JPH0894502A - In-gas nitrogen oxide absorption tube, collecting and recovering method by using it and method and device for measuring by using it - Google Patents
In-gas nitrogen oxide absorption tube, collecting and recovering method by using it and method and device for measuring by using itInfo
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- JPH0894502A JPH0894502A JP23317394A JP23317394A JPH0894502A JP H0894502 A JPH0894502 A JP H0894502A JP 23317394 A JP23317394 A JP 23317394A JP 23317394 A JP23317394 A JP 23317394A JP H0894502 A JPH0894502 A JP H0894502A
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- Japan
- Prior art keywords
- gas
- wall surface
- adsorption
- adsorption tube
- nitrogen oxides
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、大気汚染や、地球の酸
性化等、広く環境汚染の原因物質として、その排出規制
が課題となっている窒素酸化物の吸着管、この吸着管を
用いた捕集・回収方法、及び、この捕集・回収方法を用
いた測定方法及び装置に係り、特に、排気ガスや室内空
気、環境大気中の窒素酸化物を、効率良く吸着すること
が可能な吸着管、この吸着管を用いた、効率の高い捕集
・回収方法、及び、この捕集・回収方法を用いた、簡便
で、効率良く、高精度の繰返し測定が可能な測定方法及
び装置に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention uses an adsorption tube for nitrogen oxides, whose emission control is a problem as a substance causing a wide range of environmental pollution such as air pollution and acidification of the earth. The collection / recovery method described above, and the measurement method and apparatus using this collection / recovery method are particularly capable of efficiently adsorbing exhaust gas, indoor air, and nitrogen oxides in the ambient atmosphere. TECHNICAL FIELD The present invention relates to an adsorption tube, a highly efficient collection / recovery method using this adsorption tube, and a measurement method and device using this collection / recovery method that enables simple, efficient, and highly accurate repeated measurement. It is a thing.
【０００２】[0002]
【従来の技術】化石燃料の利用に伴なって発展してきた
近代文明社会において、燃焼に伴ない大気に拡散する、
人体及び生物に有害な窒素酸化物を一定濃度以下に抑制
することは、焦眉の課題である。大気中の窒素酸化物
（ＮＯx ）は、酸性雨や光化学スモッグの主たる原因物
質であり、その多くは、自動車等の移動発生源から排出
されるが、この規制のためには、排気ガスや大気中の窒
素酸化物（具体的には一酸化窒素ＮＯと二酸化窒素ＮＯ
2 ）の濃度を正確に測定することが不可欠である。2. Description of the Related Art In modern civilized society that has developed with the use of fossil fuels, it diffuses into the atmosphere as it burns,
Controlling nitrogen oxides, which are harmful to the human body and living organisms, to below a certain concentration is a problem for the eyebrows. Nitrogen oxides (NOx) in the atmosphere are the main causative substances of acid rain and photochemical smog, and most of them are emitted from mobile sources such as automobiles. Nitrogen oxides (specifically nitric oxide NO and nitrogen dioxide NO
It is essential to measure the concentration of 2 ) accurately.
【０００３】従来、ガス中の窒素酸化物濃度を測定する
方法として、ＮＯとオゾンの反応を利用した化学発光
（ケミルミネッセンス）法や、赤外・紫外線吸収を利用
した赤外・紫外線吸収法等の物理的な方法と共に、これ
らのガスを、一定量の液体に吸収させて化学的に定量分
析する方法も広く用いられている。そして、大気中の窒
素酸化物の自動測定装置や排気ガス中の窒素酸化物の測
定方法として、日本工業規格（ＪＩＳ）Ｋ０１０４にも
採用されている。Conventionally, as a method for measuring the concentration of nitrogen oxides in a gas, a chemiluminescence method utilizing the reaction of NO and ozone, an infrared / ultraviolet absorption method utilizing infrared / ultraviolet absorption, etc. In addition to the physical method described above, a method of chemically quantitatively analyzing these gases by absorbing them in a fixed amount of liquid is also widely used. It is also adopted in Japanese Industrial Standard (JIS) K0104 as an automatic measuring device for nitrogen oxides in the atmosphere and a method for measuring nitrogen oxides in exhaust gas.
【０００４】[0004]
【発明が解決しようとする問題点】しかしながら、前者
の化学発光や赤外・紫外線吸収を利用した装置は、非常
に高価で、赤外・紫外線分析計に至っては耐震対策の問
題も有り、更に、窒素酸化物の濃度が非常に低い環境大
気中の窒素酸化物の濃度を測定する際には、精度が不足
するという問題点を有していた。However, the former device utilizing chemiluminescence or infrared / ultraviolet absorption is very expensive, and the infrared / ultraviolet analyzer has a problem of seismic resistance. However, when measuring the concentration of nitrogen oxides in the ambient air where the concentration of nitrogen oxides is very low, there was a problem that the accuracy was insufficient.
【０００５】一方、後者の化学分析法では、大気中の窒
素酸化物を液体に吸収・捕集して化学分析を実施する際
に、二酸化窒素は比較的水に溶け易く、１００％近くイ
オン（亜硝酸イオン又は硝酸イオン）として回収するこ
とが可能であり、ナフチルエチレンジアミン等の発色試
薬や、イオン選択性電極等のセンサ、イオンクロマトグ
ラフ等の分析機器と組合わせて定量することが、吸収液
を選択し、吸収瓶の構造を工夫することによって可能で
あった。On the other hand, in the latter chemical analysis method, when nitrogen oxide in the atmosphere is absorbed and collected in a liquid to carry out a chemical analysis, nitrogen dioxide is relatively soluble in water and is close to 100% ion ( Nitrite ion or nitrate ion) can be recovered, and quantification in combination with a coloring reagent such as naphthylethylenediamine, a sensor such as an ion-selective electrode, or an analytical instrument such as an ion chromatograph is the absorption liquid. Was selected and the structure of the absorption bottle was devised.
【０００６】しかしながら、一酸化窒素は水に溶け難い
ため、一旦、これを酸化して二酸化窒素に変換してか
ら、吸収する以外に方法がなかった。そのため、一酸化
窒素の様々な酸化方法が考えられているが、いずれも適
切なものがなく、例えばＪＩＳに記載された、二酸化窒
素をザルツマン試薬中に吸収させてジアゾ化し、更にカ
ップリングによってアゾ色素として発色させ、これを吸
光度測定するザルツマン（吸光光度）法においては、通
常、液体酸化剤である５％の過マンガン酸カリウムと硫
酸の混合溶液を使用しているが、その酸化率は７０〜８
０％程度に過ぎなかった。However, since nitric oxide is difficult to dissolve in water, there is no other way than to oxidize it to convert it into nitrogen dioxide and then absorb it. Therefore, various oxidation methods of nitric oxide have been considered, but none of them is suitable. For example, as described in JIS, nitrogen dioxide is absorbed in a Salzmann reagent to be diazotized, and further azo is formed by coupling. In the Salzman (absorptiometric) method of developing color as a dye and measuring the absorbance, a mixed solution of 5% potassium permanganate and sulfuric acid, which is a liquid oxidizer, is usually used, but the oxidation rate is 70%. ~ 8
It was only 0%.
