JP3483208B2 - Apparatus for removing nitrogen oxides from the atmosphere by diffusion scrubber method and its use - Google Patents
Apparatus for removing nitrogen oxides from the atmosphere by diffusion scrubber method and its useInfo
- Publication number
- JP3483208B2 JP3483208B2 JP2003044989A JP2003044989A JP3483208B2 JP 3483208 B2 JP3483208 B2 JP 3483208B2 JP 2003044989 A JP2003044989 A JP 2003044989A JP 2003044989 A JP2003044989 A JP 2003044989A JP 3483208 B2 JP3483208 B2 JP 3483208B2
- Authority
- JP
- Japan
- Prior art keywords
- air
- nitrogen oxides
- parallel plates
- pair
- coating layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims description 117
- 238000009792 diffusion process Methods 0.000 title claims description 29
- 238000000034 method Methods 0.000 title claims description 28
- 239000007789 gas Substances 0.000 claims description 40
- 239000002245 particle Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000011941 photocatalyst Substances 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 14
- 239000003463 adsorbent Substances 0.000 claims description 13
- 239000011882 ultra-fine particle Substances 0.000 claims description 13
- 239000011247 coating layer Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 3
- 230000003647 oxidation Effects 0.000 claims 3
- 238000007254 oxidation reaction Methods 0.000 claims 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 2
- 229910052719 titanium Inorganic materials 0.000 claims 2
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000011109 contamination Methods 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 25
- 229910001220 stainless steel Inorganic materials 0.000 description 14
- 239000010935 stainless steel Substances 0.000 description 14
- 238000009423 ventilation Methods 0.000 description 11
- 238000004887 air purification Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 5
- 238000004378 air conditioning Methods 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 238000005273 aeration Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、大気浄化処理装
置、特に、空調装置の空気流路または排気ガス処理装置
のガス流路に付設して用いるのに適した拡散スクラバ法
による大気浄化処理装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an air purification processing apparatus, and more particularly to an air purification processing apparatus by a diffusion scrubber method suitable for being attached to an air flow path of an air conditioner or a gas flow path of an exhaust gas processing apparatus. Regarding
【０００２】[0002]
【従来の技術】大気中の窒素酸化物を除去する技術開発
は、主として、工場、自動車等の発生源対策を中心に行
われており、大規模な工場等から排出する数千ｐｐｍと
言った高濃度の窒素酸化物については、アンモニアとの
反応により窒素と水に還元する「選択接触還元法」がこ
れまで実用化されてきた。また、ガソリンエンジン車か
らの窒素酸化物の排出は、「三元触媒」、「リーンバー
ン」等の導入で改善されてきた。2. Description of the Related Art Development of technology for removing nitrogen oxides in the atmosphere is mainly carried out mainly on measures against sources such as factories and automobiles, and it is said that thousands of ppm emitted from large-scale factories, etc. For high-concentration nitrogen oxides, the "selective catalytic reduction method" of reducing nitrogen and water by reaction with ammonia has been put into practical use. Emissions of nitrogen oxides from gasoline engine vehicles have been improved by introducing "three-way catalyst" and "lean burn".
【０００３】酸化チタン光触媒を用い、太陽光を利用し
て大気中の窒素酸化物を浄化する技術も知られており、
舗装道路や道路構造物に酸化チタンを塗布することが、
最近、地方自治体の道路沿道で行われ、その浄化性能が
確認されてきた（竹内浩士、「光触媒による環境大気の
浄化・修復技術」、大気環境学会誌、３３、１３９−１
５０、１９９８年）。また、道路トンネルの排気設備に
酸化チタンを用いた例も報告されている（西方聡、「低
濃度脱硝装置」、工業材料、４５、８６−８８、１９９
７年）。There is also known a technology for purifying nitrogen oxides in the atmosphere by utilizing sunlight using a titanium oxide photocatalyst,
Applying titanium oxide to paved roads and road structures,
Recently, the purification performance has been confirmed along the roads of local governments (Hiroshi Takeuchi, "Purification / restoration technology for environmental air using photocatalyst", Journal of Atmospheric Environment, 33, 139-1).
50, 1998). Also, an example of using titanium oxide for the exhaust equipment of a road tunnel has been reported (Satoshi Nishikata, “Low-concentration denitration equipment”, Industrial Materials, 45, 86-88, 199.
7 years).
【０００４】その他、酸化チタン光触媒を用いた大気中
の窒素酸化物の除去手段としては、「自動車トンネル用
換気設備」（特開平５−２３７３８１号公報）、「汚染
物質の除去方法及び浄化材」（特開平６−３１５６１４
号公報）、「トンネル空気浄化装置」（特開平８−１５
１８９９号公報）、「トンネル内空気浄化装置およびそ
の装置に用いられるトンネル内装板」（特開平９−２７
１６３５号公報）、「高速道路上の汚染空気の浄化方
法」（特開平１０−１５１３２３号公報）、「気体浄化
・吸音部材、気体浄化装置及び気体浄化システム」（特
開平１０−２４９１６７号公報）等が公知である。In addition, as means for removing nitrogen oxides in the air using a titanium oxide photocatalyst, "Ventilation equipment for automobile tunnel" (Japanese Patent Laid-Open No. 5-237381), "Method for removing pollutants and purification material" (JP-A-6-315614
Japanese Unexamined Patent Publication No. 8-15).
1899), "Tunnel air purifying device and tunnel interior plate used for the device" (JP-A-9-27).
1635), "Purification method for polluted air on highways" (JP-A-10-151323), "Gas cleaning / sound absorbing member, gas cleaning device and gas cleaning system" (JP-A-10-249167). Etc. are known.
【０００５】酸化チタン微粒子によって気体中の窒素酸
化物を吸着する際に、酸化チタン微粒子にハイドロキシ
アパタイト粉末を混合することによって吸着効率を高め
ることができることも知られている（Y.Komazakiet a
l.,Atoms.Environ.,33,4363〜4371,(1999)）。It is also known that, when adsorbing nitrogen oxides in a gas by titanium oxide fine particles, the adsorption efficiency can be increased by mixing hydroxyapatite powder with the titanium oxide fine particles (Y. Komazaki et a.
L., Atoms. Environ., 33, 4363-4371, (1999)).
【０００６】[0006]
【発明が解決しようとする課題】大気汚染への社会的関
心の高まりから、種々の空気清浄技術の研究が行われて
きている。しかしながら、問題の重要性に比較して、そ
の多くの技術は、既存のフィルタ法、活性炭等の吸着剤
等による除去技術を単に転用したものに過ぎず、その処
理能力や処理量に疑問を持たざるを得ないものも多い。Various air purification techniques have been researched due to increasing social concern about air pollution. However, compared with the importance of the problem, many of the technologies are merely diversions of existing filter methods and removal technologies using adsorbents such as activated carbon, and there are doubts about their processing capacity and throughput. There are many things that cannot be helped.
