 25 ° C. and relative humidity of 15, 50, and 80% containing gaseous ethyl acetate is passed through cleaning bottles containing MS-V150, 330, 450, and 500 seconds have elapsed from the start of ventilation, respectively. After the dew point temperature of 0 ° C. or lower was reached later, the dew point temperature of 0 ° C. or lower was maintained until at least the elapsed time from the start of aeration when ethyl acetate was not detected by the ethyl acetate detector tube in the air that passed through the washing bottle.

＜実施例１５＞
ゼオライト系低減剤の調製例２のＭＳ−Ｖ１５０を１００ｍＬ入れた、Ｇ２球状ガラスフィルターを具備した１００ｍＬ木下式ねじ口ガス吸収洗滌瓶（以下、「洗浄瓶」という。）に、５℃の温度下、ガス状酢酸エチル濃度８００ｐｐｍ、５℃相対湿度９０％の空気を１分間に１Ｌの速度で通気した。洗浄瓶を通過した空気の温度および相対湿度を温湿度データーロガー（ＲＨＴ−１０、アズワン（株）社）を用いて１０秒間隔で測定し、また、ガス状酢酸エチル濃度を酢酸エチル検知管（Ｎｏ．１４１Ｌ、（株）ガステック社）を用いて１５分間隔で測定した。また、５℃の温度下、ガス状酢酸エチル濃度８００ｐｐｍ、５℃相対湿度９０％の空気の条件の代わりに、４０℃の温度下、ガス状酢酸エチル濃度８００ｐｐｍ、４０℃相対湿度８０％の空気を用いて、同じ通気試験を行った。表１５に、５℃相対湿度９０％、４０℃相対湿度８０％それぞれのガス状酢酸エチル捕集時間、ＭＳ−Ｖ１５０の含水率、露点温度０℃到達時間、洗浄瓶に入れたＭＳ−Ｖ１５０の重量を示し、図１５に、洗浄瓶を通過した空気の露点温度の時間毎の変化示した。図１５の横軸は洗浄瓶に通気し始めた時からの経過時間、縦軸は露点温度である。 <Example 15>
Preparation of zeolite-based reducing agent MS-V150 of Preparation Example 2 100 mL Kinoshita type screw mouth gas absorption washing bottle equipped with a G2 spherical glass filter (hereinafter referred to as “washing bottle”) at a temperature of 5 ° C. Then, air with a gaseous ethyl acetate concentration of 800 ppm and a relative humidity of 90 ° C. was aerated at a rate of 1 L per minute. The temperature and relative humidity of the air that passed through the washing bottle were measured at intervals of 10 seconds using a temperature / humidity data logger (RHT-10, ASONE Co., Ltd.), and the gaseous ethyl acetate concentration was measured with an ethyl acetate detector tube ( No. 141L, Gastec Co., Ltd.) was measured at intervals of 15 minutes. Also, instead of air having a gaseous ethyl acetate concentration of 800 ppm and 5 ° C. relative humidity of 90% at a temperature of 5 ° C., air having a gaseous ethyl acetate concentration of 800 ppm and 40 ° C. and a relative humidity of 80% at a temperature of 40 ° C. The same aeration test was conducted using Table 15 shows the collection time of gaseous ethyl acetate at 90 ° C. relative humidity of 90% and 40 ° C. relative humidity of 80%, the moisture content of MS-V150, the time to reach 0 ° C. dew point, and the MS-V150 in the washing bottle. The weight is shown, and FIG. 15 shows the change of the dew point temperature of the air passing through the washing bottle over time. The horizontal axis in FIG. 15 is the elapsed time from the start of aeration into the washing bottle, and the vertical axis is the dew point temperature.

なお、５℃相対湿度９０％の通気試験および４０℃相対湿度８０％の通気試験それぞれに使用したＭＳ−Ｖ１５０は、洗浄瓶に入れる前に、１ヘクトパスカル以下、１５０℃１０時間処理し、引き続き１ヘクトパスカル以下で５０℃以下まで冷却をする処理した。   The MS-V150 used in each of the 5 ° C. relative humidity 90% aeration test and the 40 ° C. relative humidity 80% aeration test was treated at 1 hectopascal or less at 150 ° C. for 10 hours before being put into the washing bottle. The process which cooled to 50 degrees C or less below hectopascal was performed.