【０００７】又、酸化剤として三酸化クロムを含浸した
ガラスファイバー濾紙を用いる方法もあるが、この方法
では、酸化された二酸化窒素が吸着したり、酸化率が、
湿度により変化する等の不具合があった。There is also a method of using a glass fiber filter paper impregnated with chromium trioxide as an oxidizing agent, but in this method, oxidized nitrogen dioxide is adsorbed and the oxidation rate is
There was a problem such as a change in humidity.
【０００８】なお、前記ＪＩＳ Ｋ０１０４には、気体
酸化剤であるオゾンや酸素を用いて、試料ガス中の窒素
酸化物をオゾンの存在下で吸収液に吸収させて硝酸イオ
ンとし、これを亜鉛粉末で亜硝酸イオンに還元した後、
スルファニルアミド及びナフチルエチレンジアミンと反
応させ、得られた発色液の吸光度を測定し、二酸化窒素
として定量する亜鉛還元ナフチルエチレンジアミン吸光
光度法や、試料ガス中の窒素酸化物をオゾン又は酸素の
存在下で硫酸酸性過酸化水素溶液の吸収液に吸収させて
硝酸イオンとし、フェノールジスルホン酸と反応させ、
得られた発色液の吸光度から窒素酸化物量を求め、二酸
化窒素として定量するフェノールジスルホン酸吸光光度
法が記載されている。これらの方法で用いられているオ
ゾンは、一酸化窒素の良好な気体酸化剤であるが、気体
を混合するので、試料気体を希釈することになり、取扱
いが複雑になるという問題点を有していた。According to JIS K0104, ozone oxidant which is a gas oxidizer is used to absorb nitrogen oxides in a sample gas into an absorbing solution in the presence of ozone to form nitrate ions, which are then converted into zinc powder. After reducing to nitrite with
It is reacted with sulfanilamide and naphthylethylenediamine, and the absorbance of the resulting color-developing solution is measured.Zinc reduced naphthylethylenediamine absorptiometry to quantify as nitrogen dioxide, and nitrogen oxide in sample gas is converted to sulfuric acid in the presence of ozone or oxygen. Absorb into the absorbing solution of acidic hydrogen peroxide solution to make nitrate ions, react with phenoldisulfonic acid,
A phenol disulfonic acid absorptiometric method is described in which the amount of nitrogen oxides is determined from the absorbance of the resulting color-developing solution and quantified as nitrogen dioxide. Ozone used in these methods is a good gas oxidizer for nitric oxide, but since it mixes gases, it has the problem of diluting the sample gas and complicating handling. Was there.
【０００９】一方、「工業材料」１９９３年１０月号
（Ｖol. ４１ Ｎo.１３）の５９頁〜６４頁には、光半
導性を持つ二酸化チタン（Ｔi Ｏ2 ）と活性炭（ＡＣ）
を混合したＴi Ｏ2 −ＡＣ光触媒や、このＴi Ｏ2 −Ａ
Ｃ触媒に、更に少量（１−３重量％）の二酸化鉄Ｆe 2
Ｏ3 ）を添加したＴi Ｏ3 −ＡＣ−Ｆe 2 Ｏ3 （II）触
媒を用いて、トンネルや高速道路等の大気中の低濃度の
ＮＯx を除去することが提案されているが、その性能
は、未だ十分とは言えなかった。On the other hand, "Industrial Materials" October 1993 issue (Vol. 41 No. 13), pp. 59-64, shows titanium dioxide (TiO 2 ) and activated carbon (AC) having photoconductivity.
Mixed TiO 2 -AC photocatalyst and this TiO 2 -A
C catalyst with a smaller amount (1-3% by weight) of iron dioxide Fe 2
It has been proposed to remove low-concentration NOx in the atmosphere of tunnels, expressways, etc. by using a TiO 3 -AC-Fe 2 O 3 (II) catalyst added with O 3 ). Wasn't enough yet.
【００１０】本発明は、前記従来の問題点を解消するべ
くなされたもので、排気ガスや、室内空気、環境大気等
の気体中の窒素酸化物を、効率良く吸着可能な吸着管を
提供することを第１の目的とする。The present invention has been made to solve the above-mentioned conventional problems, and provides an adsorption pipe capable of efficiently adsorbing nitrogen oxides in gases such as exhaust gas, indoor air, and ambient air. This is the first purpose.
【００１１】又、本発明は、前記吸着管を用いて、前記
各種気体中の窒素酸化物を、効率良く捕集・回収可能な
捕集・回収方法を提供することを第２の目的とする。A second object of the present invention is to provide a collection / recovery method capable of efficiently collecting / recovering nitrogen oxides in the various gases by using the adsorption tube. .
【００１２】本発明は、更に、前記捕集・回収方法を利
用して、前記各種気体中の窒素酸化物を、簡便に、効率
良く、高精度で繰返し測定することが可能な測定方法及
び装置を提供することを第３の目的とする。The present invention further uses the above-mentioned collecting / recovering method to measure nitrogen oxides in the various gases simply, efficiently, and highly accurately with high accuracy. The third purpose is to provide
【００１３】[0013]
【問題点を解決するための手段】本発明は、気体中の窒
素酸化物の吸着管において、酸化チタン微粒子とハイド
ロキシアパタイトがブレンドされ、バインダーで壁面に
成膜固定されたガス流路と、該ガス流路の壁面に紫外線
を照射する手段とを備え、前記ガス流路中に吸引された
気体中の窒素酸化物を、膜壁面に吸着させることによ
り、前記第１の目的を達成したものである。The present invention relates to a gas flow path in which titanium oxide fine particles and hydroxyapatite are blended in a nitrogen oxide adsorption tube in a gas and a film is fixed on a wall surface with a binder, A means for irradiating the wall surface of the gas flow path with ultraviolet rays, and adsorbing nitrogen oxides in the gas sucked into the gas flow path onto the wall surface of the membrane, thereby achieving the first object. is there.
【００１４】本発明は、又、気体中の窒素酸化物を捕集
・回収するに際して、図１のステップ１００〜１０６に
要旨を示す如く、酸化チタン微粒子と吸着剤が、ガス流
路壁面に成膜固定されている吸着管に気体を吸引し（ス
テップ１００）、該吸引気体中の窒素酸化物を、前記吸
着管の膜壁面に吸着せしめて捕集し（ステップ１０
２）、次いで、該吸着管のガス流路を抽出水で洗浄する
（ステップ１０４）ことにより、前記吸着管の壁面に捕
集された窒素酸化物を、前記抽出水中に溶出した亜硝酸
乃至硝酸イオンとして回収する（ステップ１０６）こと
により、前記第２の目的を達成したものである。According to the present invention, when collecting and recovering nitrogen oxides in a gas, fine particles of titanium oxide and an adsorbent are formed on the wall surface of the gas flow passage as shown in steps 100 to 106 of FIG. The gas is sucked into the adsorption tube where the membrane is fixed (step 100), and the nitrogen oxides in the sucked gas are adsorbed and collected on the wall surface of the adsorption tube (step 10).
2) Then, the gas flow path of the adsorption tube is washed with extraction water (step 104) to remove the nitrogen oxides collected on the wall surface of the adsorption tube from nitrous acid or nitric acid eluted in the extraction water. By recovering as ions (step 106), the second object is achieved.
【００１５】又、前記吸着管のガス流路壁面に紫外線を
照射して、気体中の一酸化窒素と二酸化窒素を共に捕集
し、回収するようにしたものである。Further, the wall surface of the gas passage of the adsorption tube is irradiated with ultraviolet rays to collect and collect both nitric oxide and nitrogen dioxide in the gas.