【０００７】最近では、酸化チタン光触媒を利用した空
気清浄技術も開発されてきた。この技術は、特殊な装置
を必要とせず、ＮＯXの経済的な浄化技術ではあるが、
反応槽でのバッチ的な汚染空気処理技術であるために、
汚染空気処理量が毎分数リットル程度と少なく、多量の
汚染空気処理に関しては問題である。また、塗布された
酸化チタン表面での除去効果はあるとしても、広範な空
間に拡散したＮＯXを効率的に除去することは原理的に
困難である。Recently, an air cleaning technique utilizing a titanium oxide photocatalyst has been developed. This technology does not require special equipment and is an economical NO x purification technology,
Because it is a batch-type contaminated air treatment technology in the reactor,
The amount of treated contaminated air is as small as several liters per minute, which is a problem for treating a large amount of contaminated air. In addition, even if there is a removing effect on the coated titanium oxide surface, it is theoretically difficult to efficiently remove the NO x diffused in a wide space.
【０００８】そこで、従来の技術の延長ではなく、有害
ガス成分を効率良く完全に除去し、しかも、大量の汚染
空気の処理を行える革新的な空気清浄技術の開発が必要
である。Therefore, it is necessary to develop an innovative air cleaning technology capable of efficiently and completely removing harmful gas components and treating a large amount of contaminated air, rather than extending the conventional technology.
【０００９】[0009]
【課題を解決するための手段】本発明者は、酸化チタン
超微粒子光触媒を用いて高いＮＯX除去効率を有する連
続使用可能な窒素酸化物除去装置について研究開発を続
けた結果、拡散スクラバ法による除去装置によって空気
中の代表的な有害ガス成分の窒素酸化物を効率的に除去
できることを見出した。The inventors of the present invention continued to research and develop a nitrogen oxide removing apparatus which has a high NO x removal efficiency and uses a titanium oxide ultrafine particle photocatalyst, and as a result, a diffusion scrubber method was used. It has been found that the removal device can efficiently remove nitrogen oxide, which is a typical harmful gas component in the air.
【００１０】すなわち、本発明は、（１）一対の平行板
の狭い隙間に汚染空気を流し、拡散係数の小さい粒子は
該一対の平行板の狭い隙間をそのまま通過させて該一対
の平行板の出口から排出させ、かつ該一対の平行板の内
壁面に汚染空気中の有害ガス成分を拡散させて該内壁表
面に吸着させるための、平行に向き合わせた一対の平行
板からなり、該隙間は下記の式（Gormleyの理論式）を
満たす間隔とし、該一対の平行板の該内壁表面に酸化チ
タン超微粒子光触媒と吸着剤とからなる塗布層を設ける
とともに該隙間内に光を照射できる構造としたことを特
徴とする大気中の窒素酸化物の除去処理装置、である。式：ｆ＝１−［０．９１０ｅｘｐ（−３．７７μ）＋
０．０５３１ｅｘｐ（−４２．８μ）］、μ＝ｂＤＬ／
ａＱ （ただし、ｆ：除去効率、Ｄ：対象とするガスの拡散係
数（ｃｍ 2 ／秒）、ａ：平行板の間隔（ｃｍ）、Ｌ：平
行板の長さ（ｃｍ）、μ：沈着パラメータ、Ｑ：大気吸
引流量（ｃｍ 3 ／秒）、ｂ：平行板の幅（ｃｍ）であ
る。） また、本発明は、（２）該塗布層がバインダーと
してポリテトラフロロエチレンを用いて設けられている
ことを特徴とする上記（１）の大気中の窒素酸化物の除
去処理装置、である。 また、本発明は、（３）該吸着剤
としてヒドロキシアパタイトを用いたことを特徴とする
上記（１）又は（２）の大気中の窒素酸化物の除去処理
装置、である 。 That is, according to the present invention, (1) polluted air is caused to flow in a narrow gap between a pair of parallel plates , and particles having a small diffusion coefficient are
The pair of parallel plates are passed through the narrow gap as they are,
Is discharged from the outlet of the parallel plates, and the by diffusing harmful gas components contaminated in the air to the inner wall surface of the pair of parallel plates for adsorbing to the inner wall surface, parallel pair that has parallel opposed
It consists of a plate, and the gap is calculated by the following formula (Gormley's theoretical formula)
And satisfy interval, titanium oxide on the inner wall surface of the pair of parallel plates
An apparatus for removing nitrogen oxides from the atmosphere , comprising a coating layer comprising a tan ultrafine particle photocatalyst and an adsorbent and having a structure capable of irradiating light into the gap. Formula: f = 1− [0.910exp (−3.77μ) +
0.0531 exp (-42.8 μ)], μ = bDL /
aQ (However, f: removal efficiency, D: target gas diffusion coefficient
Number (cm 2 / sec), a: Distance between parallel plates (cm), L: Flat
Row length (cm), μ: deposition parameter, Q: atmospheric absorption
Draw flow rate (cm 3 / sec), b: width of parallel plate (cm)
It ) Further , in the present invention, (2) the coating layer comprises a binder.
And provided with polytetrafluoroethylene
Removal of nitrogen oxides in the atmosphere according to (1) above
It is an aftertreatment device. The present invention also provides (3) the adsorbent.
Characterized by using hydroxyapatite as
Removal treatment of nitrogen oxides in the atmosphere of (1) or (2) above
Device .
【００１１】また、本発明は、（４）空調装置の空気流
路または排気ガス処理装置のガス流路に付設されて用い
られることを特徴とする上記（１）ないし（３）のいず
れかの大気中の窒素酸化物の除去処理装置、である。ま
た、本発明は、（５）一般家庭での可搬型空気清浄装置
として使用することを特徴とする上記（１）ないし
（３）のいずれかの大気中の窒素酸化物の除去処理装
置、である。また、本発明は、（６）水を注入して洗浄
することによって酸化チタン超微粒子光触媒と吸着剤と
からなる塗布層上で酸化・吸着された窒素酸化物をＮＯ
2 - 、ＮＯ 3 - イオンとして水で回収することを特徴とする
上記（１）ないし（５）のいずれかの窒素酸化物の除去
処理装置の使用方法、である。また、本発明は、（７）
水を注入して洗浄することによって酸化チタン超微粒子
光触媒と吸着剤とからなる塗布層上で酸化・吸着された
窒素酸化物をＮＯ 2 - 、ＮＯ 3 - イオンとして水で回収した
後、空気を流して酸化チタン超微粒子光触媒と吸着剤と
からなる塗布層表面を乾燥し、繰り返して窒素酸化物の
除去処理を行うことを特徴とする上記（１）ないし
（５）のいずれかの窒素酸化物の除去処理装置の使用方
法、である。 ( 4 ) Any one of the above (1) to (3) , wherein the present invention is used by being attached to an air passage of an air conditioner or a gas passage of an exhaust gas treatment device.
A device for removing nitrogen oxides in the atmosphere. Further, the present invention ( 5 ) is used as a portable air cleaning device in a general household, wherein the above (1) to (1)
An apparatus for removing atmospheric nitrogen oxides according to any one of (3) . The present invention also provides (6) water injection for cleaning.