なおまた、ガス状酢酸エチル捕集時間は、検知限度５ｐｐｍである酢酸エチル検知管（Ｎｏ．１４１Ｌ、（株）ガステック社）を用いて洗浄瓶通過後の空気を測定した時に、酢酸エチル検知管により検知されなかった通気開始後からの１５分間隔の時間であり、含水率は、洗浄瓶に入れた低減剤と同じものを含水率分析用の分析試料として、含水率試験を行った値である。   In addition, the gaseous ethyl acetate collection time was detected when the air passed through the washing bottle was measured using an ethyl acetate detector tube (No. 141L, Gastec Co., Ltd.) having a detection limit of 5 ppm. It is a time of 15 minutes interval after the start of aeration that was not detected by the pipe, and the moisture content was a value obtained by conducting a moisture content test using the same reducing agent placed in the washing bottle as an analysis sample for moisture content analysis. It is.

なお、そして、表１５、図１５の２５℃相対湿度８０％は、実施例１４の含水率１．１０質量％のＭＳ−Ｖ１５０のデータである。   In addition, the 25 ° C. relative humidity of 80% in Table 15 and FIG. 15 is data of MS-V150 of Example 14 having a moisture content of 1.10% by mass.

ガス状酢酸エチルが含まれる５℃相対湿度９０％の空気を、含水率１．００質量％のＭＳ−Ｖ１５０を入れた洗浄瓶に通過させた場合のガス状酢酸エチル捕集時間は、２２５分間であった。また、１ｍ３の空気に含まれる水蒸気量が２５℃相対湿度８０％の２倍を超える４０℃相対湿度８０％のガス状酢酸エチルを含む空気を、含水率０．７９質量％のＭＳ−Ｖ１５０を入れた洗浄瓶に通過させた場合においてもガス状酢酸エチル捕集時間７５分間であり、ガス状酢酸エチルの捕集能力を有していた。 Gaseous ethyl acetate collection time when air containing 90% relative humidity at 5 ° C containing gaseous ethyl acetate was passed through a washing bottle containing MS-V150 having a water content of 1.00% by mass was 225 minutes. Met. Further, the amount of water vapor contained in 1 m 3 of air is more than twice the 25 ° C. relative humidity of 80%, and the air containing gaseous ethyl acetate at 40 ° C. and 80% relative humidity is MS-V150 having a moisture content of 0.79% by mass. Even when the sample was passed through a washing bottle containing gas, the collection time of gaseous ethyl acetate was 75 minutes, and it had the ability to collect gaseous ethyl acetate.

ガス状酢酸エチルが含まれる５℃相対湿度９０％の空気をＭＳ−Ｖ１５０を入れた洗浄瓶に通過させた場合は、通気開始から２００秒間経過後に露点温度０℃以下に達した後、少なくとも洗浄瓶を通過した空気中に酢酸エチル検知管により酢酸エチルが検知されなかった通気開始からの経過時間まで、露点温度０℃以下を維持した。また、ガス状酢酸エチルが含まれる４０℃相対湿度８０％の空気をＭＳ−Ｖ１５０を入れた洗浄瓶に通過させた場合は、１ｍ３の空気に含まれる水蒸気量が２５℃相対湿度８０％の２倍を超えるにもかかわらず、通気開始から１０５０秒後に露点温度０℃に達した後、少なくとも洗浄瓶を通過した空気中に酢酸エチル検知管により酢酸エチルが検知されなかった通気開始からの経過時間まで、露点温度０℃以下を維持した。 When air containing 90% relative humidity at 5 ° C containing gaseous ethyl acetate is passed through a washing bottle containing MS-V150, at least washing is performed after the dew point temperature reaches 0 ° C or less after 200 seconds from the start of aeration. The dew point temperature of 0 ° C. or lower was maintained until the elapsed time from the start of aeration when ethyl acetate was not detected by the ethyl acetate detector tube in the air that passed through the bottle. When air at 40 ° C. and a relative humidity of 80% containing gaseous ethyl acetate is passed through a washing bottle containing MS-V150, the amount of water vapor contained in 1 m 3 of air is 25 ° C. and a relative humidity of 80%. Despite exceeding 2 times, after the dew point temperature reached 0 ° C. 1050 seconds after the start of ventilation, at least the ethyl acetate was not detected by the ethyl acetate detector tube in the air that passed through the washing bottle. Until the time, the dew point temperature was maintained below 0 ° C.