【００１６】又、前記吸着管のガス流路壁面に光が当た
らないようにして、気体中の二酸化窒素のみを捕集し、
回収するようにしたものである。Further, only the nitrogen dioxide in the gas is collected so that the gas flow path wall surface of the adsorption tube is not exposed to light,
It was designed to be collected.
【００１７】又、前記吸着剤をハイドロキシアパタイト
（ＨＡp ）とし、バインダーを用いて、前記酸化チタン
（例えばＴi Ｏ2 ）微粒子と共に、前記吸着管のガス流
路壁面に成膜固定するようにしたものである。Further, the adsorbent is hydroxyapatite (HAp), and a binder is used to form a film on the wall surface of the gas passage of the adsorption tube together with the titanium oxide (for example, TiO 2 ) fine particles. Is.
【００１８】本発明は、又、気体中の窒素酸化物を測定
するに際して、図１のステップ１００〜１０８に要旨を
示す如く、酸化チタン微粒子と吸着剤が、ガス流路壁面
に成膜固定されている吸着管に一定量の気体を吸引し
（ステップ１００）、該吸引気体中の窒素酸化物を、前
記吸着管の膜壁面に吸着せしめて捕集し（ステップ１０
２）、次いで、該吸着管のガス流路を一定量の抽出水で
洗浄し（ステップ１０４）、前記吸着管の壁面に捕集さ
れた窒素酸化物を、該一定量の抽出水中に溶出した亜硝
酸イオンＮＯ2 - 乃至硝酸イオンＮＯ3 - として回収し
（ステップ１０６）、該回収した一定量の抽出水中の亜
硝酸乃至硝酸イオンを定量する（ステップ１０８）こと
により、気体中の窒素酸化物濃度を求めるようにして、
前記第３の目的を達成したものである。更に、ガス流路
を乾燥し（ステップ１１０）、再生することにより繰返
し測定が可能となる。In the present invention, when measuring nitrogen oxides in a gas, titanium oxide fine particles and an adsorbent are film-formed and fixed on the wall surface of the gas flow path, as shown in steps 100 to 108 of FIG. A certain amount of gas is sucked into the adsorbing tube (step 100), and the nitrogen oxides in the sucked gas are adsorbed and collected on the membrane wall surface of the adsorbing tube (step 10).
2) Next, the gas flow path of the adsorption tube was washed with a certain amount of extraction water (step 104), and the nitrogen oxides collected on the wall surface of the adsorption tube were eluted into the certain amount of extraction water. Nitrite ion NO 2 − or nitrate ion NO 3 − is recovered (step 106), and the nitrite or nitrate ion in the recovered fixed amount of the extracted water is quantified (step 108) to obtain nitrogen oxide in the gas. Try to find the concentration,
The third object is achieved. Further, the gas flow path is dried (step 110) and regenerated to enable repeated measurement.
【００１９】又、前記吸着管のガス流路壁面に紫外線を
照射したときの前記抽出水中のイオン定量値と、該ガス
流路壁面に光が当たらないようにしたときの前記抽出水
中のイオン定量値の差に基づいて、気体中の一酸化窒素
濃度を求めるようにしたものである。Further, a quantitative value of ions in the extracted water when ultraviolet rays are radiated to the gas flow channel wall of the adsorption tube and an ion quantitative value of the extracted water when the gas flow channel wall surface is protected from light. The concentration of nitric oxide in the gas is calculated based on the difference in the values.
【００２０】本発明は、又、気体中の窒素酸化物の測定
装置において、酸化チタンの微粒子と吸着剤が、ガス流
路壁面に成膜固定され、該ガス流路壁面に紫外線が照射
可能とされた吸着管と、該吸着管のガス流路に、一定量
の気体を吸引する手段と、前記ガス流路に、一定量の抽
出水を導入する手段と、該ガス流路から排出された抽出
水を回収する手段と、該回収された抽出水中に溶出した
亜硝酸乃至硝酸イオンを定量するための分析手段と、前
記抽出水を排出した後のガス流路を乾燥する手段とを備
え、前記亜硝酸乃至硝酸イオンの定量結果に基づいて、
気体中の窒素酸化物濃度を求めるようにして、前記第３
の目的を達成したものである。The present invention also provides a device for measuring nitrogen oxides in a gas, wherein fine particles of titanium oxide and an adsorbent are deposited and fixed on the wall surface of the gas passage, and the wall surface of the gas passage can be irradiated with ultraviolet rays. The adsorption pipe, a means for sucking a fixed amount of gas into the gas flow path of the adsorption pipe, a means for introducing a fixed amount of extracted water into the gas flow path, and the gas being discharged from the gas flow path. A means for collecting the extracted water, an analyzing means for quantifying the nitrite or nitrate ions eluted in the recovered extracted water, and means for drying the gas flow path after discharging the extracted water, Based on the quantitative results of nitrite or nitrate ions,
The nitrogen oxide concentration in the gas is determined so that the third
Has achieved the purpose of.
【００２１】又、前記吸着管を２本備え、一方の吸着管
のガス流路壁面には紫外線を照射し、他方の吸着管のガ
ス流路壁面には光が当たらないようにして、両方の吸着
管から、それぞれ回収した抽出水中のイオン定量値の差
に基づいて、気体中の一酸化窒素濃度を求めるようにし
たもである。Further, two adsorption tubes are provided, and the gas passage wall surface of one of the adsorption tubes is irradiated with ultraviolet rays, and the gas passage wall surface of the other adsorption tube is prevented from being exposed to light. The concentration of nitric oxide in the gas was determined based on the difference in the quantitative value of ions in the extracted water collected from the adsorption tube.
【００２２】又、前記分析手段を、イオンクロマトグラ
フとしたものである。Further, the analyzing means is an ion chromatograph.
【００２３】[0023]
【作用】発明者等は、光半導体として知られるＴi Ｏ2
等の酸化チタンが、近紫外光を受けて電子的に励起さ
れ、空気中で、その酸化チタンの表面に活性酸素やヒド
ロキシラジカルを生じ、これが各種のガスに対して酸化
作用を及ぼしたり、有害ガスの分解等に使われているこ
とに着目した。そして、酸化チタンを一酸化窒素の酸化
剤として用いると共に、二酸化窒素の吸収剤としても作
用させて、適当な回収のための吸収液に亜硝酸イオン乃
至は硝酸イオンとして抽出するための条件を鋭意探索
し、検討した。The inventors of the present invention have found that TiO 2 which is known as an optical semiconductor.
Titanium oxide such as is electronically excited by receiving near-ultraviolet light and produces active oxygen and hydroxy radicals on the surface of the titanium oxide in the air, which exerts an oxidizing action on various gases and is harmful. We paid attention to the fact that it is used for gas decomposition. In addition to using titanium oxide as an oxidizing agent for nitric oxide, it also acts as an absorbent for nitrogen dioxide, and the conditions for extracting as nitrite ion or nitrate ion into the absorbent for appropriate recovery are carefully studied. Explored and examined.