By using ultrafine titanium oxide photocatalyst and adsorbent
Nitrogen oxides oxidized and adsorbed on the coating layer consisting of NO
2 -, NO 3 - and recovering water as ion
Removal of nitrogen oxide according to any one of (1) to (5) above
A method of using the processing device. The present invention also provides ( 7 )
Titanium oxide ultrafine particles by injecting water and washing
Oxidized / adsorbed on the coating layer consisting of photocatalyst and adsorbent
Nitrogen oxides NO 2 -, NO 3 - was collected with water as ion
After that, air is passed to the titanium oxide ultrafine particle photocatalyst and the adsorbent.
The surface of the coating layer consisting of
The above-mentioned (1) to (1) characterized in that the removal processing is performed
How to use the nitrogen oxide removal treatment device of any of (5)
Is the law.
【００１２】本発明において使用する拡散スクラバ法と
は、（１）平行板内壁面へガスが拡散する、（２）内壁
面へ到達したガスが内壁表面で吸着除去されるという、
拡散を利用したガスの捕集・除去法であり、ガスと粒子
の拡散係数が大きく異なることを利用し、ガスを選択的
に除去する方法である。図７に拡散スクラバ法を模式的
に示す。The diffusion scrubber method used in the present invention means that (1) the gas diffuses to the inner wall surface of the parallel plate, and (2) the gas reaching the inner wall surface is adsorbed and removed on the inner wall surface.
It is a method of collecting and removing gas using diffusion, and it is a method of selectively removing gas by utilizing the fact that the diffusion coefficients of gas and particles are greatly different. FIG. 7 schematically shows the diffusion scrubber method.
【００１３】この拡散スクラバ法において、大気中のガ
ス成分の除去効率は、下記のＧｏｒｍｌｅｙの理論式
（P.G.Gormley,Proceedings of the Royal Irish Acade
my,Vol.45,59-63,(1938）)に基づいて算出できる。In this diffusion scrubber method, the removal efficiency of gas components in the atmosphere is determined by the following Gormley 's theoretical formula (PG Gormley, Proceedings of the Royal Irish Academy).
It can be calculated based on my, Vol.45,59-63, (1938) .
【００１４】ｆ＝１−［０．９１０ｅｘｐ（−３．７７
μ）＋０．０５３１ｅｘｐ（−４２．８μ）］、μ＝ｂ
ＤＬ／ａＱ
なお、上記の式において、ｆ：除去効率、Ｄ：対象とす
るガスの拡散係数（ｃｍ2／秒）、ａ：平行板の間隔
（ｃｍ）、Ｌ：平行板の長さ（ｃｍ）、μ：沈着パラメ
ータ、Ｑ：大気吸引流量（ｃｍ3／秒）、ｂ：平行板の
幅（ｃｍ）である。F = 1− [0.910exp (−3.77)
μ) + 0.0531exp (−42.8μ)], μ = b
DL / aQ In the above formula, f: removal efficiency, D: diffusion coefficient of target gas (cm 2 / sec ) , a: distance between parallel plates
(Cm) , L: parallel plate length (cm), μ: deposition parameter, Q: atmospheric suction flow rate (cm 3 / sec), b: parallel plate width (cm).
【００１５】本発明の除去処理装置は、表面の平らな平
行板の内壁表面に酸化チタン超微粒子光触媒と吸着剤の
平らな塗布層を設け、平行板の隙間を流れる空気中の有
害ガス成分を平行板の内壁の塗布面で除去するものであ
る。平行板の隙間に空気を流すので、フィルタ等の濾過
方式とは異なり、通気抵抗は極めて少ない。In the removal treatment apparatus of the present invention, a flat coating layer of titanium oxide ultrafine particle photocatalyst and adsorbent is provided on the inner wall surface of a parallel plate having a flat surface to remove harmful gas components in the air flowing through the gap between the parallel plates. It is to be removed on the coated surface of the inner wall of the parallel plate. Since air flows through the gaps between the parallel plates, the ventilation resistance is extremely low, unlike filtration methods such as filters.
【００１６】光触媒を用いた「光脱硝法」の場合には、
ＮＯXをＮＯ2やＨＮＯ3に化学変化させ、これを水で洗
い流すので、平行板は極めて腐食性の高い条件で使用さ
れるために耐蝕性が大きいステンレス鋼板が適する。ま
た、ステンレス鋼板は、その表面にＴｉＯ2とヒドロキ
シアパタイト（以下適宜、「ＨＡＰ」と表記する）をポ
リテトラフロロエチレン等のバインダとアセトンなどの
有機溶媒中で混合して塗布乾燥するだけで優れた接着性
を示し、かつ長期間の使用において強度、耐久性に問題
がない。In the case of the "photodenitrification method" using a photocatalyst,
Since NO x is chemically changed to NO 2 or HNO 3 , and this is washed away with water, the parallel plate is used under extremely corrosive conditions, and therefore a stainless steel plate having high corrosion resistance is suitable. Also, the stainless steel plate has TiO 2 and hydroxyl on its surface.
Siapatite (hereinafter appropriately referred to as " HAP ") is mixed in a binder such as polytetrafluoroethylene in an organic solvent such as acetone, coated and dried to show excellent adhesion, and for long-term use There is no problem in strength and durability.
【００１７】平行板の大きさは、装置の規模に応じて適
宜定めることができるが、例えば、図３に示すように、
空気の流路面が１０×０．５ｃｍ（通気断面積５ｃ
ｍ2）、流路長３５ｃｍ程度の基本ユニットを製作し、
この様なユニットを装置の規模に応じて積層して組み合
わせて使用すればよい。The size of the parallel plate can be appropriately determined according to the scale of the apparatus. For example, as shown in FIG.
Air flow surface is 10 x 0.5 cm (ventilation cross section 5c
m 2 ), manufacture a basic unit with a flow path length of about 35 cm,
Such units may be laminated and used according to the scale of the device.
【００１８】平行板の間隔は、平行板の内壁表面が有害
ガス成分に対して理想的な完全吸着面と仮定した図７に
模式的に示す拡散スクラバ法におけるＧｏｒｍｌｅｙの
理論式により設定することができる。上記の基本ユニッ
トの場合、通気流量１０リットル／分（風速０．３３ｍ
／秒）の条件で、０．５ｃｍ程度の平行板の間隔にすれ
ば、ほぼ１００％近く有害ガス成分を除去できる。The distance between the parallel plates is determined by Gormley 's theoretical formula in the diffusion scrubber method schematically shown in FIG. 7 assuming that the inner wall surface of the parallel plates is an ideal perfect adsorption surface for harmful gas components. Can be set. In the case of the above basic unit, the ventilation flow rate is 10 liters / minute (wind speed 0.33 m
/ Sec), if the distance between the parallel plates is about 0.5 cm, the harmful gas component can be removed by almost 100%.
【００１９】図２には、平行板の内壁表面が有害ガス成
分の窒素酸化物に対して完全吸着面であると仮定したＧ
ｏｒｍｌｅｙの理論式によって求めた除去効率と小型平
行板型拡散スクラバの窒素酸化物除去装置ユニットによ
る除去効率（実験値）とを比較して示す。（１）ＴｉＯ
2：平均粒径１００ｎｍ／ＨＡＰ：平均粒径３０μｍの
組み合わせの塗布面では、◇印で示す様に、窒素酸化物
の除去効率は理論値より低い結果であるが、（２）Ｔｉ
Ｏ2：平均粒径７ｎｍ／ＨＡＰ：平均粒径３μｍの組み
合わせの塗布面の場合には、△印で示す様に、理論値の
線と一致し、風速０．３３ｍ／秒でほぼ１００％近い除
去効率が得られる。この結果から、ＴｉＯ2とＨＡＰの
特定の組み合わせによって窒素酸化物に対して理想的な
完全吸着面を形成できることが分かる。In FIG. 2, it is assumed that the inner wall surface of the parallel plate is a perfect adsorption surface for nitrogen oxide, which is a harmful gas component.