＜実施例１６＞
１ヘクトパスカル以下、１５０℃、１０時間加熱処理したゼオライト系低減剤の調製例２のＭＳ−Ｖ１５０を入れた、Ｇ２球状ガラスフィルターを具備した１００ｍＬ木下式ねじ口ガス吸収洗滌瓶（以下、「洗浄瓶」という。）に、２５℃の温度下、ガス状Ｎ，Ｎ−ジメチルホルムアミド濃度３０ｐｐｍ、２５℃相対湿度８０％の空気を１分間に１Ｌの速度で通気した。洗浄瓶を通過した空気の温度および相対湿度を温湿度データーロガー（ＲＨＴ−１０、アズワン（株）社）を用いて１０秒間隔で測定し、また、ガス状Ｎ，Ｎ−ジメチルホルムアミド濃度をＮ，Ｎ−ジメチルホルムアミド検知管（Ｎｏ．１８３、（株）ガステック社）を用いて１５分間隔で測定した。また、ガス状Ｎ，Ｎ−ジメチルホルムアミドの代わりに、ガス状１，４−ジオキサン、ガス状エピクロロヒドリン、ガス状メチルエチルケトン、ガス状アセトン、ガス状クロロホルム、ガス状メタノール、ガス状１−ブタノール、ガス状イソブチルアルコール、ガス状二硫化炭素を用いて同様な実験を行った。表１６に、ガス状Ｎ，Ｎ−ジメチルホルムアミド、ガス状１，４−ジオキサン、ガス状エピクロロヒドリン、ガス状メチルエチルケトン、ガス状アセトン、ガス状クロロホルム、ガス状メタノール、ガス状１−ブタノール、ガス状イソブチルアルコール、ガス状二硫化炭素の濃度を測定するために用いたそれぞれのガステック社製検知管、使用したガステック社製検知管の検知限度、洗浄瓶に導入したガス状Ｎ，Ｎ−ジメチルホルムアミド、ガス状１，４−ジオキサン、ガス状エピクロロヒドリン、ガス状メチルエチルケトン、ガス状アセトン、ガス状クロロホルム、ガス状メタノール、ガス状１−ブタノール、ガス状イソブチルアルコール、ガス状二硫化炭素それぞれの初発濃度、ガス状Ｎ，Ｎ−ジメチルホルムアミド、ガス状１，４−ジオキサン、ガス状エピクロロヒドリン、ガス状メチルエチルケトン、ガス状アセトン、ガス状クロロホルム、ガス状メタノール、ガス状１−ブタノール、ガス状イソブチルアルコール、ガス状二硫化炭素それぞれの捕集時間、洗浄瓶に入れたＭＳ−Ｖ１５０の含水率、露点温度０℃到達時間、洗浄瓶に入れたＭＳ−Ｖ１５０の重量を示した。また、図１６、図１７、図１８に、ガス状Ｎ，Ｎ−ジメチルホルムアミド、ガス状１，４−ジオキサン、ガス状エピクロロヒドリン、ガス状メチルエチルケトン、ガス状アセトン、ガス状クロロホルム、ガス状メタノール、ガス状１−ブタノール、ガス状イソブチルアルコール、ガス状二硫化炭素を含むそれぞれの空気が洗浄瓶を通過した後の空気の露点温度の時間毎の変化を示した。図１６、図１７、図１８の横軸は洗浄瓶に通気し始めた時からの経過時間、縦軸は露点温度である。 <Example 16>
100 mL Kinoshita-type screw mouth gas absorption washing bottle (hereinafter referred to as “washing bottle”) equipped with a G2 spherical glass filter containing MS-V150 of Preparation Example 2 of zeolitic reducing agent heated at 150 ° C. for 10 hours at 1 hectopascal or less. The gas N, N-dimethylformamide concentration was 30 ppm and air at 25 ° C. and a relative humidity of 80% was aerated at a rate of 1 L per minute at a temperature of 25 ° C. The temperature and relative humidity of the air that passed through the washing bottle were measured at intervals of 10 seconds using a temperature and humidity data logger (RHT-10, ASONE Co., Ltd.), and the concentration of gaseous N, N-dimethylformamide was determined as N , N-dimethylformamide detector tube (No. 183, Gastec Co., Ltd.), and measured at intervals of 15 minutes. Further, instead of gaseous N, N-dimethylformamide, gaseous 1,4-dioxane, gaseous epichlorohydrin, gaseous methyl ethyl ketone, gaseous acetone, gaseous chloroform, gaseous methanol, gaseous 1-butanol A similar experiment was conducted using gaseous isobutyl alcohol and gaseous carbon disulfide. Table 16 shows gaseous N, N-dimethylformamide, gaseous 1,4-dioxane, gaseous epichlorohydrin, gaseous methyl ethyl ketone, gaseous acetone, gaseous chloroform, gaseous methanol, gaseous 1-butanol, Gastec detector tubes used to measure the concentrations of gaseous isobutyl alcohol and gaseous carbon disulfide, detection limits of the gastech detector tubes used, and gaseous N and N introduced into the cleaning bottle -Dimethylformamide, gaseous 1,4-dioxane, gaseous epichlorohydrin, gaseous methyl ethyl ketone, gaseous acetone, gaseous chloroform, gaseous methanol, gaseous 1-butanol, gaseous isobutyl alcohol, gaseous disulfide Initial concentration of each carbon, gaseous N, N-dimethylformamide, gaseous 1,4-di Xane, gaseous epichlorohydrin, gaseous methyl ethyl ketone, gaseous acetone, gaseous chloroform, gaseous methanol, gaseous 1-butanol, gaseous isobutyl alcohol, gaseous carbon disulfide collection time, in the cleaning bottle The moisture content of MS-V150, the dew point temperature reaching 0 ° C., and the weight of MS-V150 in the washing bottle are shown. In addition, FIG. 16, FIG. 17, and FIG. 18 show gaseous N, N-dimethylformamide, gaseous 1,4-dioxane, gaseous epichlorohydrin, gaseous methyl ethyl ketone, gaseous acetone, gaseous chloroform, gaseous The time-dependent change of the dew point temperature of the air after each air containing methanol, gaseous 1-butanol, gaseous isobutyl alcohol, and gaseous carbon disulfide passed the washing bottle was shown. 16, 17, and 18, the horizontal axis represents the elapsed time from the start of aeration into the washing bottle, and the vertical axis represents the dew point temperature.