【００２４】その結果、酸化チタンの微粒子を、試料ガ
スが通過するガラス乃至は石英管の内壁表面に、ガス吸
着剤であるハイドロキシアパタイト（水酸化リン酸カル
シウムＣa 5 （ＯＨ）（ＰＯ4 ）3 ）と共にブレンドし
て、水性のポリテトラフルオルエチレン（ＰＴＦＥ）等
のフッ素樹脂をバインダーとして成膜化して、吸着管と
して配置すると共に、この表面に近紫外線を照射する方
法を検討した。As a result, the fine particles of titanium oxide were deposited on the inner wall surface of the glass or quartz tube through which the sample gas passed, together with hydroxyapatite (calcium hydroxide phosphate Ca 5 (OH) (PO 4 ) 3 ) as a gas adsorbent. A method of blending, forming a film with a fluororesin such as aqueous polytetrafluoroethylene (PTFE) as a binder, arranging it as an adsorption tube, and irradiating this surface with near ultraviolet rays was examined.
【００２５】この方法によると、図２に示す如く、例え
ば二酸化チタン（Ｔi Ｏ2 ）の微粒子の表面で、紫外線
照射（ｈν）による電子励起の結果、発生した活性種に
よって、一定の試料ガス流速では、図３に示す如く、二
酸化窒素（ＮＯ2 ）は勿論、一酸化窒素（ＮＯ）も酸化
されて二酸化窒素になり、ハイドロキシアパタイト（Ｈ
Ａp ）の吸着効果も作用して、膜表面に吸着される。そ
して、その後、この膜表面を抽出水、例えば脱イオン水
に一定時間接触させるだけで、これらの窒素酸化物を亜
硝酸イオンＮＯ2 - 、又は硝酸イオンＮＯ3 - として、
高い効率で抽出することができるので、この抽出水中の
亜硝酸イオンと硝酸イオンを定量することによって、計
算により試料ガス中の窒素酸化物の濃度を求めることが
できる。According to this method, as shown in FIG. 2, for example, on the surface of fine particles of titanium dioxide (TiO 2 ), a constant sample gas flow rate is generated depending on the active species generated as a result of electronic excitation by ultraviolet irradiation (hν). Then, as shown in FIG. 3, not only nitrogen dioxide (NO 2 ), but also nitric oxide (NO) is oxidized to nitrogen dioxide, and hydroxyapatite (H 2
Ap) is also adsorbed on the surface of the membrane due to the effect of adsorption. Thereafter, extraction water the membrane surface, only to contact for a predetermined time, for example, deionized water, these nitrogen oxides nitrite NO 2 -, or nitrate ions NO 3 - as,
Since the extraction can be performed with high efficiency, the concentration of nitrogen oxide in the sample gas can be obtained by calculation by quantifying the nitrite ion and the nitrate ion in the extracted water.
【００２６】又、この方法では、紫外線を照射しないで
試料ガスを吸引すると、図４に示す如く、二酸化窒素は
吸着する一方、一酸化窒素は通過するので、二酸化窒素
のみの濃度を求めることができる。Further, in this method, when the sample gas is sucked without irradiating with ultraviolet rays, as shown in FIG. 4, nitrogen dioxide is adsorbed while nitric oxide passes, so that the concentration of nitrogen dioxide alone can be obtained. it can.
【００２７】更に、この吸着管を２本配置して、一方の
吸着管には紫外線を照射し、もう一方の吸着管には紫外
線を照射しないで、同流速、同時間、試料ガスを採取し
て、同量の抽出水でイオンとして回収し、定量して、そ
の値の差をとることによって、一酸化窒素の濃度を分別
測定することも可能である。Further, by arranging two of these adsorption tubes, one adsorption tube is irradiated with ultraviolet rays and the other adsorption tube is not irradiated with ultraviolet rays, and the sample gas is sampled at the same flow rate and at the same time. Then, it is also possible to separately measure the concentration of nitric oxide by recovering as ions with the same amount of extracted water, quantifying, and taking the difference between the values.
【００２８】この吸着管は、水抽出した後に、エタノー
ル処理したり、乾燥ガスを通過させたり、加温すること
で、短時間で乾燥させることができ、窒素酸化物ガスの
酸化、吸着を繰返して行うことができるので、この方法
を利用した気体中の窒素酸化物の連続測定装置を構成す
ることも可能となる。This adsorption tube can be dried in a short time by subjecting it to ethanol treatment, passing a dry gas, or heating after water extraction, and repeating oxidation and adsorption of nitrogen oxide gas. Since it can be carried out by using the above method, it is possible to configure a continuous measuring apparatus for nitrogen oxides in a gas using this method.
【００２９】[0029]
【実施例】以下、図面を参照して、本発明の実施例を詳
細に説明する。Embodiments of the present invention will be described below in detail with reference to the drawings.
【００３０】図５乃至図７に、本発明に係る吸着管の実
施例の構成を示す。5 to 7 show the construction of an embodiment of the adsorption tube according to the present invention.
【００３１】この吸着管１０は、酸化チタン微粒子とハ
イドロキシアパタイトがブレンドされ、バインダーであ
るＰＴＦＥを用いて内壁面に塗布されたガラス管１２
と、その内側に装入された石英管１４と、中心部に装入
された紫外線ランプ１６と、その上端及び下端を固定す
る上下のコネクタ２０、３０により構成されており、前
記ガラス管１２と石英管１４の間がガス流路となってい
る。The adsorption tube 10 is a glass tube 12 in which fine particles of titanium oxide and hydroxyapatite are blended and coated on the inner wall surface using PTFE as a binder.
And a quartz tube 14 charged inside thereof, an ultraviolet lamp 16 charged in the center, and upper and lower connectors 20 and 30 for fixing the upper and lower ends thereof, and the glass tube 12. Gas passages are formed between the quartz tubes 14.
【００３２】前記上側コネクタ２０には、図６に詳細に
示す如く、吸着管１０のガラス管１２と石英管１４の間
のガス流路に試料ガスを導入するための試料ガス吸引口
２２と、試料ガスが、ガラス管１２の内壁面に吸着され
た後で、抽出水を流入させるための抽出水流入口２４
と、抽出水の排出が終了した後で、次回の測定に備え
て、前記ガス流路に乾燥用のパージガスを導入するため
のパージガス流入口２６とが形成されている。As shown in detail in FIG. 6, the upper connector 20 has a sample gas suction port 22 for introducing a sample gas into the gas flow path between the glass tube 12 and the quartz tube 14 of the adsorption tube 10. After the sample gas is adsorbed on the inner wall surface of the glass tube 12, the extraction water inlet 24 for injecting the extraction water
After the discharge of the extracted water is completed, a purge gas inlet 26 for introducing a drying purge gas into the gas passage is formed in preparation for the next measurement.
【００３３】一方、下側コネクタ３０には、図７に詳細
に示す如く、ガス流路に導入された試料ガス及びパージ
ガスを排気するための、吸引ポンプに接続される排気口
３２と、抽出水を排出するための抽出水出口３４が形成
されている。On the other hand, in the lower connector 30, as shown in detail in FIG. 7, an exhaust port 32 connected to a suction pump for exhausting the sample gas and the purge gas introduced into the gas passage, and the extracted water. An extraction water outlet 34 for discharging the water is formed.