The removal efficiency obtained by the Ormley's theoretical formula and the removal efficiency (experimental value) by the nitrogen oxide removal device unit of the small parallel plate type diffusion scrubber are shown in comparison. (1) TiO
2 : On the coated surface of the combination of the average particle diameter of 100 nm / HAP: the average particle diameter of 30 μm, the nitrogen oxide removal efficiency is lower than the theoretical value, as indicated by ⋄, but (2) Ti
In the case of the coated surface having a combination of O 2 : average particle size 7 nm / HAP: average particle size 3 μm, as indicated by the triangle, it coincides with the theoretical value line, and is almost 100% at a wind speed of 0.33 m / sec Removal efficiency is obtained. From this result, it can be seen that an ideal complete adsorption surface for nitrogen oxide can be formed by a specific combination of TiO 2 and HAP.
【００２０】大気の通気流量が大きくなるとＮＯガスが
装置内に滞在する時間が短くなり、当然のことながらＮ
ＯXの除去効率は低下する。また、導入するＮＯ濃度が
高いと除去効率が低下する傾向がみられる。これは、Ｔ
ｉＯ2の表面に発生しているラジカル量の分だけしかＮ
Ｏとの反応が起こらないためであり、導入されるＮＯの
量があまり多くなると壁面へ拡散しても反応せず、平行
板型拡散スクラバを通過するＮＯが多くなる。As the air flow rate increases, the time during which the NO gas stays in the device shortens.
O X removal efficiency decreases. Further, when the introduced NO concentration is high, the removal efficiency tends to decrease. This is T
The amount of radicals generated on the surface of iO 2 is N
This is because the reaction with O does not occur, and when the amount of introduced NO is too large, it does not react even if it diffuses to the wall surface, and more NO passes through the parallel plate diffusion scrubber.
【００２１】本発明の装置によるＮＯXの除去容量は、
ＴｉＯ／ＨＡＰの単位塗布面積当たり、１００ｍｍｏｌ
／ｍ2と極めて高く、１ｐｐｍのＮＯXの空気を２４００
ｍ3除去処理することが可能である。また、トンネル内
の空気中のＮＯX濃度は数ｐｐｍに達する場合もあると
報告されているが、表１に示すように、本発明の装置に
よるｐｐｍレベルのＮＯガスの除去効率はほぼ１００％
近くにすることができる。The NO x removal capacity of the device of the present invention is
100 mmol per unit coating area of TiO / HAP
/ M 2 and very high, the air 1ppm of NO X 2400
m 3 removal treatment is possible. Further, it is reported that the NO x concentration in the air in the tunnel may reach several ppm, but as shown in Table 1, the removal efficiency of the NO level of the NO level of the apparatus of the present invention is almost 100%.
Can be close.
【００２２】本発明の拡散スクラバ法による大気浄化処
理装置の構造は、簡便な構造であり、既存の空調施設等
に簡単に組み込むことができ、また、単なる水の循環使
用により有害ガス成分を効率的に除去処理できる。した
がって、温度・湿度の調整のために行ってきたビル等に
おける空調装置に本発明の大気浄化処理装置を付設して
有害ガス成分を除去処理し、質の高い生活環境を提供す
ることができる。The structure of the air purification treatment apparatus by the diffusion scrubber method of the present invention is a simple structure and can be easily incorporated into an existing air conditioning facility or the like, and the toxic gas component can be efficiently used by simply circulating water. Can be removed. Therefore, the air purification device of the present invention can be attached to an air conditioner in a building or the like that has been used for adjusting temperature and humidity to remove harmful gas components and provide a high quality living environment.
【００２３】また、本発明の大気浄化処理装置は、ビル
の空調設備に組み込むばかりでなく、自動車トンネル、
地下駐車場等の空気循環経路の空調設備や建設・工事車
両等の群小固定発生源の排気ガス処理装置に付設して効
率的なＮＯX除去処理が行える。さらに、装置自身は簡
単に小型化できるので、一般家庭での可搬型空気清浄装
置としても使用できること等極めて応用範囲が多岐に亘
る。Further, the air purification processing device of the present invention is not only incorporated into the air conditioning equipment of a building, but also an automobile tunnel,
Efficient NO X removal processing can be performed by attaching it to an air-conditioning system for an air circulation route such as an underground parking lot or an exhaust gas treatment device of a small fixed source such as construction and construction vehicles. Further, since the device itself can be easily miniaturized, it can be used as a portable air cleaning device in a general household, and thus has a very wide range of applications.
【００２４】[0024]
【作用】本発明の拡散スクラバ法を用いた大気浄化処理
装置による大気中ＮＯXの除去原理を図１に示す。Ｔｉ
Ｏ 2 ／ＨＡＰ（１）を表面に塗布した平行板、例えば、
ステンレス鋼板（２）を２枚向き合わせ、２枚のステン
レス鋼板（２）の隙間にはＵＶランプ（５）等により光
を照射してＴｉＯ2を活性化させる。[Action] The removal principle of atmospheric NO X by diffusion scrubber method air purification processing apparatus using the present invention shown in FIG. Ti
A parallel plate whose surface is coated with O 2 / HAP (1), for example,
Two stainless steel plates (2) are faced to each other, and the gap between the two stainless steel plates (2) is irradiated with light from a UV lamp (5) or the like to activate TiO 2 .
【００２５】一端側を汚染空気の入口として、２枚のス
テンレス鋼板の隙間に汚染空気（３）を流すと、拡散係
数の大きいＮＯXガス（４）は、ＴｉＯ2／ＨＡＰ（１）
が塗布されたステンレス鋼板（２）の内壁面へ拡散す
る。内壁表面へ到達したＮＯXガス（４）は、ＴｉＯ2に
より生じたＨＯ2、ＯＨラジカルによりＮＯ2、ＨＮＯ3
に酸化され、ＴｉＯ2／ＨＡＰ（１）の表面に吸着さ
れ、汚染空気中から除去され、清浄空気（７）が出口側
から排出される。ＴｉＯ2は、吸着したＮＯ、ＮＯ2を保
持する能力が低いために、ＮＯ2がＨＮＯ3になる前に脱
着してしまう可能性が高い。この脱着したＮＯ2を確実
に除去するために、ＮＯ2の吸着剤としてＨＡＰをＴｉ
Ｏ2に混合して使用する。When polluted air (3) is caused to flow through the gap between the two stainless steel plates with one end side being the inlet for polluted air, NO x gas (4) having a large diffusion coefficient is converted into TiO 2 / HAP (1).