なお、ガス状１，４−ジオキサンの濃度の測定には、テトラヒドロフラン検知管（Ｎｏ．１５９、（株）ガステック社）を用い、検知管の検知限度は前記テトラヒドロフラン検知管により１，４−ジオキサンを測定した時の測定範囲の最低値２５ｐｐｍ未満とし、ガス状エピクロロヒドリンの濃度の測定には、エチレンオキシド検知管（Ｎｏ．１６３Ｌ、（株）ガステック社）を用い、検知管の検知限度は前記エチレンオキシド検知管によりエピクロロヒドリンを測定した時の測定範囲の最低値１．２ｐｐｍ未満とした。   For the measurement of the concentration of gaseous 1,4-dioxane, a tetrahydrofuran detector tube (No. 159, Gastec Co., Ltd.) was used, and the detection limit of the detector tube was 1,4-dioxane using the tetrahydrofuran detector tube. The measurement range is less than 25 ppm, and the concentration of gaseous epichlorohydrin is measured using an ethylene oxide detector tube (No.163L, Gastec Co., Ltd.). Was less than 1.2 ppm of the minimum value of the measurement range when epichlorohydrin was measured with the ethylene oxide detector tube.


なお、含水率は、ガス状Ｎ，Ｎ−ジメチルホルムアミド、ガス状１，４−ジオキサン、ガス状エピクロロヒドリン、ガス状メチルエチルケトン、ガス状アセトン、ガス状クロロホルム、ガス状メタノール、ガス状１−ブタノール、ガス状イソブチルアルコール、ガス状二硫化炭素をそれぞれ含む空気を通過させた洗浄瓶に入れた低減剤と同じものを含水率分析用の試料として含水率試験を行った値である。ガス状Ｎ，Ｎ−ジメチルホルムアミドの捕集時間は、検知限度０．１ｐｐｍであるＮ，Ｎ−ジメチルホルムアミド検知管（Ｎｏ．１８３、（株）ガステック社）を用いて洗浄瓶通過後の空気を測定した時に、Ｎ，Ｎ−ジメチルホルムアミド検知管により検知されなかった通気開始後からの１５分間隔の時間であり、ガス状１，４−ジオキサンの捕集時間は、検知限度が２５ｐｐｍより小さい値である１，４-ジオキサンの測定が可能であるテトラヒドロフラン検知管（Ｎｏ．１５９、（株）ガステック社）を用いて洗浄瓶通過後の空気を測定した時に、テトラヒドロフラン検知管により検知されなかった通気開始後からの１５分間隔の時間であり、ガス状エピクロロヒドリンの捕集時間は、検知限度が１．２ｐｐｍより小さい値であるエピクロロヒドリンの測定が可能であるエチレンオキシド検知管（Ｎｏ．１６３Ｌ、（株）ガステック社）を用いて洗浄瓶通過後の空気を測定した時に、エチレンオキシド検知管により検知されなかった通気開始後からの１５分間隔の時間であり、ガス状メチルエチルケトンの捕集時間は、検知限度２０ｐｐｍであるメチルエチルケトン検知管（Ｎｏ．１５２、（株）ガステック社）を用いて洗浄瓶通過後の空気を測定した時に、メチルエチルケトン検知管により検知されなかった通気開始後からの１５分間隔の時間であり、ガス状アセトンの捕集時間は、検知限度３０ｐｐｍであるアセトン検知管（Ｎｏ．１５１、（株）ガステック社）を用いて洗浄瓶通過後の空気を測定した時に、アセトン検知管により検知されなかった通気開始後からの１５分間隔の時間であり、ガス状クロロホルムの捕集時間は、検知限度０．２ｐｐｍであるクロロホルム検知管（Ｎｏ．１３７ＬＡ、（株）ガステック社）を用いて洗浄瓶通過後の空気を測定した時に、クロロホルム検知管により検知されなかった通気開始後からの１５分間隔の時間であり、ガス状メタノールの捕集時間は、検知限度１５ｐｐｍであるメタノール検知管（Ｎｏ．１１１Ｌ、（株）ガステック社）を用いて洗浄瓶通過後の空気を測定した時に、メタノール検知管により検知されなかった通気開始後からの１５分間隔の時間であり、ガス状二硫化炭素の捕集時間は、検知限度０．３ｐｐｍである二硫化炭素検知管（Ｎｏ．１３、（株）ガステック社）を用いて洗浄瓶通過後の空気を測定した時に、二硫化炭素検知管により検知されなかった通気開始後からの１５分間隔の時間である。ガス状１−ブタノールの捕集時間は、検知限度１ｐｐｍである１−ブタノール検知管（Ｎｏ．１１４、（株）ガステック社）を用いて洗浄瓶通過後の空気を測定した時に、通気開始から３００分間経過後において１−ブタノール検知管により検知されず、検知管による洗浄瓶通過後の空気の１−ブタノール濃度測定を止めたことを示し、ガス状イソブチルアルコールの捕集時間は、検知限度３ｐｐｍであるイソブチルアルコール検知管（Ｎｏ．１１６Ｌ、（株）ガステック社）を用いて洗浄瓶通過後の空気を測定した時に、通気開始から２４０分間経過後においてイソブチルアルコール検知管により検知されず、検知管による洗浄瓶通過後の空気のイソブチルアルコール濃度測定を止めたことを示す。   The water content is as follows: gaseous N, N-dimethylformamide, gaseous 1,4-dioxane, gaseous epichlorohydrin, gaseous methyl ethyl ketone, gaseous acetone, gaseous chloroform, gaseous methanol, gaseous 1- This is a value obtained by performing a moisture content test using the same reducing agent as that contained in a washing bottle through which air containing butanol, gaseous isobutyl alcohol, and gaseous carbon disulfide has been passed, as a sample for moisture content analysis. The collection time of gaseous N, N-dimethylformamide is the air after passing through the washing bottle using an N, N-dimethylformamide detector tube (No. 183, Gastec Co., Ltd.) having a detection limit of 0.1 ppm. Was measured at intervals of 15 minutes after the start of aeration, which was not detected by the N, N-dimethylformamide detector tube, and the detection time for the collection of gaseous 1,4-dioxane