【００３４】前記吸着管１０に試料ガスが導入される
と、紫外線を照射された酸化チタンの光触媒作用によ
り、窒素酸化物は亜硝酸や硝酸に酸化され、酸化チタン
とハイドロキシアパタイトの上に吸着・捕集される。捕
集された亜硝酸及び硝酸は、抽出水により亜硝酸イオン
又は硝酸イオンとして、容易に抽出される。そこで、抽
出液中の亜硝酸イオンや硝酸イオンを、例えばイオンク
ロマトグラフ等の分析手段で定量することにより、窒素
酸化物の量が算出される。When the sample gas is introduced into the adsorption tube 10, nitrogen oxide is oxidized into nitrous acid or nitric acid by the photocatalytic action of titanium oxide irradiated with ultraviolet rays, and is adsorbed on titanium oxide and hydroxyapatite. To be collected. The collected nitrous acid and nitric acid are easily extracted as nitrite ion or nitrate ion with extraction water. Therefore, the amount of nitrogen oxides is calculated by quantifying the nitrite ion and nitrate ion in the extract with an analyzing means such as an ion chromatograph.
【００３５】又、抽出操作を終えた吸着管１０の光触媒
活性は、エタノールや乾燥空気で乾燥することにより完
全に回復し、窒素酸化物の繰返し捕集が可能である。The photocatalytic activity of the adsorption tube 10 after the extraction operation is completely recovered by drying with ethanol or dry air, and nitrogen oxides can be repeatedly collected.
【００３６】前記ガラス管１２の内壁面に塗布される塗
布剤の構成は、例えば、二酸化チタン２５重量％、ハイ
ドロキシアパタイト２５重量％、ＰＴＦＥ５０重量％と
され、前記ガラス管１２の直径は２１mm、石英管１４の
直径は１９．５mm、有効長は２５cm、ガス流路の容積は
１３．５ml、抽出水の液量は１５ml、紫外線ランプ１６
による照射光の波長は２５４nm、強度は８Ｗ／cm2 、試
料ガスの流速は０．２l ／min とすることができる。The composition of the coating agent applied to the inner wall surface of the glass tube 12 is, for example, 25% by weight of titanium dioxide, 25% by weight of hydroxyapatite and 50% by weight of PTFE, and the diameter of the glass tube 12 is 21 mm and quartz. The diameter of the tube 14 is 19.5 mm, the effective length is 25 cm, the volume of the gas flow path is 13.5 ml, the amount of extracted water is 15 ml, and the ultraviolet lamp 16 is used.
The wavelength of the irradiation light by 254 nm, the intensity is 8 W / cm 2 , and the flow rate of the sample gas can be 0.2 l / min.
【００３７】前記吸着管１０にＮＯx 標準ガスを導入
し、出口ガス中のＮＯx 濃度を、ＮＯとＯ3 の気相反応
による化学発光を検出して、ＮＯx の濃度を連続測定す
るＮＯx 濃度計で測定したところ、ハイドロキシアパタ
イトを加えたものは、二酸化チタン単独のものや、二酸
化チタンに銀を加えたものに比べて、ＮＯx の捕集力が
大きく、捕集効率がほぼ１００％になることが確認でき
た。A NOx concentration meter for continuously measuring the NOx concentration by introducing NOx standard gas into the adsorption tube 10 and detecting the NOx concentration in the outlet gas by detecting chemiluminescence due to the gas phase reaction of NO and O 3. As a result of measurement, it was found that the one with hydroxyapatite added had a larger NOx trapping power, and the trapping efficiency was almost 100%, as compared with titanium dioxide alone or titanium dioxide with silver. It could be confirmed.
【００３８】更に、吸着管１０に、試料ガスを０．２l
／min で３０分間流した後、純水１５mlを吸着管１０に
入れて５分間保持し、抽出水中の亜硝酸イオン、硝酸イ
オンをイオンクロマトグラフで定量したところ、吸着管
１０に捕集された窒素酸化物のほぼ全量が亜硝酸イオ
ン、硝酸イオンに変換され、図８に示す如く、２回の抽
出操作でほぼ１００％回収されることが確認できた。図
８は、３回同じ実験を行い、その平均値（抽出効率）を
図にプロットしたものである。図において「▽」印及び
「△」印は、平均値上下の標準偏差を示す。Further, 0.2 l of sample gas is put into the adsorption tube 10.
After flowing for 30 minutes at 30 psi / min, 15 ml of pure water was put into the adsorption tube 10 and kept for 5 minutes, and nitrite ion and nitrate ion in the extracted water were quantified by ion chromatography. It was confirmed that almost all of the nitrogen oxides were converted to nitrite ions and nitrate ions, and as shown in FIG. 8, almost 100% was recovered by the two extraction operations. In FIG. 8, the same experiment was performed three times, and the average value (extraction efficiency) was plotted in the figure. In the figure, “∇” marks and “Δ” marks indicate standard deviations above and below the average value.
【００３９】又、前記化学発光法によるＮＯx 濃度計に
より測定したＮＯx 濃度とのクロスチェックでも、高い
相関が認められ、本発明法の有効性が確認できた。Also, a high correlation was confirmed by cross-checking with the NOx concentration measured by the NOx concentration meter by the chemiluminescence method, confirming the effectiveness of the method of the present invention.
【００４０】この吸着管１０とイオンクロマトグラフと
を接続し、各部に取り付けた自動バルブ及びポンプのオ
ンオフをシーケンサーでプログラム制御することによ
り、ＮＯx の自動連続測定が可能となる。このような自
動測定装置の実施例を図９に示す。By connecting the adsorption tube 10 and the ion chromatograph and program-controlling the on / off of the automatic valves and pumps attached to each part by a sequencer, it is possible to perform automatic continuous measurement of NOx. An embodiment of such an automatic measuring device is shown in FIG.
【００４１】この自動測定装置は、試料ガスを捕集し、
回収する前記吸着管１０を備えた試料ガス捕集回収部４
０と、該試料ガス捕集回収部４０で回収された抽出水を
送液する送液ポンプ８０と、該送液ポンプ８０により送
られてくる抽出水中の硝酸イオン及び亜硝酸イオンを測
定するイオンクロマトグラフ８２と、各部に取付けた自
動バルブ及びポンプのオンオフをプログラム制御する制
御部（例えばシーケンサー）９０とから構成されてい
る。This automatic measuring device collects a sample gas,
Sample gas collection and collection section 4 equipped with the adsorption tube 10 for collection
0, a liquid feed pump 80 that feeds the extracted water collected by the sample gas collection and collection unit 40, and ions that measure nitrate ions and nitrite ions in the extracted water sent by the liquid feed pump 80 It comprises a chromatograph 82 and a control unit (for example, a sequencer) 90 that programmatically controls on / off of automatic valves and pumps attached to each unit.