Diffuses to the inner wall surface of the coated stainless steel plate (2). NO X gas having reached the inner wall surface (4), NO 2, HNO 3 by HO 2, OH radicals generated by TiO 2
Is oxidized to be adsorbed on the surface of TiO 2 / HAP (1), removed from the polluted air, and clean air (7) is discharged from the outlet side. Since TiO 2 has a low ability to retain adsorbed NO and NO 2 , there is a high possibility that it will be desorbed before NO 2 becomes HNO 3 . In order to surely remove the desorbed NO 2 , HAP is used as an NO 2 adsorbent.
Used as a mixture with O 2 .
【００２６】一方、除去装置を使用する層流条件では拡
散係数の小さい粒子（６）は壁面へ拡散しない内に一対
のステンレス鋼板（２）の平行板をそのまま通過してし
まう。そして、一対のステンレス鋼板（２）の平行板の
出口側から排出される。したがって、原理的に空気中の
粒子はステンレス鋼板の平行板内に付着せず、空気を処
理する際の粒子による除去装置への汚れの影響は極めて
少ない。On the other hand, under the laminar flow condition using the removing device, the particles (6) having a small diffusion coefficient pass through the parallel plates of the pair of stainless steel plates (2) without being diffused to the wall surface. Then, it is discharged from the exit side of the parallel plates of the pair of stainless steel plates (2). Therefore, in principle, particles in the air do not adhere to the parallel plate of the stainless steel plate, and the influence of dirt on the removing device by the particles when processing the air is extremely small.
【００２７】ＴｉＯ2やＨＡＰの表面に吸着したＮＯ2や
ＨＮＯ3は、水で簡単に洗い流すことができるので、定
期的に塗布した表面を水で洗うことにより半永久的に使
用できる。吸着剤としては活性炭等も知られているが、
活性炭の場合は水洗して再使用することが困難である。The NO 2 and HNO 3 adsorbed on TiO 2 and HAP surfaces, it is possible to wash easily with water, semipermanently usable by washing regularly coated surface with water. Activated carbon is also known as an adsorbent,
In the case of activated carbon, it is difficult to wash it with water and reuse it.
【００２８】この様に、拡散スクラバ法を用いると、汚
染空気を濾過する化学フィルタの原理とは全く異なり、
一対の平行板の隙間に汚染空気を流すので通気抵抗によ
る圧力損失が非常に少なく、小さなエネルギで大容量の
汚染空気を清浄化処理できる。As described above, when the diffusion scrubber method is used, the principle of a chemical filter for filtering contaminated air is completely different,
Since the contaminated air flows through the gap between the pair of parallel plates, the pressure loss due to the ventilation resistance is very small, and a large amount of contaminated air can be cleaned with a small amount of energy.
【００２９】[0029]
【発明の実施の形態】本発明は、「拡散スクラバ法」の
原理に基づき、平行に向き合わせた一対の平行板の狭い
隙間に汚染空気を流し、その平行板の内壁面に拡散して
きたガス成分を内壁表面で除去処理する方法であり、汚
染空気を流しながら連続的に有害ガスの除去処理が行え
る。BEST MODE FOR CARRYING OUT THE INVENTION The present invention is based on the principle of the "diffusion scrubber method", in which contaminated air is caused to flow through a narrow gap between a pair of parallel plates facing in parallel, and the gas diffused to the inner wall surface of the parallel plates. It is a method of removing components on the inner wall surface, and can continuously remove harmful gas while flowing contaminated air.
【００３０】平行板は、耐蝕性に優れたステンレス鋼板
が好ましいが、ステンレス鋼板に限定されるものではな
い。平行板に塗布するＴｉＯ2超微粒子としては平均粒
径７ｎｍ程度が最も好ましい。また、ＨＡＰ微粒子とし
ては、平均粒径３μｍ程度が最も好ましい。ＴｉＯ2超
微粒子とＨＡＰ微粒子は、重量比が２：１〜１：２にな
るようにアセトン等の有機溶媒中で混合し、これにポリ
テトラフロロエチレン等のバインダを適宜加えて公知の
塗布手段、例えば、スプレーガン等により乾燥後の厚み
が１０ｍｇ／ｃｍ2（厚さ数十μｍ）程度となるように
塗布する。The parallel plate is preferably a stainless steel plate having excellent corrosion resistance, but is not limited to the stainless steel plate. The average particle size of about 7 nm is most preferable for the TiO 2 ultrafine particles applied to the parallel plates. The HAP fine particles most preferably have an average particle size of about 3 μm. The TiO 2 ultrafine particles and the HAP fine particles are mixed in an organic solvent such as acetone so that the weight ratio is 2: 1 to 1: 2, and a binder such as polytetrafluoroethylene is appropriately added to the mixture, and the known coating means is used. For example, it is applied by a spray gun or the like so that the thickness after drying is about 10 mg / cm 2 (thickness: several tens of μm).
【００３１】この平行板（２）を２枚を用いて塗布面を
向かい合わせて、図３に示すように、５ｍｍ程度の狭い
間隔で平行に並べて平行板の両端の保持部材８を固定部
材９で固定し、平行板（２）の一端側の隙間に極細のＵ
Ｖランプ（５）を設置して隙間内に光を照射できる構造
とし、小型平行板型拡散スクラバ法による大気浄化処理
装置ユニットとする。Two parallel plates (2) are used so that their coating surfaces face each other, and as shown in FIG. 3, the holding members 8 at both ends of the parallel plates are arranged in parallel at a narrow interval of about 5 mm, and the fixing members 9 are provided. Fixed with a U-shaped thin plate in the gap on one end side of the parallel plate (2).
A V-lamp (5) is installed to have a structure capable of irradiating light into the gap, and an air purification treatment device unit by a small parallel plate type diffusion scrubber method is used.
【００３２】このユニットの大きさは、本体は４４０×
１５０×３８ｍｍ、ＴｉＯ2／ＨＡＰを塗布してある通
気流路面は３５０×１００ｍｍ（面積、３５０ｃｍ2）
である。このユニットを単体または所定枚数を組み合わ
せて大気浄化処理装置とし、これを空調設備等に付設
し、汚染空気を平行板（２）の隙間に流し、ＵＶランプ
（５）によって光触媒面に紫外線を照射すると、ＮＯX
が内壁表面のＴｉＯ2／ＨＡＰによって酸化、吸着除去
される。The size of this unit is 440 × for the main body.
150 × 38 mm, the ventilation channel surface coated with TiO 2 / HAP is 350 × 100 mm (area, 350 cm 2 ).
Is. This unit is used alone or in combination with a predetermined number to form an air purification treatment device, which is attached to an air conditioner or the like, and contaminated air is caused to flow in the gap between the parallel plates (2) and the photocatalyst surface is irradiated with ultraviolet rays by the UV lamp (5). Then NO X
Are oxidized and adsorbed and removed by TiO 2 / HAP on the inner wall surface.
【００３３】図１に原理を示した様に、紫外線の照射下
でＴｉＯ2／ＨＡＰ上で、窒素酸化物（ＮＯ、ＮＯ2）
は、ＮＯ2またはＨＮＯ3に酸化され、吸着除去される。
その後、水を注入して洗浄することによってＴｉＯ2／
ＨＡＰ上で酸化・吸着された窒素酸化物をＮＯ2 -、ＮＯ
3 -イオンとして水で簡単に回収することができる。As shown in the principle of FIG. 1, nitrogen oxides (NO, NO 2 ) were formed on TiO 2 / HAP under irradiation of ultraviolet rays.