was less than 25 ppm. When the air after passing through the washing bottle was measured using a tetrahydrofuran detector tube (No.159, Gastec Co., Ltd.) capable of measuring the value 1,4-dioxane, it was not detected by the tetrahydrofuran detector tube Epichlorohydrin is collected at an interval of 15 minutes after the start of aeration, and the collection time of gaseous epichlorohydrin is an epichrome whose detection limit is less than 1.2 ppm. 15 measured from the start of aeration that was not detected by the ethylene oxide detector tube when the air after passing through the washing bottle was measured using an ethylene oxide detector tube (No. 163L, Gastec Co., Ltd.) that can measure rhohydrin. It is time of minute interval, and the collection time of gaseous methyl ethyl ketone is measured when the air after passing through the washing bottle is measured using a methyl ethyl ketone detector tube (No. 152, Gastec Co., Ltd.) having a detection limit of 20 ppm. Acetone detector tube (No. 151, Gastech Co., Ltd.), which is a 15 minute interval after the start of ventilation that was not detected by the methyl ethyl ketone detector tube, and the collection time of gaseous acetone is a detection limit of 30 ppm. 15 minutes after the start of ventilation that was not detected by the acetone detector tube when the air after passing through the washing bottle was measured using The time for collecting gaseous chloroform was measured when the air after passing through the washing bottle was measured using a chloroform detector tube (No. 137LA, Gastec Co., Ltd.) having a detection limit of 0.2 ppm. Methanol detector tube (No. 111L, Gastec Co., Ltd.), which is a 15 minute interval after the start of aeration that was not detected by the chloroform detector tube, and the collection time of gaseous methanol was 15 ppm. ) Was used to measure the air after passing through the washing bottle, and was 15 minutes after the start of aeration, which was not detected by the methanol detector tube. When the air after passing the cleaning bottle was measured using a carbon disulfide detector tube (No. 13, Gastec Co., Ltd.) of 3 ppm, it was not detected by the carbon disulfide detector tube. It was the time of 15-minute intervals after the start ventilation. The collection time of gaseous 1-butanol was measured from the start of ventilation when the air after passing through the washing bottle was measured using a 1-butanol detector tube (No. 114, Gastec Co., Ltd.) having a detection limit of 1 ppm. After 300 minutes, it was not detected by the 1-butanol detector tube, indicating that measurement of the 1-butanol concentration in the air after passing through the washing bottle by the detector tube was stopped, and the collection time of gaseous isobutyl alcohol was 3 ppm detection limit. When the air after passing through the washing bottle was measured using an isobutyl alcohol detector tube (No. 116L, Gastec Co., Ltd.), it was not detected by the isobutyl alcohol detector tube after 240 minutes from the start of ventilation. It shows that the measurement of the isobutyl alcohol concentration in the air after passing through the washing bottle by the tube was stopped.