【００４２】前記試料ガス捕集回収部４０は、例えば大
気中の試料ガスを吸引する試料ガス吸引口４２と、校正
用のゼロガスを生成するゼロガス生成器４４と、前記試
料ガス吸引口４２から吸引された試料ガス、又は、前記
ゼロガス生成器４４で生成されたゼロガスのいずれか一
方を吸着管１０に流すための三方弁４６と、該三方弁４
６により選択された試料ガス又はゼロガスの流量を、所
定値、例えば０．２l／min に調整して、試料ガス吸引
口２２より、吸着管１０のガス流路に導入するための流
量調整器４８と、試料ガス又はゼロガスが吸着された吸
着管１０のガス流路に抽出水を注入するための抽出水注
入器５０と、該抽出水注入器５０より吸着管１０の抽出
水流入口２４に供給される抽出水をオンオフ制御するた
めのオンオフ弁５２と、抽出水排出後、吸着管１０のガ
ス流路を、次回の測定に備えて乾燥するためのパージガ
スを生成するパージガス生成器５４と、該パージガス生
成器５４から吸着管１０のパージガス流入口２６に導入
されるパージガスをオンオフ制御するためのオンオフ弁
５６と、吸着管１０の乾燥を迅速に行うための加温装置
５８と、吸着管１０の排気口３２より排出される試料ガ
ス及びパージガスのオンオフを制御するためのオンオフ
弁６０と、該オンオフ弁６０を通った試料ガス又はパー
ジガス中の水分を除去するためのミストストラップ６２
と、該ミストストラップ６２に接続された試料ガス吸引
ポンプ６４と、前記吸着管１０の抽出水出口３４から回
収される抽出水のオンオフを制御するためのオンオフ弁
６６と、該オンオフ弁６６を介して導入される抽出水を
計量するための、光ファイバーセンサ７０を備えた抽出
水計量部６８とを備えている。The sample gas collecting / collecting section 40 sucks the sample gas suction port 42 for sucking the sample gas in the atmosphere, the zero gas generator 44 for generating the zero gas for calibration, and the sample gas suction port 42, for example. A three-way valve 46 for flowing either the sample gas thus generated or the zero gas generated by the zero gas generator 44 into the adsorption pipe 10, and the three-way valve 4
The flow rate controller 48 for adjusting the flow rate of the sample gas or zero gas selected by 6 to a predetermined value, for example, 0.2 l / min, and introducing the sample gas into the gas flow path of the adsorption tube 10 from the sample gas suction port 22. And an extraction water injector 50 for injecting extraction water into the gas flow path of the adsorption tube 10 in which the sample gas or zero gas is adsorbed, and the extraction water injector 50 supplies the extraction water inflow port 24 of the adsorption tube 10. An on / off valve 52 for controlling the on / off of the extracted water, a purge gas generator 54 for generating a purge gas for drying the gas flow path of the adsorption pipe 10 in preparation for the next measurement after discharging the extracted water, and the purge gas. An on / off valve 56 for controlling on / off of the purge gas introduced from the generator 54 to the purge gas inlet 26 of the adsorption pipe 10, a heating device 58 for rapidly drying the adsorption pipe 10, and an adsorption pipe 10. Mist strap 62 for removing the off valve 60 for controlling on and off of the sample gas and the purge gas is exhausted from the exhaust port 32, the moisture in the sample gas or the purge gas passing through the on-off valve 60
Via the sample gas suction pump 64 connected to the mist strap 62, the on / off valve 66 for controlling the on / off of the extraction water recovered from the extraction water outlet 34 of the adsorption tube 10, and the on / off valve 66. And an extracted water measuring unit 68 having an optical fiber sensor 70 for measuring the extracted water introduced.
【００４３】この測定装置によれば、各部に取付けた自
動バルブ及びポンプのオンオフを、制御部９０でプログ
ラム制御することにより、吸着管１０によるガスの捕集
から、イオンクロマトグラフ８２による抽出水中の亜硝
酸イオン、硝酸イオンの分析に至る全ての操作が自動的
に行われる。According to this measuring apparatus, the control unit 90 program-controls ON / OFF of the automatic valves and pumps attached to the respective units, so that the adsorption pipe 10 collects the gas and the ion chromatograph 82 extracts water. All the operations up to the analysis of nitrite ion and nitrate ion are automatically performed.
【００４４】特に、前記イオンクロマトグラフ８２の分
離カラムとして、一般に濃縮カラムと呼ばれる短いカラ
ムを用いた場合には、分析時間が８分以内に短縮され、
１時間サイクルでの繰返し測定が可能となる。In particular, when a short column generally called a concentration column is used as the separation column of the ion chromatograph 82, the analysis time is shortened to within 8 minutes,
Repeated measurement in 1 hour cycle becomes possible.
【００４５】本実施例においては、抽出水計量部６８で
光ファイバーセンサ７０を用いて一定容量を計量してい
るので、測定精度と再現性が著しく向上できた。In this embodiment, since the extracted water metering unit 68 measures the constant volume using the optical fiber sensor 70, the measurement accuracy and reproducibility can be remarkably improved.
【００４６】又、本実施例においては、一定のガス流速
でサンプリングしているので、窒素酸化物を定量的に捕
集、回収できる。なお、吸着管１０に導入される試料ガ
スの容積を一定とする方法はこれに限定されず、流量調
整器４８の代わりに、一定量の容積を導入可能な制御弁
を用いてもよい。Further, in this embodiment, since the sampling is carried out at a constant gas flow rate, nitrogen oxides can be quantitatively collected and collected. Note that the method of making the volume of the sample gas introduced into the adsorption tube 10 constant is not limited to this, and a control valve capable of introducing a certain amount of volume may be used instead of the flow rate regulator 48.
【００４７】更に、本実施例においては、吸着管１０の
周囲に加温装置５８を配設しているので、吸着管１０の
ガス流路を迅速に乾燥することができる。なお、加温装
置５８は省略することも可能である。Further, in this embodiment, since the heating device 58 is arranged around the adsorption pipe 10, the gas flow path of the adsorption pipe 10 can be dried quickly. The warming device 58 can be omitted.
【００４８】更に、ＮＯx を捕集した抽出水中の亜硝酸
と硝酸イオンの比は約２：１で安定しているので、検出
器に吸光光度計を組込んだフローインジェクションシス
テムとザルツマン法とにより自動計測することも可能で
ある。Furthermore, since the ratio of nitrous acid to nitrate ion in the extracted water in which NOx is collected is stable at about 2: 1, the flow injection system incorporating the absorptiometer into the detector and the Salzman method are used. It is also possible to automatically measure.
【００４９】[0049]
【発明の効果】以上説明した通り、本発明の吸着管によ
れば、排気ガスや、室内空気、環境大気等の気体中の窒
素酸化物を、効率良く吸着することが可能である。又、
吸着管の吸着容量は、ハイドロキシアパタイト等の吸着
剤のブレンド比で調節可能であり、高容量にすること
で、高濃度の排気ガス測定にも用いることができる。更
に、吸着管は、乾燥処理することにより、繰返し使用可
能であるので、一酸化窒素と二酸化窒素を自動測定する
ことが可能となる。As explained above, according to the adsorption pipe of the present invention, it is possible to efficiently adsorb nitrogen oxides in exhaust gas, gas such as indoor air and ambient air. or,
The adsorption capacity of the adsorption tube can be adjusted by the blending ratio of an adsorbent such as hydroxyapatite, and by increasing the capacity, it can be used for measuring exhaust gas of high concentration. Furthermore, since the adsorption tube can be repeatedly used by being dried, it becomes possible to automatically measure nitric oxide and nitrogen dioxide.
【００５０】又、本発明の捕集・回収方法によれば、前
記のような各種気体中の窒素酸化物を、簡便に、効率良
く捕集することができる。特に、吸着管に紫外線を照射
するか否かでＮＯx とＮＯの分別捕集が可能であるた
め、分別測定が可能である。更に、脱イオン水によって
高効率でイオンとして抽出可能なので、定量操作が極め
て容易である。Further, according to the collection / recovery method of the present invention, nitrogen oxides in various gases as described above can be collected simply and efficiently. In particular, since it is possible to separately collect NOx and NO depending on whether or not the adsorption tube is irradiated with ultraviolet rays, it is possible to perform a separate measurement. Furthermore, since it can be extracted as ions with high efficiency using deionized water, the quantitative operation is extremely easy.