Is oxidized to NO 2 or HNO 3 and adsorbed and removed.
Then, by injecting water and washing, TiO 2 /
The nitrogen oxides are oxidized and adsorbed on the HAP NO 2 -, NO
It can be easily recovered with water as 3 - ions.
【００３４】水で回収されたＮＯ2 -、ＮＯ3 -イオンは、
イオン交換樹脂により簡単に処理できる。そして、水に
よる洗浄後、空気を流しＴｉＯ2／ＨＡＰ表面が乾燥す
れば、繰り返して窒素酸化物（ＮＯ、ＮＯ2）の除去処
理を行うことができる。この様にして、本発明の除去処
理装置は長期間に亘り水を循環処理しながら窒素酸化物
（ＮＯ、ＮＯ2）を除去処理することが可能である。The NO 2 − and NO 3 − ions recovered with water are
Can be easily treated with ion exchange resin. Then, after washing with water, if air is passed and the TiO 2 / HAP surface is dried, the removal treatment of nitrogen oxides (NO, NO 2 ) can be repeated. In this way, the removal treatment apparatus of the present invention can remove nitrogen oxides (NO, NO 2 ) while circulating water for a long period of time.
【００３５】[0035]
【実施例】実施例１
ＴｉＯ2粉末（和光純薬工業、平均粒径１００ｎｍ）と
ＨＡＰ粉末（信州セラミックス、平均粒径３０μｍ）を
３３．３重量％：３３．３重量％の割合で３３．３重量
％のテトラフロロエチレン樹脂バインダ（ＴｉＯ2：Ｈ
ＡＰ：ＰＴＦＥ＝１：１：１）とアセトン等の有機溶媒
中で混合し、スプレーガンによりステンレス鋼板表面に
塗布し、乾燥した。このステンレス鋼板を用いて実施態
様に記載した図３に示すユニットを製作した。ＵＶラン
プとしては、外径、４ｍｍφのもの（東芝冷陰極蛍光ラ
ンプ）を用いた。Example 1 TiO 2 powder (Wako Pure Chemical Industries, average particle size 100 nm) and HAP powder (Shinshu Ceramics, average particle size 30 μm) were used at a ratio of 33.3% by weight: 33.3% by weight to 33. 3% by weight of tetrafluoroethylene resin binder (TiO 2 : H
AP: PTFE = 1: 1: 1) was mixed with an organic solvent such as acetone, coated on the surface of a stainless steel plate with a spray gun, and dried. Using this stainless steel plate, the unit shown in FIG. 3 described in the embodiment was manufactured. A UV lamp having an outer diameter of 4 mmφ (Toshiba cold cathode fluorescent lamp) was used.
【００３６】このユニットについて、下記により評価試
験を行った。ＮＯの標準ガスボンベより供給されたＮＯ
ガスを、清浄空気により数ｐｐｍの濃度レベルに適宜希
釈し、この希釈されたＮＯガスをＵＶランプ（５）を点
灯していない状態で、小型平行板型拡散スクラバ除去装
置へ導入し、装置通過後のガスのＮＯ濃度を測定した。
除去装置の入口、出口のＮＯ濃度が一致したのを確認し
た後にＵＶランプ（５）を点灯し、ランプ点灯後の除去
装置出口のＮＯ濃度の変化から除去装置によるＮＯの除
去効率を算出した。除去効率は前述した式によって求め
た。An evaluation test was conducted on this unit as follows. NO supplied from a standard NO gas cylinder
The gas is appropriately diluted with clean air to a concentration level of several ppm, and the diluted NO gas is introduced into a small parallel plate type diffusion scrubber removal device without turning on the UV lamp (5) and passed through the device. The NO concentration of the latter gas was measured.
After confirming that the NO concentrations at the inlet and outlet of the removing device were the same, the UV lamp (5) was turned on, and the NO removing efficiency by the removing device was calculated from the change in the NO concentration at the outlet of the removing device after the lamp was turned on. The removal efficiency was obtained by the above-mentioned formula.
【００３７】通気流量４Ｌ／ｍｉｎ、ＮＯ濃度６７３ｐ
ｐｂの条件で空気を処理した場合の汚染空気処理のＮＯ
濃度変化およびＮＯX除去効率の経時変化を図４に示
す。図４より、ＵＶランプ（５）を点灯すると６７３ｐ
ｐｂのＮＯ濃度が急激に下がり７５ｐｐｂ以下となり、
時間とともに除去装置を通過後のＮＯ濃度が僅かづつ上
昇してくることが判る。これは、ＴｉＯ2に付着したＨ
ＮＯ3がＴｉＯ2に光が当たるのを阻害しているためであ
る。しかしながら、約７時間経過しても除去効率の大幅
な低下は認められず、その後、ＵＶランプを消灯すると
ＮＯ濃度がランプ点灯前の６７３ｐｐｂに戻った。図４
より、この実施例１においては、ＮＯXを８０％以上の
高い除去効率で除去できることが確認された。Ventilation flow rate 4 L / min, NO concentration 673 p
NO for treating contaminated air when treating air under pb conditions
FIG. 4 shows changes in concentration and NO X removal efficiency with time. From Figure 4, 673p when the UV lamp (5) is turned on.
The NO concentration of pb drops sharply to 75 ppb or less,
It can be seen that the NO concentration after passing through the removing device gradually increases with time. This is the H attached to TiO 2.
This is because NO 3 prevents the TiO 2 from being exposed to light. However, no significant decrease in removal efficiency was observed even after about 7 hours, and when the UV lamp was turned off thereafter, the NO concentration returned to 673 ppb before the lamp was turned on. Figure 4
From this, in this Example 1, it was confirmed that NO X can be removed with a high removal efficiency of 80% or more.
【００３８】実施例２
実施例１と同じ装置を用いて、通気流量４Ｌ／ｍｉ
ｎ、ＮＯ濃度２７０５ｐｐｂ、通気流量１０Ｌ／ｍｉ
ｎ、ＮＯ濃度２６４５ｐｐｂの各条件で空気を処理した
ところ、除去効率は、表１に示すとおり、が８３．０
％、が４６．０％であった。の条件で汚染空気を処
理した場合のＮＯ濃度の経時変化を図５に示す。Example 2 Using the same apparatus as in Example 1, the ventilation flow rate was 4 L / mi.
n, NO concentration 2705 ppb, aeration flow rate 10 L / mi
When the air was treated under the conditions of n and NO concentration of 2645 ppb, the removal efficiency was 83.0 as shown in Table 1.
% Was 46.0%. FIG. 5 shows the change over time in the NO concentration when the contaminated air was treated under the conditions of.