ＭＳ−Ｖ１５０は、ガス状のＮ，Ｎ−ジメチルホルムアミド、１，４−ジオキサン、エピクロロヒドリン、メチルエチルケトン、アセトン、クロロホルム、メタノール、二硫化炭素すべてを捕集し、また、露点温度０℃に通気開始から５００〜１２００秒で到達した後、ガス状のＮ，Ｎ−ジメチルホルムアミド、１，４−ジオキサン、エピクロロヒドリン、メチルエチルケトン、アセトン、クロロホルム、メタノール、二硫化炭素それぞれの有機化合物濃度を測定するために使用した検知管により少なくとも各洗浄瓶を通過した空気中にそれぞれの有機化合物が検知されなかった通気開始からの経過時間まで、露点温度０℃以下を維持した。ガス状の１−ブタノール、イソブチルアルコールにおいては、ＭＳ−Ｖ１５０は、ガス状の１−ブタノール、イソブチルアルコールをそれぞれ３００、２４０分間以上捕集し、また、露点温度０℃に通気開始から１２７０、５９０秒後にそれぞれ到達した後、少なくとも通気開始からそれぞれ１８０００、１４４００秒後まで露点温度０℃以下を維持した。   MS-V150 collects all gaseous N, N-dimethylformamide, 1,4-dioxane, epichlorohydrin, methyl ethyl ketone, acetone, chloroform, methanol, carbon disulfide, and has a dew point temperature of 0 ° C. After reaching 500 to 1200 seconds from the start of aeration, the organic compound concentrations of gaseous N, N-dimethylformamide, 1,4-dioxane, epichlorohydrin, methyl ethyl ketone, acetone, chloroform, methanol, carbon disulfide are determined. The dew point temperature was maintained at 0 ° C. or lower until the elapsed time from the start of aeration in which the respective organic compounds were not detected in at least the air passed through each washing bottle by the detection tube used for the measurement. In gaseous 1-butanol and isobutyl alcohol, MS-V150 collects gaseous 1-butanol and isobutyl alcohol for 300 and 240 minutes or more, respectively, and at a dew point of 0 ° C. from the start of aeration 1270, 590 After reaching each after 2 seconds, the dew point temperature was maintained at 0 ° C. or lower until at least 18000 and 14400 seconds after the start of ventilation.