【００５１】又、本発明の測定方法及び装置によれば、
前記のような各種気体中の窒素酸化物の濃度を、簡便
に、効率良く、高精度で繰返し測定することが可能とな
る。According to the measuring method and apparatus of the present invention,
The concentration of nitrogen oxides in the various gases as described above can be repeatedly measured easily, efficiently, and with high accuracy.
【図１】本発明に係る気体中の窒素酸化物の捕集・回収
方法及びこれを用いた測定方法の要旨を示す流れ図FIG. 1 is a flow chart showing the outline of a method for collecting and recovering nitrogen oxides in a gas and a measuring method using the same according to the present invention.
【図２】本発明に係る吸着管における窒素酸化物の捕集
機構を示す線図FIG. 2 is a diagram showing a nitrogen oxide collection mechanism in the adsorption tube according to the present invention.
【図３】同じく窒素酸化物の捕集状態を示す線図[Fig. 3] Similarly, a diagram showing the state of collection of nitrogen oxides.
【図４】同じく二酸化窒素の選択捕集状態を示す線図FIG. 4 is a diagram showing a state of selective collection of nitrogen dioxide.
【図５】本発明に係る吸着管の実施例の構成を示す縦断
面図FIG. 5 is a vertical cross-sectional view showing the configuration of an embodiment of an adsorption pipe according to the present invention.
【図６】図５のVI−VI線に沿う横断面図6 is a cross-sectional view taken along line VI-VI of FIG.
【図７】同じく図５のVII −VII 線に沿う横断面図FIG. 7 is a transverse sectional view taken along line VII-VII of FIG.
【図８】前記吸着管の実施例における、一酸化窒素を捕
集した吸着管の水抽出回数と抽出効率との関係の例を示
す線図FIG. 8 is a diagram showing an example of the relationship between the number of times of extraction of water and the extraction efficiency of an adsorption tube in which nitric oxide is collected in the example of the adsorption tube.
【図９】本発明に係る窒素酸化物の測定装置の実施例の
構成を示す管路図FIG. 9 is a conduit diagram showing a configuration of an embodiment of a nitrogen oxide measuring apparatus according to the present invention.
１０…吸着管 １２…ガラス管 １４…石英管 １６…紫外線ランプ ４０…試料ガス捕集回収部 ４２…試料ガス吸引口 ４８…流量調整器 ５０…抽出水注入器 ５４…パージガス生成器 ５８…加温装置 ６４…試料ガス吸引ポンプ ６８…抽出水計量部 ８０…送液ポンプ ８２…イオンクロマトグラフ ９０…制御部 10 ... Adsorption tube 12 ... Glass tube 14 ... Quartz tube 16 ... Ultraviolet lamp 40 ... Sample gas collection and recovery section 42 ... Sample gas suction port 48 ... Flow rate regulator 50 ... Extracted water injector 54 ... Purge gas generator 58 ... Heating Apparatus 64 ... Sample gas suction pump 68 ... Extracted water metering unit 80 ... Liquid feed pump 82 ... Ion chromatograph 90 ... Control unit
───────────────────────────────────────────────────── フロントページの続き (72)発明者 宮井 迅吉 東京都武蔵野市吉祥寺北町４丁目13番14号 電気化学計器株式会社内 (72)発明者 猪俣 保 東京都武蔵野市中町一丁目15番５号 三鷹 高木ビル 横河アナリティカルシステムズ 株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Miyakichi Shinkichi 4-13-14 Kitacho, Kichijoji, Musashino-shi, Tokyo Electrochemical Instruments Co., Ltd. (72) Inventor Ho Inomata 1-15-5 Nakamachi, Musashino-shi, Tokyo No. Mitaka Takagi Building Yokogawa Analytical Systems Co., Ltd.
Claims (10)
トがブレンドされ、バインダーで壁面に成膜固定された
ガス流路と、 該ガス流路の壁面に紫外線を照射する手段とを備え、 前記ガス流路中に吸引された気体中の窒素酸化物を、膜
壁面に吸着させることを特徴とする、気体中の窒素酸化
物の吸着管。1. A gas flow path comprising a mixture of titanium oxide fine particles and hydroxyapatite, a wall surface of which is fixed by a binder to form a film, and a means for irradiating the wall surface of the gas flow path with ultraviolet rays. An adsorption tube for nitrogen oxides in a gas, which adsorbs nitrogen oxides in the gas sucked into a wall surface of a film.
面に成膜固定されている吸着管に気体を吸引し、 該吸引気体中の窒素酸化物を、前記吸着管の膜壁面に吸
着せしめて捕集し、 次いで、該吸着管のガス流路を抽出水で洗浄することに
より、 前記吸着管の壁面に捕集された窒素酸化物を、前記抽出
水中に溶出した亜硝酸乃至硝酸イオンとして回収するこ
とを特徴とする、気体中の窒素酸化物の捕集・回収方
法。2. Titanium oxide fine particles and an adsorbent suck a gas into an adsorption pipe fixed to a wall surface of a gas flow channel, and nitrogen oxide in the suction gas is adsorbed to a wall surface of the adsorption pipe. By collecting at least, then, by cleaning the gas flow path of the adsorption tube with extraction water, the nitrogen oxides collected on the wall surface of the adsorption tube, nitrous acid or nitrate ions eluted in the extraction water A method for collecting and recovering nitrogen oxides in a gas, characterized in that
壁面に紫外線を照射して、気体中の一酸化窒素と二酸化
窒素を共に捕集し、回収することを特徴とする、気体中
の窒素酸化物の捕集・回収方法。3. The gas according to claim 2, wherein the gas channel wall surface of the adsorption tube is irradiated with ultraviolet rays to capture and recover both nitric oxide and nitrogen dioxide in the gas. Method for collecting and recovering nitrogen oxides.
壁面に光が当たらないようにして、気体中の二酸化窒素
のみを捕集し、回収することを特徴とする、気体中の窒
素酸化物の捕集・回収方法。4. The nitrogen in the gas according to claim 2, wherein only the nitrogen dioxide in the gas is collected and recovered so that the wall surface of the gas passage of the adsorption tube is not exposed to light. Oxide collection and recovery method.
前記吸着剤がハイドロキシアパタイトとされ、バインダ
ーを用いて、前記酸化チタン微粒子と共に、前記吸着管
のガス流路壁面に成膜固定されていることを特徴とす
る、気体中の窒素酸化物の捕集・回収方法。5. The method according to any one of claims 2 to 4,
The adsorbent is hydroxyapatite, and a binder is used to form a film on the gas channel wall surface of the adsorption tube together with the titanium oxide fine particles, and the nitrogen oxide in the gas is collected.・ Collection method.