【００３９】[0039]
【表１】 [Table 1]
【００４０】実施例３
ＴｉＯ2として、平均粒径７ｎｍ（石原産業ＳＴ−０
１）、ＨＡＰとして平均粒径３μｍ（富田製薬）とした
以外は実施例１と同じ装置で、通気流量４Ｌ／ｍｉ
ｎ、ＮＯ濃度３２０５ｐｐｂ、通気流量１０Ｌ／ｍｉ
ｎ、ＮＯ濃度３３４１ｐｐｂ、通気流量１５Ｌ／ｍｉ
ｎ、ＮＯ濃度３２２２ｐｐｂの各条件で汚染空気を処理
したところ、除去効率は、表１に示すとおり、が１０
０．０％、が９５．７％、が８９．０％と非常に高
い除去効率が得られた。の条件で汚染空気を処理した
場合のＮＯ濃度と除去効率の経時変化を図６に示す。Example 3 As TiO 2 , an average particle size of 7 nm (Ishihara Sangyo ST-0
1), the same device as in Example 1 except that the HAP had an average particle size of 3 μm (Tomita Pharmaceutical Co., Ltd.), and an air flow rate of 4 L / mi.
n, NO concentration 3205 ppb, ventilation flow rate 10 L / mi
n, NO concentration 3341 ppb, ventilation flow rate 15 L / mi
When the contaminated air was treated under the conditions of n and NO concentration of 3222 ppb, the removal efficiency was 10 as shown in Table 1.
A very high removal efficiency of 0.0%, 95.7%, and 89.0% was obtained. FIG. 6 shows the changes over time in the NO concentration and removal efficiency when the contaminated air was treated under the conditions.
【００４１】実施例４
実施例１と同じ装置を用いて、ＴｉＯ2：ＨＡＰの比を
１：２に変えて実施例２のの条件で汚染空気を処理し
た場合のＮＯ濃度の経時変化を実施例２のの条件の場
合と比較して図５に示す。図５より、初期のＮＯ除去効
率は、実施例２のＴｉＯ2：ＨＡＰ＝１：１の場合が若
干優れているが、ＮＯの除去容量については実施例４の
ＴｉＯ2：ＨＡＰ＝１：２の方が優れていた。Example 4 Using the same apparatus as in Example 1, the NO concentration was changed with time when the contaminated air was treated under the conditions of Example 2 while changing the TiO 2 : HAP ratio to 1: 2. FIG. 5 shows a comparison with the case of the condition of Example 2. From FIG. 5, the initial NO removal efficiency is slightly superior in the case of TiO 2 : HAP = 1: 1 of Example 2, but the NO removal capacity is TiO 2 : HAP = 1: 2 of Example 4. Was better.
【００４２】実施例５
図３に示した小型平行板型拡散スクラバによる窒素酸化
物除去装置ユニットを５０枚束ねた直方体の装置を製作
した。ステンレス鋼板に５０×５０ｃｍのエリアで酸化
チタン超微粒子光触媒（石原産業ＳＴ−０１、平均粒径
７ｎｍ）とヒドロキシアパタイト微粒子（富田製薬、平
均粒径３μｍ）をテトラフロロエチレン樹脂バインダを
用いて塗布した。この装置により小型平行板型拡散スク
ラバ式窒素酸化物除去装置ユニットの２５０倍の窒素酸
化物ＮＯXの除去処理能力を有し、毎分２．５ｍ3（１５
０ｍ3／ｈ）の空気を処理することができた。Example 5 A rectangular parallelepiped apparatus was manufactured by bundling 50 units of nitrogen oxide removing apparatus units by the small parallel plate type diffusion scrubber shown in FIG. Titanium oxide ultrafine particle photocatalyst (Ishihara Sangyo ST-01, average particle size 7 nm) and hydroxyapatite fine particles (Tomita Pharmaceutical Co., Ltd., average particle size 3 μm) were applied to a stainless steel plate in an area of 50 × 50 cm using a tetrafluoroethylene resin binder. . With this device, it has 250 times more nitrogen oxide NO x removal processing capacity than a small parallel plate type diffusion scrubber type nitrogen oxide removal device unit, and it has a capacity of 2.5 m 3 (15
0 m 3 / h) of air could be treated.
【００４３】[0043]
【発明の効果】本発明の大気浄化浄処理装置は、光触
媒を塗布した平行板による単純な構造の処理装置である
こと、空気中の粒子は平行板の除去装置を原理的に通
過し、平行板の内壁表面に付着しないので粒子による除
去装置への汚れの影響は少ないこと、単なる水を洗浄
液として用いて除去した有害ガス成分のＮＯXをＮＯ2 -
およびＮＯ3 -として簡単に回収でき、除去装置を乾燥す
れば繰り返し連続して使用できること、洗浄液の再生
処理も既存のイオン交換樹脂を使用でき、省エネルギ・
ランニングコストの面で優れていること、フィルタに
よる濾過捕集とは異なり通気抵抗が小さく空気の処理量
が極めて大きいこと、除去装置の構造がシンプルであ
り、移動でき、又、トンネル、屋内駐車場等の既存の空
調設備等にも簡単に組み込めること等実用的な価値が高
い。EFFECT OF THE INVENTION The air purification processing apparatus of the present invention is a processing apparatus having a simple structure with parallel plates coated with a photocatalyst, and particles in the air pass through the parallel plate removing apparatus in principle, it does not adhere to the inner wall surface of the plate influences the stains on the removal device according particles less, the nO X of harmful gas components were removed using a simple water as a wash nO 2 -
And NO 3 - as can be easily recovered and removing apparatus that can be used repeatedly continuously be dried, also can use the existing ion exchange resin regeneration process of the cleaning solution, saving energy
It is excellent in running cost, has a small ventilation resistance unlike filtration and collection by a filter, and has an extremely large amount of air to be treated. The structure of the removing device is simple and mobile, and it can be used in tunnels and indoor parking lots. It has a high practical value such that it can be easily incorporated into existing air-conditioning equipment.
【図１】図１は、ＴｉＯ2超微粒子とヒドロキシアパタ
イト微粒子の混合物を用いた平行板型拡散スクラバによ
る窒素酸化物除去処理装置の原理を示す模式図である。FIG. 1 is a schematic diagram showing the principle of a nitrogen oxide removing treatment apparatus by a parallel plate type diffusion scrubber using a mixture of TiO 2 ultrafine particles and hydroxyapatite fine particles.
【図２】図２は、Ｇｏｒｍｌｅｙの理論式より算出した
大気中窒素酸化物の理論効率と実験値との比較を示すグ
ラフである。FIG. 2 is a graph showing a comparison between the theoretical efficiency of nitrogen oxides in the atmosphere calculated from the theoretical equation of Gormley and the experimental value.
【図３】図３は、本発明の平行板型拡散スクラバ法を用
いた窒素酸化物除去処理装置の斜視図である。FIG. 3 is a perspective view of a nitrogen oxide removing apparatus using the parallel plate type diffusion scrubber method of the present invention.
【図４】図４は、実施例１における汚染空気処理のＮＯ
濃度変化およびＮＯX 除去効率を示すグラフである。[Fig. 4] Fig. 4 is NO of polluted air treatment in Example 1.
Is a graph showing the change in concentration and NO X removal efficiency.
【図５】図５は、実施例２および実施例４における汚染
空気処理のＮＯ濃度変化を示すグラフである。FIG. 5 is a graph showing changes in NO concentration during treatment of polluted air in Example 2 and Example 4.