本発明の方法によれば、天然からも産出する、モルデナイト型ゼオライト、クリノプチロライト型ゼオライトのうち、少なくとも１つの鉱物を含むゼオライトを有機化合物と水蒸気の低減剤として用いることにより、ガス状有機化合物と水蒸気が含まれる空気から、ガス状有機化合物と水蒸気の両方を安価、かつ高効率に捕集し、ガス状有機化合物濃度と水蒸気量を同時に低下させることができる。したがって、産業上利用価値が高い発明である。   According to the method of the present invention, by using a zeolite containing at least one mineral among mordenite-type zeolite and clinoptilolite-type zeolite produced from nature as a reducing agent for organic compounds and water vapor, From the air containing the compound and water vapor, both the gaseous organic compound and water vapor can be collected at low cost and with high efficiency, and the concentration of the gaseous organic compound and the amount of water vapor can be reduced simultaneously. Therefore, the invention has high industrial utility value.

Claims (4)

モルデナイト型ゼオライト、クリノプチロライト型ゼオライトのうち、少なくとも１つの鉱物を含むゼオライトであることを特徴とするガス状有機化合物と水蒸気の低減剤。   A gaseous organic compound and water vapor reducing agent characterized by being a zeolite containing at least one mineral among mordenite type zeolite and clinoptilolite type zeolite. ガス状芳香族化合物と水蒸気を同時に捕集できることを特徴とする請求項１に記載のガス状有機化合物と水蒸気の低減剤。   The gaseous organic compound and water vapor reducing agent according to claim 1, wherein the gaseous aromatic compound and water vapor can be collected simultaneously. ガス状脂肪族化合物、ガス状二硫化炭素のうち、少なくとも１つの有機化合物と水蒸気を同時に捕集できることを特徴とする請求項１に記載のガス状有機化合物と水蒸気の低減剤。   The gaseous organic compound and water vapor reducing agent according to claim 1, wherein at least one organic compound and water vapor can be simultaneously collected from the gaseous aliphatic compound and gaseous carbon disulfide. 含水率が６．２６質量％以下、水素の含有率が０．０３質量％を超えるゼオライトであることを特徴とする、請求項１から請求項３までのいずれか１項に記載のガス状有機化合物と水蒸気の低減剤。   The gaseous organic according to any one of claims 1 to 3, characterized in that it is a zeolite having a water content of 6.26% by mass or less and a hydrogen content of more than 0.03% by mass. Compound and water vapor reducing agent.
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