面に成膜固定されている吸着管に一定量の気体を吸引
し、 該吸引気体中の窒素酸化物を、前記吸着管の膜壁面に吸
着せしめて捕集し、 次いで、該吸着管のガス流路を一定量の抽出水で洗浄
し、 前記吸着管の壁面に捕集された窒素酸化物を、該一定量
の抽出水中に溶出した亜硝酸乃至硝酸イオンとして回収
し、 該回収した一定量の抽出水中の亜硝酸乃至硝酸イオンを
定量することにより、 気体中の窒素酸化物濃度を求めることを特徴とする、気
体中の窒素酸化物の測定方法。6. Titanium oxide fine particles and an adsorbent suck a certain amount of gas into an adsorption tube that is film-formed and fixed on the wall surface of a gas channel, and remove nitrogen oxide in the aspirated gas into a film of the adsorption tube. It is adsorbed and collected on the wall surface, then the gas flow path of the adsorption tube is washed with a fixed amount of extraction water, and the nitrogen oxides collected on the wall surface of the adsorption tube are mixed with the fixed amount of extraction water. Nitrogen in gas is characterized in that it is recovered as eluted nitrite or nitrate ion, and the concentration of the nitrous acid or nitrate ion in the extracted fixed amount of extraction water is quantified to obtain the nitrogen oxide concentration in the gas. Oxide measurement method.
壁面に紫外線を照射したときの前記抽出水中のイオン定
量値と、該ガス流路壁面に光が当たらないようにしたと
きの前記抽出水中のイオン定量値の差に基づいて、気体
中の一酸化窒素濃度を求めることを特徴とする、気体中
の窒素酸化物の測定方法。7. The quantified value of ions in the extracted water when the gas flow passage wall surface of the adsorption pipe is irradiated with ultraviolet rays, and the gas flow passage wall surface of the adsorption pipe when light is prevented from shining. A method for measuring nitrogen oxides in a gas, which comprises determining the concentration of nitric oxide in the gas based on the difference in the quantitative value of ions in the extracted water.
壁面に成膜固定され、該ガス流路壁面に紫外線が照射可
能とされた吸着管と、 該吸着管のガス流路に、一定量の気体を吸引する手段
と、 前記ガス流路に、一定量の抽出水を導入する手段と、 該ガス流路から排出された抽出水を回収する手段と、 該回収された抽出水中に溶出した亜硝酸乃至硝酸イオン
を定量するための分析手段と、 前記抽出水を排出した後のガス流路を乾燥する手段とを
備え、 前記亜硝酸乃至硝酸イオンの定量結果に基づいて、気体
中の窒素酸化物濃度を求めることを特徴とする、気体中
の窒素酸化物の測定装置。8. An adsorption pipe in which fine particles of titanium oxide and an adsorbent are film-fixed on a wall surface of a gas passage, and ultraviolet rays can be irradiated on the wall surface of the gas passage, and a gas passage of the adsorption pipe, A unit for sucking a fixed amount of gas, a unit for introducing a fixed amount of extraction water into the gas flow channel, a unit for collecting the extraction water discharged from the gas flow channel, and a unit for collecting the extraction water in the recovery channel. An analysis means for quantifying the eluted nitrite or nitrate ion, and means for drying the gas flow path after discharging the extracted water, based on the quantification result of the nitrite or nitrate ion, in the gas An apparatus for measuring nitrogen oxides in a gas, characterized in that the concentration of nitrogen oxides of is determined.
られ、一方の吸着管のガス流路壁面には紫外線が照射さ
れ、他方の吸着管のガス流路壁面には光が当たらないよ
うにされ、両方の吸着管から、それぞれ回収された抽出
水中のイオン定量値の差に基づいて、気体中の一酸化窒
素濃度を求めることを特徴とする、気体中の窒素酸化物
の測定装置。9. The adsorption tube according to claim 8, wherein two adsorption tubes are provided, one of the adsorption tubes is irradiated with ultraviolet rays, and the other adsorption tube is not exposed to light. A device for measuring nitrogen oxides in a gas, characterized in that the concentration of nitric oxide in the gas is obtained based on the difference in the quantitative value of ions in the extracted water recovered from both adsorption tubes. .
が、イオンクロマトグラフであることを特徴とする、気
体中の窒素酸化物の測定装置。10. An apparatus for measuring nitrogen oxides in a gas according to claim 8 or 9, wherein the analyzing means is an ion chromatograph.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23317394A JP3406968B2 (en) | 1994-09-28 | 1994-09-28 | Adsorption tube for nitrogen oxides in gas, collection / recovery method using the same, and measurement method and apparatus using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23317394A JP3406968B2 (en) | 1994-09-28 | 1994-09-28 | Adsorption tube for nitrogen oxides in gas, collection / recovery method using the same, and measurement method and apparatus using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0894502A true JPH0894502A (en) | 1996-04-12 |
| JP3406968B2 JP3406968B2 (en) | 2003-05-19 |
Family
ID=16950878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23317394A Expired - Fee Related JP3406968B2 (en) | 1994-09-28 | 1994-09-28 | Adsorption tube for nitrogen oxides in gas, collection / recovery method using the same, and measurement method and apparatus using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3406968B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999033566A1 (en) * | 1997-12-25 | 1999-07-08 | Japan As Represented By Director General Of The Agency Of Industrial Science And Technology | Photocatalyst powder for environmental purification, polymer composition containing the powder and molded article thereof, and processes for producing these |
| US6033459A (en) * | 1997-07-15 | 2000-03-07 | Nec Corporation | Gas collection apparatus, gas analyzing apparatus using the same and gas analyzing method |
| JP2006113006A (en) * | 2004-10-18 | 2006-04-27 | Nikkiso Co Ltd | Pretreatment device for chemical analysis |
| JP2008275327A (en) * | 2007-04-25 | 2008-11-13 | Mitsubishi Chemical Analytech Co Ltd | Analyzer for nitrogen, sulfur and/or halogen in sample |
| JP2009010392A (en) * | 2001-09-24 | 2009-01-15 | Entegris Inc | System and method for determining and controlling contamination |
| JP2009222563A (en) * | 2008-03-17 | 2009-10-01 | Shibata Kagaku Kk | Gas component collection apparatus and gas component collection method |
| JP2017122661A (en) * | 2016-01-07 | 2017-07-13 | 紀本電子工業株式会社 | Volatile organic compound measuring device and volatile organic compound measuring method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2751852B2 (en) | 1994-06-06 | 1998-05-18 | 日本電気株式会社 | Gas analyzer, analysis method thereof, and gas sampling device |
-
1994
- 1994-09-28 JP JP23317394A patent/JP3406968B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6033459A (en) * | 1997-07-15 | 2000-03-07 | Nec Corporation | Gas collection apparatus, gas analyzing apparatus using the same and gas analyzing method |
| WO1999033566A1 (en) * | 1997-12-25 | 1999-07-08 | Japan As Represented By Director General Of The Agency Of Industrial Science And Technology | Photocatalyst powder for environmental purification, polymer composition containing the powder and molded article thereof, and processes for producing these |
| JP2009010392A (en) * | 2001-09-24 | 2009-01-15 | Entegris Inc | System and method for determining and controlling contamination |
| JP2006113006A (en) * | 2004-10-18 | 2006-04-27 | Nikkiso Co Ltd | Pretreatment device for chemical analysis |
| JP4549152B2 (en) * | 2004-10-18 | 2010-09-22 | 日機装株式会社 | Pretreatment equipment for chemical analysis |
| JP2008275327A (en) * | 2007-04-25 | 2008-11-13 | Mitsubishi Chemical Analytech Co Ltd | Analyzer for nitrogen, sulfur and/or halogen in sample |
| JP2009222563A (en) * | 2008-03-17 | 2009-10-01 | Shibata Kagaku Kk | Gas component collection apparatus and gas component collection method |
| JP2017122661A (en) * | 2016-01-07 | 2017-07-13 | 紀本電子工業株式会社 | Volatile organic compound measuring device and volatile organic compound measuring method |
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