【図６】図６は、実施例４における汚染空気処理のＮＯ
濃度変化およびＮＯX 除去効率を示すグラフである。FIG. 6 is a NO of polluted air treatment in Example 4.
Is a graph showing the change in concentration and NO X removal efficiency.
【図７】図７は、Ｇｏｒｍｌｅｙの理論式に基づく大気
中ガス成分の除去効率の算出式のための拡散スクラバ法
の模式図である。Figure 7 is a schematic diagram of diffusion scrubber method for calculation formula removal efficiency of atmospheric gas components based on the theoretical formula of Gormley.
───────────────────────────────────────────────────── フロントページの続き 早期審査対象出願 (72)発明者 飯嶋 和明 東京都千代田区有楽町１−４−１ 三機 工業株式会社内 (56)参考文献 特開2002−126451（ＪＰ，Ａ) 特開 平10−253508（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 21/00 - 38/74 ─────────────────────────────────────────────────── ─── Continuation of the front page Application for accelerated examination (72) Inventor Kazuaki Iijima 1-4-1 Yurakucho, Chiyoda-ku, Tokyo Sanki Industry Co., Ltd. (56) Reference JP 2002-126451 (JP, A) JP, 10-253508 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) B01J 21/00-38/74
Claims (7)
し、拡散係数の小さい粒子は該一対の平行板の狭い隙間
をそのまま通過させて該一対の平行板の出口から排出さ
せ、かつ該一対の平行板の内壁面に汚染空気中の有害ガ
ス成分を拡散させて該内壁表面に吸着させるための、平
行に向き合わせた一対の平行板からなり、該隙間は下記
の式（Gormleyの理論式）を満たす間隔とし、該一対の
平行板の該内壁表面に酸化チタン超微粒子光触媒と吸着
剤とからなる塗布層を設けるとともに該隙間内に光を照
射できる構造としたことを特徴とする大気中の窒素酸化
物の除去処理装置。式：ｆ＝１−［０．９１０ｅｘｐ（−３．７７μ）＋
０．０５３１ｅｘｐ（−４２．８μ）］、μ＝ｂＤＬ／
ａＱ （ただし、ｆ：除去効率、Ｄ：対象とするガスの拡散係
数（ｃｍ 2 ／秒）、ａ：平行板の間隔（ｃｍ）、Ｌ：平
行板の長さ（ｃｍ）、μ：沈着パラメータ、Ｑ：大気吸
引流量（ｃｍ 3 ／秒）、ｂ：平行板の幅（ｃｍ）であ
る。） 1. A flow of contaminated air to the narrow gap pair of parallel plates, small particles of the diffusion coefficient is discharged from the outlet of the pair of parallel plates as it is passed through a narrow gap <br/> of the pair of parallel plates It
Allowed, and for adsorbing to the inner wall surface by diffusing harmful gas components of the inner wall surface contamination in the air of the pair of parallel plates, flat
It consists of a pair of parallel plates facing each other, and the gap is
Expression of the interval satisfying (theoretical formula of Gormley), the pair of <br/> the inner wall surface of the adsorption and the titanium oxide ultrafine particles photocatalyst parallel plate
Nitrogen oxidation in the atmosphere , characterized in that a coating layer made of an agent is provided and the structure is such that light can be irradiated into the gap.
Object removal processing equipment. Formula: f = 1− [0.910exp (−3.77μ) +
0.0531 exp (-42.8 μ)], μ = bDL /
aQ (However, f: removal efficiency, D: target gas diffusion coefficient
Number (cm 2 / sec), a: Distance between parallel plates (cm), L: Flat
Row length (cm), μ: deposition parameter, Q: atmospheric absorption
Draw flow rate (cm 3 / sec), b: width of parallel plate (cm)
It )
ロロエチレンを用いて設けられていることを特徴とする
請求項１記載の大気中の窒素酸化物の除去処理装置。 2. The coating layer comprises polytetraf as a binder.
It is characterized by being provided by using polyethylene glycol
The apparatus for removing atmospheric nitrogen oxides according to claim 1.
いたことを特徴とする請求項１又は２記載の大気中の窒
素酸化物の除去処理装置。 3. Use of hydroxyapatite as the adsorbent
The atmospheric nitrogen according to claim 1 or 2, characterized in that
Equipment for removing elemental oxides.
装置のガス流路に付設されて用いられることを特徴とす
る請求項１ないし３のいずれかに記載の大気中の窒素酸
化物の除去処理装置。4. Nitrogen acid in the atmosphere according to any one of claims 1 to 3 is attached to the gas flow path of the air passage or the exhaust gas treatment device characterized in that it is used in the air conditioner
Compound removal treatment equipment.
使用することを特徴とする請求項１ないし３のいずれか
に記載の大気中の窒素酸化物の除去処理装置。5. Use as a portable air purifying device in a general household .
The apparatus for removing atmospheric nitrogen oxides according to 1 .
チタン超微粒子光触 媒と吸着剤とからなる塗布層上で酸
化・吸着された窒素酸化物をＮＯ 2 - 、ＮＯ 3 - イオンとし
て水で回収することを特徴とする請求項１ないし５のい
ずれかに記載の窒素酸化物の除去処理装置の使用方法。 6. Oxidation by washing with water
Acid on the coating layer composed of titanium ultrafine particles light catalytic and adsorbent
Reduction and adsorbed nitrogen oxides NO 2 -, NO 3 - and ion
And recovering with water.
A method for using the nitrogen oxide removal treatment device according to any one of the above.
チタン超微粒子光触媒と吸着剤とからなる塗布層上で酸
化・吸着された窒素酸化物をＮＯ 2 - 、ＮＯ 3 - イオンとし
て水で回収した後、空気を流して酸化チタン超微粒子光
触媒と吸着剤とからなる塗布層表面を乾燥し、繰り返し
て窒素酸化物の除去処理を行うことを特徴とする請求項
１ないし５のいずれかに記載の窒素酸化物の除去処理装
置の使用方法。 7. Oxidation by injecting water and washing
Acid on the coating layer consisting of titanium ultrafine particle photocatalyst and adsorbent
Reduction and adsorbed nitrogen oxides NO 2 -, NO 3 - and ion
After recovering with water, air is blown and the titanium oxide ultrafine particle light is emitted.
The coating layer surface consisting of catalyst and adsorbent is dried and repeated.
A process for removing nitrogen oxides is performed by using
1. A device for removing nitrogen oxides according to any one of 1 to 5.
How to use the table.
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|---|---|---|---|
| JP2000318316A Division JP2002126451A (en) | 2000-10-18 | 2000-10-18 | Device for removing nitrogen oxides in air |
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| Publication Number | Publication Date |
|---|---|
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| JP2005245550A (en) * | 2004-03-02 | 2005-09-15 | Hokuei:Kk | Air control method of air cleaner using photocatalyst |
| JP4843907B2 (en) * | 2004-04-23 | 2011-12-21 | パナソニック株式会社 | Fuel cell power generator |
| JP7375100B1 (en) | 2022-04-27 | 2023-11-07 | 日機装株式会社 | air purifier |
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